Oct. 2022, 日本化学会コロイドおよび界面化学部会, 第73回コロイドおよび界面化学討論会若手口頭講演賞　　　　　　　　　　　　　　　
Formation scheme of ZnTe microspheres via hot injection method
Yuen-ting Rachel Chau, Mai Thanh Nguyen, Tetsu Yonezawa

Aug. 2022, National Taipei University of Technology, Horonary International Chair Professor　　　　　　　　　　　　　　　

Jan. 2022, 化学系学協会北海道支部2022年冬季研究発表会, 優秀講演賞（口頭発表部門）　　　　　　　　　　　　　　　
Cu2O形成を抑制することでネッキング促進されるカルボン酸被覆銅微粒子
戸倉凜太郎;米澤 徹

2016, Royal Society of Chemistry, Fellow　　　　　　　　　　　　　　　
Tetsu Yonezawa

Apr. 2015, Pekin University, Xinda Lectureship　　　　　　　　　　　　　　　
Tetsu Yonezawa

Oct. 2012, Japanese Society for Analytical Chemistry, Most Cited Paper Award Analytical Sciences 2011　　　　　　　　　　　　　　　
Tetsu Yonezawa

Mar. 2009, Japanese Society for Analytical Chemistry, Hot Article Award　　　　　　　　　　　　　　　
Tetsu Yonezawa

3D Hierarchical MOF-Derived Defect-Rich NiFe Spinel Ferrite as a Highly Efficient Electrocatalyst for Oxygen Redox Reactions in Zinc–Air Batteries
Mohan Gopalakrishnan, Wathanyu Kao-ian, Meena Rittiruam, Supareak Praserthdam, Piyasan Praserthdam, Wanwisa Limphirat, Mai Thanh Nguyen, Tetsu Yonezawa, Soorathep Kheawhom
ACS Applied Materials & Interfaces, 16, 9, 11537, 11551, 06 Mar. 2024, [Peer-reviewed]
English, Scientific journal

In situ self-assembly of molybdenum carbide and iron carbide heterostructures on N-doped carbon for an efficient oxygen reduction reaction
Sagar Ingavale, Mohan Gopalakrishnan, Phiralang Marbaniang, Woranunt Lao-atiman, Ahmad Azmin Mohamad, Mai Thanh Nguyen, Tetsu Yonezawa, Anita Swami, Soorathep Kheawhom
Nanoscale, 2024
Scientific journal

Detailed discussion on the structure of alloy nanoparticles synthesized via magnetron sputter deposition onto liquid poly(ethylene glycol)
Mai Thanh Nguyen, Pichaya Pattanasattayavong, Tetsu Yonezawa
Nanoscale Advances, 2024
Scientific journal

Unexpected Reactivity of Cationic-to-Cationic Thiolate Ligand-Exchange Reaction on Au25 Clusters
Donghoon Lee, Yohei Ishida, Tetsu Yonezawa
Langmuir, 20 Jun. 2023
Scientific journal

Unveiling the role of water in enhancing the performance of zinc-ion batteries using dimethyl sulfoxide electrolyte and the manganese dioxide cathode
Wathanyu Kao-ian, Jinnawat Sangsawang, Pinit Kidkhunthod, Suttipong Wannapaiboon, Manaswee Suttipong, Amornrat Khampunbut, Prasit Pattananuwat, Mai Thanh Nguyen, Tetsu Yonezawa, Soorathep Kheawhom
Journal of Materials Chemistry A, 11, 20, 10584, 10595, 20 Apr. 2023, [Peer-reviewed]
English, Scientific journal

Mechanistic consideration of ZnTe microspheres formation in a PVP-contained polyol system via hot injection method
Yuen-ting Rachel Chau, Mai Thanh Nguyen, Tomoharu Tokunaga, Tetsu Yonezawa
Advanced Powder Technology, 34, 4, 103970, 103970, Elsevier BV, Apr. 2023, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal

Critical roles of metal–organic frameworks in improving the Zn anode in aqueous zinc-ion batteries
Mohan Gopalakrishnan, Sunantha Ganesan, Mai Thanh Nguyen, Tetsu Yonezawa, Supareak Praserthdam, Rojana Pornprasertsuk, Soorathep Kheawhom
Chemical Engineering Journal, Feb. 2023, [Peer-reviewed]
English, Scientific journal

Sputter-Deposited Binder-Free Nanopyramidal Cr/γ-Mo2N TFEs for High-Performance Supercapacitors
Durai Govindarajan, Nithyadharseni Palaniyandy, Karthik Kumar Chinnakutti, Mai Thanh Nguyen, Tetsu Yonezawa, Jiaqian Qin, Soorathep Kheawhom
Nanoscale Research Letters, 17, 1, Springer Science and Business Media LLC, Dec. 2022, [Peer-reviewed], ［Internationally co-authored］, [International Magazine]
English, Scientific journal, Due to their outstanding power density, long cycle life and low cost, supercapacitors have gained much interest. As for supercapacitor electrodes, molybdenum nitrides show promising potential. Molybdenum nitrides, however, are mainly prepared as nanopowders via a chemical route and require binders for the manufacture of electrodes. Such electrodes can impair the performance of supercapacitors. Herein, binder-free chromium (Cr)-doped molybdenum nitride (Mo₂N) TFEs having different Cr concentrations are prepared via a reactive co-sputtering technique. The Cr-doped Mo₂N films prepared have a cubic phase structure of γ-Mo₂N with a minor shift in the (111) plane. While un-doped Mo₂N films exhibit a spherical morphology, Cr-doped Mo₂N films demonstrate a clear pyramid-like surface morphology. The developed Cr-doped Mo₂N films contain 0–7.9 at.% of Cr in Mo₂N lattice. A supercapacitor using a Cr-doped Mo₂N electrode having the highest concentration of Cr reveals maximum areal capacity of 2780 mC/cm², which is much higher than that of an un-doped Mo₂N electrode (110 mC/cm²). Furthermore, the Cr-doped Mo₂N electrode demonstrates excellent cycling stability, achieving ~ 94.6% capacity retention for about 2000 cycles. The reactive co-sputtering proves to be a suitable technique for fabrication of binder-free TFEs for high-performance energy storage device applications.

Graphical Abstract

Spatio-temporal control of THz emission
Hsin-hui Huang, Saulius Juodkazis, Eugene G. Gamaly, Takeshi Nagashima, Tetsu Yonezawa, Koji Hatanaka
Communications Physics, 5, 1, Springer Science and Business Media LLC, Dec. 2022, [Peer-reviewed], ［Internationally co-authored］, [International Magazine]
English, Scientific journal, Abstract

Intense THz sources are expected for further progresses in nonlinear THz science and technology. Liquids like water are durable and continuously-reusable under intense laser irradiation for THz emission though such studies on THz emission from water targets are so far limited. Polarisation fine control of THz emission is demonstrated with a tilted micro-thin water flow by the irradiation of two cross-linearly-polarised femtosecond laser pulses (800nm, 35fs, transform-limited) with spatio-temporal offsets. With an optimized horizontal offset at ∼11 μm between the ∼8 μm focal spots and time delay at 4.7ns, circularly-polarised THz emission is obtained with its intensity enhancement more than 1,500-times if compared with the single pulse irradiation. It is shown that the photon-number-based efficiency from the laser to THz at 7.1 x 10⁻³ is achieved with the optimisation of the double pulse irradiation. Polarisation-resolved THz time-domain spectroscopy and time-resolved shadowgraphy imaging reveal that the circularly-polarised THz emission originates from the focal volume in front of the water flow. Coupling between a shockwave due to air-breakdown and water ablation-mediated mass transport by the pre-pulse with a laser wake-field along the optical path of the main pulse is responsible for the point-like single-cycle THz emission.

Injectable Fiducial Marker for Image-Guided Radiation Therapy Based on Gold Nanoparticles and a Body Temperature-Activated Gel-Forming System
Haoran Liu, Naoki Miyamoto, Mai Thanh Nguyen, Hiroki Shirato, Tetsu Yonezawa
ACS Applied Bio Materials, 08 Sep. 2022, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
Scientific journal

Mixed-Metal-Atom Markers Enable Simultaneous Imaging of Spatial Distribution in Two-Dimensional Heterogeneous Molecular Assembly by Scanning Transmission Electron Microscopy
Ikumi Akita, Yohei Ishida, Tetsu Yonezawa
ACS Measurement Science Au, American Chemical Society (ACS), 03 Aug. 2022, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, Scientific journal, Atomic-scale observation by aberration-corrected scanning transmission electron microscopy (STEM) is essential for characterizing supramolecular assemblies with nonperiodic structures. Identifying the relative spatial arrangement in a mixture of molecular species in an assembly is crucial for understanding chemical reaction systems occurring in the assembly. Herein, we report the first direct observation of supramolecular assemblies comprising anionic clay mineral nanosheets and two types of cationic porphyrin complexes with Pt and Pd atom markers by annular dark-field STEM, enabling the simultaneous imaging of well-mixed spatial molecular distributions. The results expand the possibility of applying electron microscopy to self-assembly structures constructed via weak supramolecular interactions on relatively thick nanosheet materials and on one- to few-atom-thick graphene analogues, which will provide important guidelines for future material design.

Green and effective synthesis of gold nanoparticles as an injectable fiducial marker for real-time image gated proton therapy
Haoran Liu, Naoki Miyamoto, Mai Thanh Nguyen, Hiroki Shirato, Tetsu Yonezawa
Materials Advances, 3, 13, 5430, 5441, Royal Society of Chemistry ({RSC}), May 2022, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, Scientific journal, Fiducial markers are crucial for reducing damage to surrounding healthy tissues in real-time image gated proton therapy (RGPT) by boosting geometric accuracy and precision. This study aims to develop an injectable fiducial marker based on gold nanoparticles (Au NPs) synthesized by a green ethanol reduction method, as well as to determine the factors that affect their injectability and imaging capability. Au NPs synthesized in the ethanol-only system had an improved injectability (through 18G and 21G needles) and their imaging performance was almost identical to current fiducial markers used in the clinic. The reducing capacity of the ethanol system was significantly enhanced through the introduction of sodium alginate. Meanwhile, the addition of sodium alginate could also control the size of Au NPs, ranging from 21.8 to 14.1 nm. The product alg-Au NPs with smaller sizes enabled an injectability up to 100% even through 25G needles with an extrusion force less than 17 N, which is superior for the injection of high-concentration Au NPs. A better imaging performance of alg-Au NPs was also verified in the X-ray visualization test. The work describes the green synthesis of Au NPs via the high-efficiency reducing system ethanol/alginate without the use of toxic reducing, capping, or stabilizing agents. The alg-Au NPs were found to exhibit promise as a fiducial marker for RGPT based on the injectability and imaging test

Preparation of Biopex-Supported Gold Nanoparticles as Potential Fiducial Markers for Image-Guided Radiation Therapy
Kai Ikeda, Haoran Liu, Naoki Miyamoto, Mai Thanh Nguyen, Hiroki Shirato, Tetsu Yonezawa
ACS Applied Bio Materials, 5, 3, 1259, 1266, American Chemical Society ({ACS}), 21 Mar. 2022, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, Scientific journal, Image-guided radiation therapy (IGRT) has emerged as a promising technique for cancer treatment to improve radiation precision and accuracy, thereby reducing the treatment toxicity and optimizing therapeutic efficacy. In IGRT, fiducial markers are required to be inserted near the tumor to get the spatial information of the tumor. Currently used metal fiducial markers with large sizes would be highly invasive; therefore, it is critical to develop minimally invasive alternatives to these markers. In this work, an injectable marker based on Biopex-supported Au NPs with adequate radio-opacity for X-ray visualization was developed. Biopex can function as a substrate for the growth of Au NPs and avoid excessive reaction-induced aggregation and precipitation. The self-curing property of Biopex prevents the leakage and elimination of isolated Au NPs, enabling long-term X-ray observation and radiotherapy. The effect of Biopex amount, gold precursor concentration, and reaction time were evaluated. The visibility of samples prepared by the optimized formula was also examined. The developed Biopex-Au NPs could be injected through a 21 G needle and exhibit great visibility in the X-ray visualization test, showing great potential as a fiducial marker for image-guided radiation therapy.

Anisotropic Growth of Copper Nanorods Mediated by Cl– Ions
Min Jia Saw, Mai Thanh Nguyen, Yuji Kunisada, Tomoharu Tokunaga, Tetsu Yonezawa
ACS Omega, 7, 8, 7414, 7420, American Chemical Society ({ACS}), 01 Mar. 2022, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

Recent advances in oxygen electrocatalysts based on tunable structural polymers
M. Gopalakrishnan, A.A. Mohamad, M.T. Nguyen, T. Yonezawa, J. Qin, P. Thamyongkit, A. Somwangthanaroj, S. Kheawhom
Materials Today Chemistry, 23, 100632, 100632, Elsevier {BV}, Mar. 2022, [Peer-reviewed], ［Internationally co-authored］, [International Magazine]
English, Scientific journal, Due to their high energy density, great safety and eco-friendliness, zinc-air batteries (ZABs) attract much attention. During the process of charging and discharging, the two key processes viz. oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) limit their efficiency. In general, the noble metal-based electrocatalysts (ORR: platinum (Pt); OER: iridium (IV) oxide [IrO2] and ruthenium oxide [RuO2]) have long been used. Nonetheless, these noble metal electrocatalysts also have their limitations owing to high cost and poor stability. As alternatives, polymers are found to be most promising on account of their tunable structure, uniform network, high surface morphology and strong durability. Polymers are capable catalysts. In this review, recent advances as well as insight into the architecture of covalent organic polymers (COPs), metal coordination polymers (MCPs) and pyrolysis-free polymers (PFPs) are duly outlined.

Alginate-Stabilized Gold Nanoparticles Prepared Using the Microwave-Induced Plasma-in-Liquid Process with Long-Term Storage Stability for Potential Biomedical Applications
Haoran Liu, Kai Ikeda, Mai Thanh Nguyen, Susumu Sato, Naoki Matsuda, Hiroki Tsukamoto, Tomoharu Tokunaga, Tetsu Yonezawa
ACS Omega, American Chemical Society ({ACS}), 22 Feb. 2022, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

Tailoring the MOF structure via ligand optimization afforded a dandelion flower like CoS/Co–Nx/CoNi/NiS catalyst to enhance the ORR/OER in zinc–air batteries
Mohan Gopalakrishnan, Mohamad Etesami, Jayaraman Theerthagiri, Myong Yong Choi, Suttipong Wannapaiboon, Mai Thanh Nguyen, Tetsu Yonezawa, Soorathep Kheawhom
Nanoscale, 2022, [Peer-reviewed], ［Internationally co-authored］, [International Magazine]
English, Scientific journal

Co-sputtered CuPt/Ag alloy nanoparticles and comparative catalytic performance of mono-, bi-, and tri-metallic nanoparticles in the oxygen reduction reaction
Mingbei Zhu, Mai Thanh Nguyen, Wei Jian Sim, Tetsu Yonezawa
Materials Advances, 2022, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
Scientific journal

CoxNi1−xO-NiCo2O4/rGO synergistic bifunctional electrocatalysts for high-rate rechargeable zinc–air batteries
Zixuan Huang, Mai Thanh Nguyen, Wei Jian Sim, Masayuki Takahashi, Soorathep Kheawhom, Tetsu Yonezawa
Sustainable Energy & Fuels, Royal Society of Chemistry ({RSC}), 2022, [Peer-reviewed], [Last author, Corresponding author], ［Internationally co-authored］, [International Magazine]
English, Scientific journal

A liquid metal catalyst for the conversion of ethanol into graphitic carbon layers under an ultrasonic cavitation field
Hideya Kawasaki, Tomoko Otsuki, Fumiya Sugino, Ken Yamamoto, Tomoharu Tokunaga, Rintaro Tokura, Tetsu Yonezawa
Chemical Communications, Royal Society of Chemistry ({RSC}), 2022, [Last author, Corresponding author]
Scientific journal

Efficient iron–cobalt oxide bifunctional electrode catalysts in rechargeable high current density zinc–air batteries
Wei Jian Sim, Mai Thanh Nguyen, Zixuan Huang, Soorathep Kheawhom, Chularat Wattanakit, Tetsu Yonezawa
Nanoscale, Royal Society of Chemistry ({RSC}), 2022, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal

The role of surface oxides and stabilising carboxylic acids of copper nanoparticles during low-temperature sintering
Rintaro Tokura, Hiroki Tsukamoto, Tomoharu Tokunaga, Mai Thanh Nguyen, Tetsu Yonezawa
Materials Advances, Royal Society of Chemistry (RSC), 2022, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, 1-Hexanoic acid stabilised copper nanoparticles were obtained. Cu₆₄O phase could be found on the particle surface. During sintering, the stabilising molecule, 1-hexanoic acid, reduced Cu₆₄O to Cu and it introduced neckings between the particles.

Benchmarking superfast electrodeposited bimetallic (Ni, Fe, Co, and Cu) hydroxides for oxygen evolution reaction
Mohammad Etesami, Ahmad Azmin Mohamad, Mai Thanh Nguyen, Tetsu Yonezawa, Rojana Pornprasertsuk, Anongnat Somwangthanaroj, Soorathep Kheawhom
Journal of Alloys and Compounds, 889, 161738, 161738, Elsevier BV, Jan. 2022, [Peer-reviewed]
English, Scientific journal

Surface Menshutkin SN2 Reaction on Basic Gold Clusters Provides Novel Opportunities for the Cationization and Functionalization of Molecular Metal Clusters
Kunihiro Narita, Yohei Ishida, Shuichi Nukui, Zhong Huang, Tetsu Yonezawa
The Journal of Physical Chemistry Letters, 12, 49, 11761, 11765, American Chemical Society ({ACS}), 02 Dec. 2021, [Peer-reviewed], [Last author, Corresponding author], ［Internationally co-authored］, [International Magazine]
English, Scientific journal

Control of nanoparticles synthesized via vacuum sputter deposition onto liquid: a review
Mai Thanh Nguyen, Lianlian Deng, Tetsu Yonezawa
Soft Matter, Royal Society of Chemistry (RSC), 23 Nov. 2021, [Peer-reviewed], [Invited], [Last author, Corresponding author]
English, Scientific journal, Sputter deposition onto a low volatile liquid matrix is a recently developed green synthesis method of metal/metal oxide nanoparticles (NPs). In this review, we introduce the synthesis method and highlight...

A durable rechargeable zinc-air battery via self-supported MnOx-S air electrode
Nikdalila Radenahmad, Ramin Khezri, Ahmad Azmin Mohamad, Mai Thanh Nguyen, Tetsu Yonezawa, Anongnat Somwangthanaroj, Soorathep Kheawhom
Journal of Alloys and Compounds, 883, 160935, 160935, Elsevier BV, Nov. 2021, [Peer-reviewed]
English, Scientific journal

Highly stable rechargeable zinc-ion battery using dimethyl sulfoxide electrolyte
W. Kao-ian, M.T. Nguyen, T. Yonezawa, R. Pornprasertsuk, J. Qin, S. Siwamogsatham, S. Kheawhom
Materials Today Energy, 21, 100738, 100738, Elsevier {BV}, Sep. 2021, [Peer-reviewed]
Scientific journal

Impact of Binder Functional Groups on Controlling Chemical Reactions to Improve Stability of Rechargeable Zinc-Ion Batteries
Natta Jaikrajang, Wathanyu Kao-Ian, Tatsuki Muramatsu, Rungroj Chanajaree, Tetsu Yonezawa, Zakaria Y. Al Balushi, Soorathep Kheawhom, Rongrong Cheacharoen
ACS Applied Energy Materials, 4, 7, 7138, 7147, American Chemical Society ({ACS}), 30 Jun. 2021, [Peer-reviewed]
English, Scientific journal

Pt/Ag Solid Solution Alloy Nanoparticles in Miscibility Gaps Synthesized by Cosputtering onto Liquid Polymers
Mingbei Zhu, Mai Thanh Nguyen, Yuen-ting Rachel Chau, Lianlian Deng, Tetsu Yonezawa
Langmuir, 37, 19, 6096, 6105, American Chemical Society ({ACS}), 18 May 2021, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Pt/Ag solid solution alloy nanoparticles (NPs) with mean size below 3 nm were obtained with composition in miscibility gaps by cosputtering onto liquid polyethylene glycol (PEG, MW = 600). Adjusting the sputtering currents from 10 to 50 mA did not influence the particle sizes obviously but caused a substantial difference in the composition and distributions of Pt/Ag NPs. This is different from sputtered Pt/Au NPs where particle size is correlated with composition. For a pair of sputtering currents, the formed Pt/Ag alloy NPs have a range of compositions. The normal distribution with Pt of 60.2 +/- 16.2 at % is observed for the Pt/Ag sample with a nominal Pt content of 55.9 at %, whereas Pt-rich (85.1 +/- 14.0 at % Pt) and Ag-rich (19.8 +/- 12.2 at % Pt) Pt/Ag samples with nominal Pt contents of 90.9 and 11.9 at % contain more pure Pt and pure Ag NPs, respectively. Different from NPs obtained in PEG, the sputtered NPs on TEM grids had more uniform composition for a longer sputtering time along with a significant increase of particle sizes. This reveals that PEG hindered the combination of NPs and clusters, resulting in small particle sizes even for long time sputtering and broader composition distributions. Thus, the samples obtained in PEG have the compositions mainly determined by the random atom combination in the vacuum chamber and possibly in initial landing of atom/clusters on the PEG surface.

Direct Imaging of Individual Organic Molecules in Supramolecular Assembly Strongly Fixed via Multivalent Electrostatic Interactions
Ikumi Akita, Yohei Ishida, Tetsu Yonezawa
The Journal of Physical Chemistry C, 125, 8, 4917, 4923, American Chemical Society ({ACS}), 04 Mar. 2021, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

CHAPTER 15: Miscellaneous Reductants
Tetsu Yonezawa, Shilei Zhu, Mai Thanh Nguyen
RSC Nanoscience and Nanotechnology, 2021-, 50, 393, 459, Royal Society of Chemistry, 2021
English, In book, Miscellaneous reductants are of focus for their role in colloidal synthesis/preparation of metal nanoparticles. Their reductivity from weak to medium is first demonstrated with selective effect to noble and less reactive transition metals with respect to different synthesis conditions. After this, we discuss the origin of the reductant property. Besides, other important and delicate functions of these reductants in the synthesis will be reviewed including the stabilizing effect and the size- and shape-controlling capability. It is also important to emphasize that reductants in this chapter compose a group of much greener and less toxic reagents for the nanoparticle synthesis.

Micro- and nano-encapsulated metal and alloy-based phase-change materials for thermal energy storage
Shilei Zhu, Mai Thanh Nguyen, Tetsu Yonezawa
Nanoscale Advances, 3, 16, 4626, 4645, Royal Society of Chemistry ({RSC}), 2021, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, An overview of recent literature on the micro- and nano-encapsulation of metallic phase-change materials (PCMs) is presented in this review to facilitate an understanding of the basic knowledge, selection criteria, and classification of commonly used PCMs for thermal energy storage (TES). Metals and alloys with high thermal conductivity can be used as PCMs for rapid heat storage in compact systems owing to their high volumetric TES density. The emerging application of metal PCMs in different fields such as solar thermal energy management, smart wearable devices with thermal comfort control, and cooling of electronic devices call for the need of micro- and nano-TES particles, which can be synthesised in different forms to satisfy specific requirements. As metals are easily oxidised, especially at the micro- and nano-level, encapsulation of metal-based PCM particles is important for sustainable use at high operating temperature in ambient conditions. Recent studies focusing on the encapsulation of metallic PCMs at the micro- and nano-level have been reviewed and classified in terms of the melting point of metal/alloy PCMs used and types of encapsulation materials, such as oxides, polymers, carbon, and metals. The current review is expected to provide an outlook on novel metal and alloy PCMs with function-directed structures and superior TES properties for a broad range of applications.

THz wave emission from the Cu2O/Cu interface under femtosecond laser irradiation
Yuen-Ting Rachel Chau, Hsin-hui Huang, Mai Thanh Nguyen, Koji Hatanaka, Tetsu Yonezawa
Applied Physics Express, 14, 1, 012006, 012006, {IOP} Publishing, 01 Jan. 2021, [Peer-reviewed], [Last author, Corresponding author], ［Internationally co-authored］, [International Magazine]
Scientific journal, Cu or Cu/Au (80 nm thick Cu, 50 nm thick Au) sputtered on Si were kept at 25 °C for a week or annealed at a temperature from 80 to 300 °C, then tested for THz emission under femtosecond laser irradiation (35 fs-800 nm). THz radiation was detected from samples annealed from 80 to 170 °C, which had a Cu₂O/Cu interface as the THz source. Cu/Au/Si annealed at 80 °C emitted the highest THz radiation because of high laser absorption by the porous Cu₂O layer formed at low temperature and the Au film reflected THz radiation and/or increased the laser absorption by the Fabry–Pérot effect.

Synergistic Effect of the Oleic Acid and Oleylamine Mixed-Liquid Matrix on Particle Size and Stability of Sputtered Metal Nanoparticles
Mai Thanh Nguyen, Krittaporn Wongrujipairoj, Hiroki Tsukamoto, Soorathep Kheawhom, Shuang Mei, Vipada Aupama, Tetsu Yonezawa
ACS Sustainable Chemistry & Engineering, 8, 49, 18167, 18176, American Chemical Society ({ACS}), 14 Dec. 2020, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

Surfactant-stabilized copper paticles for low-temperature sintering: Paste preparation using a milling with small zirconia beads: Effect of pre-treatment with the disperse medium
Shuai Liu, Rintaro Tokura, Mai Thanh Nguyen, Hiroki Tsukamoto, Tetsu Yonezawa
Advanced Powder Technology, 31, 11, 4570, 4575, Elsevier {BV}, Nov. 2020, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

Enhanced Cycling Performance of Rechargeable Zinc–Air Flow Batteries Using Potassium Persulfate as Electrolyte Additive
Ramin Khezri, Soraya Hosseini, Abhishek Lahiri, Shiva Rezaei Motlagh, Mai Thanh Nguyen, Tetsu Yonezawa, Soorathep Kheawhom
International Journal of Molecular Sciences, 21, 19, 7303, 7303, {MDPI} {AG}, Oct. 2020, [Peer-reviewed]
Scientific journal, Zinc–air batteries (ZABs) offer high specific energy and low-cost production. However, rechargeable ZABs suffer from a limited cycle life. This paper reports that potassium persulfate (KPS) additive in an alkaline electrolyte can effectively enhance the performance and electrochemical characteristics of rechargeable zinc–air flow batteries (ZAFBs). Introducing redox additives into electrolytes is an effective approach to promote battery performance. With the addition of 450 ppm KPS, remarkable improvement in anodic currents corresponding to zinc (Zn) dissolution and limited passivation of the Zn surface is observed, thus indicating its strong effect on the redox reaction of Zn. Besides, the addition of 450 ppm KPS reduces the corrosion rate of Zn, enhances surface reactions and decreases the solution resistance. However, excess KPS (900 and 1350 ppm) has a negative effect on rechargeable ZAFBs, which leads to a shorter cycle life and poor cyclability. The rechargeable ZAFB, using 450 ppm KPS, exhibits a highly stable charge/discharge voltage for 800 cycles. Overall, KPS demonstrates great promise for the enhancement of the charge/discharge performance of rechargeable ZABs.

Circularly-polarized THz wave emission from a micro-thin water flow
Hsin-Hui Huang, Saulius Juodkazis, Eugene Gamaly, Takeshi Nagashima, Tetsu Yonezawa, Koji Hatanaka
Research Square Platform {LLC}, 23 Sep. 2020, [Peer-reviewed]
Scientific journal

Ethylene Glycol/Ethanol Anolyte for High Capacity Alkaline Aluminum-Air Battery With Dual-Electrolyte Configuration
Tanawat Phusittananan, Wathanyu Kao-Ian, Mai Thanh Nguyen, Tetsu Yonezawa, Rojana Pornprasertsuk, Ahmad Azmin Mohamad, Soorathep Kheawhom
Frontiers in Energy Research, 8, Frontiers Media SA, 31 Jul. 2020, [Peer-reviewed]
English, Scientific journal

THz Wave Emission from ZnTe Nano-colloidal Aqueous Dispersion Irradiated by Femtosecond Laser
Hsin-hui Huang, Yuen-ting Rachel Chau, Tetsu Yonezawa, Mai Thanh Nguyen, Shilei Zhu, Dan Deng, Takeshi Nagashima, Koji Hatanaka
Chemistry Letters, 49, 6, 597, 600, The Chemical Society of Japan, 05 Jun. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal

MnO₂ Heterostructure on Carbon Nanotubes as Cathode Material for Aqueous Zinc-Ion Batteries
Sonti Khamsanga, Mai Thanh Nguyen, Tetsu Yonezawa, Patchanita Thamyongkit, Rojana Pornprasertsuk, Prasit Pattananuwat, Adisorn Tuantranont, Siwaruk Siwamogsatham, Soorathep Kheawhom
International Journal of Molecular Sciences, 21, 13, 4689, 4689, {MDPI} {AG}, Jun. 2020, [Peer-reviewed]
English, Scientific journal

Atomic-Scale Imaging of a Free-Standing Monolayer Clay Mineral Nanosheet Using Scanning Transmission Electron Microscopy
Ikumi Akita, Yohei Ishida, Tetsu Yonezawa
The Journal of Physical Chemistry Letters, 11, 9, 3357, 3361, American Chemical Society ({ACS}), 07 May 2020, [Peer-reviewed], [Last author, Corresponding author]
Scientific journal

High-Capacity Dual-Electrolyte Aluminum–Air Battery with Circulating Methanol Anolyte
Pemika Teabnamang, Wathanyu Kao-ian, Mai Thanh Nguyen, Tetsu Yonezawa, Rongrong Cheacharoen, Soorathep Kheawhom
Energies, May 2020, [Peer-reviewed]
Scientific journal

Binder-Free α-MnO2 Nanowires on Carbon Cloth as Cathode Material for Zinc-Ion Batteries
Ryan Dula Corpuz, Lyn Marie De Juan-Corpuz, Mai Thanh Nguyen, Tetsu Yonezawa, Heng-Liang Wu, Anongnat Somwangthanaroj, Soorathep Kheawhom
International Journal of Molecular Sciences, 21, 9, 3113, 3113, {MDPI} {AG}, 28 Apr. 2020, [Peer-reviewed]
Scientific journal

Synthesis of Au@Cu2O Core–Shell Nanoparticles with Tunable Shell Thickness and Their Degradation Mechanism in Aqueous Solutions
Shilei Zhu, Dan Deng, Mai Thanh Nguyen, Yuen-ting Rachel Chau, Cheng-Yen Wen, Tetsu Yonezawa
Langmuir, 36, 13, 3386, 3392, American Chemical Society ({ACS}), 07 Apr. 2020, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Metal@semiconductor core-shell nanoparticles (NPs) are widely used in photocatalysts, sensors, and optical applications owing to their unique metal-semiconductor interface and the integration of the properties from both core and shell materials. Although many efforts have been made toward the precise synthesis of Au@Cu2O core-shell structures, the chemical stability of Au@Cu2O aqueous suspensions, which is of great significance in many related applications, is not mentioned in any published research. Herein we report the synthesis of Au@Cu2O core-shell NPs with small shell thickness from 2 to 40 nm through a wet-chemistry method. The UV-vis absorption properties are found to be tunable with Cu2O thickness in the range of 2-40 nm. Furthermore, the chemical stability of Au@Cu2O core-shell nanoparticle suspensions in water/ethanol mixed solvents is investigated. It is found that water/ethanol mixed solvents with a larger amount of water are more likely to deteriorate the stability of Au@Cu2O NPs by oxidizing Cu2O to CuO. The results from this work may provide useful information for the preparation of metal@Cu2O water-based suspensions that are expected to be used for SERS, photocatalyst, or photothermal applications.

In situ TEM observation of liquid-state Sn nanoparticles vanishing in a SiO2 structure: a potential synthetic tool for controllable morphology evolution from core-shell to yolk-shell and hollow structures
Shilei Zhu, Mai Thanh Nguyen, Tomoharu Tokunaga, Cheng-Yen Wen, Tetsu Yonezawa
NANOSCALE ADVANCES, 2, 4, 1456, 1464, ROYAL SOC CHEMISTRY, Apr. 2020
English, Scientific journal, Precise design of hollow nanostructures can be realized via various approaches developed in the last two decades, endowing nanomaterials with unique structures and outstanding performances, showing their usefulness in a broad range of fields. Herein, we demonstrate the formation of SnO2@SiO2 hollow nanostructures, for the first time, by interaction between liquid state Sn cores and SiO2 shell structures inside Sn@SiO2 core-shell nanoparticles with real-time observation via in situ transmission electron microscopy (TEM). Based on the in situ results, designed transformation of the nanoparticle structure from core-shell Sn@SiO2 to yolk-shell Sn@SiO2 and hollow SnO2@SiO2 is demonstrated, showing the controllable structure of core-shell Sn@SiO2 nanoparticles via fixing liquid-state Sn inside a SiO2 shell which has a certain Sn containing capacity. The present approach expands the toolbox for the design and preparation of yolk-shell and hollow nanostructures, thus providing us with a new strategy for fabrication of more complicated nanostructures.

Highly Correlated Size and Composition of Pt/Au Alloy Nanoparticles via Magnetron Sputtering onto Liquid
Lianlian Deng, Mai Thanh Nguyen, Jingming Shi, Yuen-ting Rachel Chau, Tomoharu Tokunaga, Masaki Kudo, Syo Matsumura, Naoyuki Hashimoto, Tetsu Yonezawa
Langmuir, 36, 12, 3004, 3015, American Chemical Society ({ACS}), 31 Mar. 2020, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, Scientific journal, Pt/Au alloy nanoparticles (NPs) in a wide composition range have been synthesized by room-temperature simultaneous sputter deposition from two independent magnetron sources onto liquid PEG (MW = 600). The prepared NPs were alloyed with the face-centered cubic (fcc) structure. In addition, the particle sizes, composition, and shape are strongly correlated but can be tailored by an appropriate variation of the sputtering parameters. No individual particle but large agglomerates with partial alloy structure formed at Pt content of less than 16 atom %. Highly dispersed NPs with no agglomeration were observed in PEG when the quantity of Pt is more than 26 atom %. On the other hand, a small amount of Pt could terminate the agglomeration of Au when sputtering on the grids for transmission electron microscope observation. Our experiment and computer simulation carried out by two different methods indicate that the composition-dependent particle size of Pt/Au can be explained by the atomic concentration, formation energy of the cluster, and interaction between different metal atoms and the PEG molecule.

Giant Enhancement of THz Wave Emission under Double-Pulse Excitation of Thin Water Flow
Hsin-hui Huang, Takeshi Nagashima, Tetsu Yonezawa, Yasutaka Matsuo, Soon Hock Ng, Saulius Juodkazis, Koji Hatanaka
Applied Sciences, 10, 6, 2031, 2031, {MDPI} {AG}, Mar. 2020, [Peer-reviewed]
English, Scientific journal, Simultaneous measurements of THz wave and hard X-ray emission from thin and flat water flow when irradiated by double femtosecond laser pulses (800 nm, 35 fs/transform-limited, 0.5 kHz, delay times up to 15 ns) were carried out. THz wave measurements by time-domain spectroscopy and X-ray detection by Geiger counters were performed at the transmission and the reflection sides of the flow. THz wave emission spectra show their dynamic peak shifts toward the low frequency with the highest intensity enhancements more than 1.5 × 10 3 times in |E| 2 accumulated over the whole spectrum range of 0–3 THz at the delay time of 4.7 ns between the two pulses. On the other hand, X-ray intensity enhancements are limited to about 20 times at 0 ns under the same experimental conditions. The mechanisms for the spectral changes and the intensity enhancements in THz wave emission are discussed from the viewpoint of laser ablation on the water flow induced by the pre-pulse irradiation.

Desorption and ionization of amino acid compounds observed by negative ion mode surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using titanium oxide nanoparticles
Tetsu Yonezawa, Takashi Asano, Mai Thanh Nguyen
Nano Biomedicine, 12, 2, 101, 109, National Institute of Informatics, 2020
English, Scientific journal, Surface-assisted laser desorption / ionization mass spectroscopy (SALDI-MS) in negative mode of various amino acids with commercial TiO2 nanoparticles as the DI assisting material is reported. SALDI-MS gives clear spectra of these low molecular weight negative ions, such as drugs and bio-related organic compounds. With commercially available TiO2 nanoparticles, 20 common amino acids used could be clearly detected as [M-H]- molecular ions. The ion intensity of [M-H]molecular ions is well linear correlated with the gas-phase acidity but less correlation with the hydrophobicity. But the concentration of the amino acids on the TiO2 nanoparticle surface also affected the ion intensity.

Distinctive stability of a free-standing monolayer clay mineral nanosheet via transmission electron microscopy
Ikumi Akita, Yohei Ishida, Tetsu Yonezawa
Physical Chemistry Chemical Physics, 2020, [Peer-reviewed]
Scientific journal

Silver Decorated Reduced Graphene Oxide as Electrocatalyst for Zinc–Air Batteries
Laksanaporn Poolnapol, Wathanyu Kao-ian, Anongnat Somwangthanaroj, Falko Mahlendorf, Mai Thanh Nguyen, Tetsu Yonezawa, Soorathep Kheawhom
Energies, 13, 2, 462, 462, {MDPI} {AG}, Jan. 2020, [Peer-reviewed]
English, Scientific journal

Synthesis of composition-tunable Pd–Cu alloy nanoparticles by double target sputtering
Yuen-ting Rachel Chau, Mai Thanh Nguyen, Mingbei Zhu, Arnaud Romier, Tomoharu Tokunaga, Tetsu Yonezawa
New Journal of Chemistry, 44, 12, 4704, 4712, Royal Society of Chemistry (RSC), 2020
Scientific journal,

In this work, we introduce a green synthesis technique, double-target sputtering into a liquid polymer – polyethylene glycol (PEG, M. W. = 600), to synthesize palladium–copper (Pd–Cu) alloy nanoparticles (NPs) dispersed in PEG.

Annealing induced a well-ordered single crystal δ-MnO2 and its electrochemical performance in zinc-ion battery
Ryan Dula Corpuz, Lyn Marie Z. De Juan, Supareak Praserthdam, Rojana Pornprasertsuk, Tetsu Yonezawa, Mai Thanh Nguyen, Soorathep Kheawhom
Scientific Reports, 9, 1, Nature Publishing Group, 01 Dec. 2019
English, Scientific journal, Herein, the formation and electrochemical performance of a novel binder-free turbostratic stacked/ well-ordered stacked δ-MnO2-carbon fiber composite cathodes in deep eutectic solvent (DES) based zinc-ion battery (ZIB) is reported. Results of morphological, elemental, and structural analyses revealed directly grown and interconnected δ-MnO2 crumpled nanosheets on a carbon fiber substrate. Moreover, an improvement via a simple annealing strategy in the stacking, surface area and conductivity of the δ-MnO2 sheets was observed. Annealing induces the rearrangement of δ-MnO2 sheets resulting in the transformation from turbostratic stacking to a well-ordered stacking of δ-MnO2 sheets, as indicated by the selected area electron diffraction (SAED) hexagonal single crystal pattern. Besides, the formation of the well-ordered stacking of δ-MnO2 sheets exhibited improved electrochemical performance and cyclability, as cathode material for ZIB. The novel strategy described in this study is an essential step for the development of binder-free δ-MnO2-C fiber composite with a well-ordered stacking of δ-MnO2 sheets. This study also demonstrated comparable electrochemical performance between the turbostratic δ-MnO2 sheets and the well-ordered stacked δ-MnO2 sheets.

Binder-Free Centimeter-Long V₂O₅ Nanofibers on Carbon Cloth as Cathode Material for Zinc-Ion Batteries
Lyn Marie De Juan - Corpuz, Ryan Dula Corpuz, Anongnat Somwangthanaroj, Mai Thanh Nguyen, Tetsu Yonezawa, Jianmin Ma, Soorathep Kheawhom
Energies, 13, 31, Dec. 2019, [Peer-reviewed]
English, Scientific journal

Green Synthesis of Size-Tunable Iron Oxides and Iron Nanoparticles in a Salt Matrix
Mai Thanh Nguyen, Kai Yu, Tomoharu Tokunaga, Kornkit Boonyaperm, Soorathep Kheawhom, Masashi Arita, Tetsu Yonezawa
ACS SUSTAINABLE CHEMISTRY & ENGINEERING, 7, 21, 17697, 17705, AMER CHEMICAL SOC, Nov. 2019, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, This research is devoted for the synthesis of Fe oxide and Fe nanoparticles (NPs) via, respectively, thermal decomposition of iron(III) oleate and H-2 reduction of either iron(III) oleate or iron oxide NPs in a NaCl matrix. Lowering the weight ratios of metal precursor to NaCl and synthesis temperature results in smaller particle sizes. A higher uniformity of Fe NPs can be achieved with a two-step synthesis, that is, thermal decomposition of iron oleate followed by H-2 reduction of iron oxides, with the milling of iron oxides and NaCl prior to the reduction step. Fe NPs obtained in this study are stable in the air for long-time storage. It is found that thin oxide and C layers on the particle surface are responsible for their stability.

High Aspect Ratio and Post-processing Free Silver Nanowires as Top Electrodes for Inverted-structured Photodiode
Min JIa Saw, Batu Ghosh, Mai Thanh Nguyen, Kridsada Jirasattayaporn, Soorathep Kheawhom, Naoto Shirahata, Tetsu Yonezawa
ACS Omega, 4, 8, 13303, 13308, Aug. 2019, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Silver nanowires (Ag NWs) as transparent conducting electrodes are widely used in many applications such as organic light-emitting diodes (OLEDs), polymer light-emitting diodes, touch screens, solar cells, and transparent heaters. In this work, using a large-scale synthesis, the synthesized Ag NWs had a high aspect ratio of 2820. The Ag NWs could be applied as a top transparent electrode in a device by simple drop-casting without any post-processing steps. The fabricated device comprised 4,4′-bis(carbazol-9-yl)biphenyl/MoO3 organic/inorganic layers which are parts of the inverted structure OLEDs or solar cells. The photodiode characteristics at the UV range were observed in the device. The ability of Ag NWs to replace opaque metals as top electrodes in a device has been demonstrated.

Super Polycationic Molecular Compounds: Au144(SR+)60 Clusters
Kunihiro Narita, Yohei Ishida, Tetsu Yonezawa, Zhong Huang
The Journal of Physical Chemistry C, in press, 35, 21768, 21773, AMER CHEMICAL SOC, Aug. 2019, [Peer-reviewed], [Corresponding author]
English, Scientific journal, We have recently pioneered per-cationized molecular gold (Au) cluster compounds. Herein, we present a new series of per-cationized Au cluster compounds, Au144(SR+)60, which is the largest reported compound with the most stable and studied Au clusters. Although it is typically difficult to obtain a single composition of an Au144 cluster due to the existence of similar-sized quasi-stable compounds, optimized thermal etching and selective precipitation made strict size focusing into a single Au144 composition possible and produced Au144(SR+)60 with high atomic precision. In positive-mode high-resolution ESI-MS, per-cationized Au144(SR+)60 clusters with different numbers of PF6− counter anions for the +12 to +21-charged states were observed. The Au144(SR+)60, 60(+) termini distributed over a spherical surface of radius ~ 2.5 nm, presented here is, to the best of our knowledge, the most polycationic molecular compound reported thus far.

Dispersion of Copper Fine Particles for Conductive Inks and Pastes
Tetsu YONEZAWA, Masaki MATSUBARA
Journal of the Japan Society of Colour Material, 92, 7, 205, 209, Japan Society of Colour Material, 20 Jul. 2019, [Peer-reviewed], [Invited], [Lead author, Corresponding author]
Scientific journal

Basic [Au25(SCH2CH2Py)18]−·Na+ Clusters: Synthesis, Layered Crystallographic Arrangement, and Unique Surface Protonation
Zhong Huang, Yohei Ishida, Tetsu Yonezawa
Angewante Chemie International Edition, in press, Jul. 2019, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, The synthesis of high‐purity and high‐yield Au25 clusters protected by the basic pyridyl ethanethiol (HSCH2CH2Py, 4‐PyET and 2‐PyET) is presented. Single‐crystal X‐ray diffraction of the [Au25(4‐PyET)18]−⋅Na+ clusters has revealed a structure similar to that known for the phenyl ethanethiolate analogue, but with pyridyl‐N coordination to Na+, a more relaxed ligand shell, and a profoundly layered arrangement in the solid state. Because of the pendant Py moiety, the [Au25(PyET)18]− clusters are endowed with unique (de)protonation equilibria, which has been characterized in detail by UV/Vis absorption and 1H NMR spectroscopy. [Au25(PyET)18]− clusters showed an unexpectedly H+‐dependent solubility that is tunable in aqueous and organic solvents. The successful synthesis of the basic Py‐terminated thiolate‐protected Au25 clusters paves the way to realize a new family of metalloid clusters possessing basic properties.

Sintering Copper nanoparticles with photonic additive for printed conductive patterns by intense pulsed light
Wan-Yu Chung, Yi-Chin Lai, Tetsu Yonezawa, Ying-Chih Liao
Nanomaterials, 9, 8, 1071, Jul. 2019, [Peer-reviewed], [Corresponding author]
English, Scientific journal, In this study, an ink formulation was developed to prepare conductive copper thin films with compact structure by using intense pulsed light (IPL) sintering. To improve inter-particle connections in the sintering process, a cuprous oxide shell was synthesized over copper nanoparticles (CuNP). This cuprous oxide shell can be reduced by IPL with the presence of a reductant and fused to form connection between large copper particles. However, the thermal yield stress after strong IPL sintering resulted in cracks of conductive copper film. Thus, a multiple pulse sintering with an off time of 2 s was needed to reach a low resistivity of 10−5 Ω·cm. To increase the light absorption efficiency and to further decrease voids between CuNPs in the copper film, cupric oxide nanoparticles (CuONP) of 50 nm, were also added into ink. The results showed that these CuONPs can be reduced to copper with a single pulse IPL and fused with the surrounding CuNPs. With an optimal CuNP/CuONP weight ratio of 1/80, the copper film showed a lowest resistivity of 7 × 10−5 Ω·cm, ~25% conductivity of bulk copper, with a single sintering energy at 3.08 J/cm2. The ink can be printed on flexible substrates as conductive tracks and the resistance remained nearly the same after 10,000 bending cycles.

Preparation and Growth Mechanism of Pt/Cu Alloy Nanoparticles by Sputter Deposition onto a Liquid Polymer.
Lianlian Deng, Mai Thanh Nguyen, Shuang Mei, Tomoharu Tokunaga, Masaki Kudo, Syo Matsumura, Tetsu Yonezawa
Langmuir : the ACS journal of surfaces and colloids, 35, 25, 8418, 8427, 25 Jun. 2019, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, Scientific journal, We use a green sputtering technique to deposit a Pt/Cu alloy target on liquid polyethylene glycol (PEG) to obtain well-dispersed and stable Pt29Cu71 alloy nanoparticles (NPs). The effects of sputtering current, rotation speed of the stirrer, sputtering time, sputtering period, and temperature of PEG on the particle size are studied systematically. Our key results demonstrate that the aggregation and growth of Pt/Cu alloy NPs occurred at the surface as well as inside the liquid polymer after the particles landed on the liquid surface. According to particle size analysis, a low sputtering current, high rotation speed for the stirrer, short sputtering period, and short sputtering time are found to be favorable for producing small-sized single crystalline alloy NPs. On the other hand, varying the temperature of the liquid PEG does not have any significant impact on the particle size. Thus, our findings shed light on controlling NP growth using the newly developed green sputtering deposition technique.

Size-Tunable Alumina-Encapsulated Sn-Based Phase Change Materials for Thermal Energy Storage
Shilei Zhu, Mai Thanh Nguyen, Tomoharu Tokunaga, Tetsu Yonezawa
ACS APPLIED NANO MATERIALS, 2, 6, 3752, 3760, AMER CHEMICAL SOC, Jun. 2019, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, The most commonly used phase change materials (PCMs), like organic compounds and inorganic salts, were limited in application by their low thermal conductivity. Herein, for the first time, alumina-encapsulated metallic Sn-based PCMs, named Sn@Al2O3, were successfully fabricated with tunable size (60-2000 nm) by a facile process from low-cost chemicals. The robust fabrication process consists of a surfactant-free solvothermal synthesis of SnO2 spheres, boehmite treatment on SnO2 spheres, calcination in the air, and the final hydrogen reduction to transform SnO2 to metallic Sn, endowing the PCMs with high potential for mass production. The as-obtained Sn@Al2O3 showed a core-shell structure, in which a main metallic Sn core located in the center covered with an Al2O3 shell with small Sn nanoparticles distributed inside. The boehmite treatment, in which the penetration of aluminum species into SnO2 spheres played an important role, was found to be responsible for the unique structure formation of final Sn@Al2O3. The understanding of structure formation mechanism gives the possibilities of a new facile way for the synthesis of metal nanoparticles and particle-distributed nanostructures. The obtained Sn@Al2O3 particles not only have high PCM content (92.37 wt %) but also show a stable thermal behavior and morphology during 100 melt freeze cycles in the air atmosphere. Furthermore, the low melting temperature of the PCM core, combined with high thermal conductivity of both core material (Sn, 66.8 W m(-1) K-1) and shell material (Al2O3, 35 W m(-1) K-1), makes Sn@Al2O3 potentially suitable for rapid thermal energy storage in the range 100-300 degrees C.

δ-MnO2 nanoflower/graphite cathode for rechargeable aqueous zinc ion batteries
Sonti Khamsanga, Rojana Pornprasertsuk, Tetsu Yonezawa, Ahmad Azmin Mohamad, Soorathep Kheawhom
Scientific Reports, 9, 8441, Jun. 2019, [Peer-reviewed]
English, Scientific journal, Manganese oxide (MnO2) is one of the most promising intercalation cathode materials for zinc ion batteries (ZIBs). Specifically, a layered type delta manganese dioxide (δ-MnO2) allows reversible insertion/extraction of Zn2+ ions and exhibits high storage capacity of Zn2+ ions. However, a poor conductivity of δ-MnO2, as well as other crystallographic forms, limits its potential applications. This study focuses on δ-MnO2 with nanoflower structure supported on graphite flake, namely MNG, for use as an intercalation host material of rechargeable aqueous ZIBs. Pristine δ-MnO2 nanoflowers and MNG were synthesized and examined using X-ray diffraction, electron spectroscopy, and electrochemical techniques. Also, performances of the batteries with the pristine δ-MnO2 nanoflowers and MNG cathodes were studied in CR2032 coin cells. MNG exhibits a fast insertion/extraction of Zn2+ ions with diffusion scheme and pseudocapacitive behavior. The battery using MNG cathode exhibited a high initial discharge capacity of 235 mAh/g at 200 mA/g specific current density compared to 130 mAh/g which is displayed by the pristine δ-MnO2 cathode at the same specific current density. MNG demonstrated superior electrical conductivity compared to the pristine δ-MnO2. The results obtained pave the way for improving the electrical conductivity of MnO2 by using graphite flake support. The graphite flake support significantly improved performances of ZIBs and made them attractive for use in a wide variety of energy applications.

Electrochemical exploration of the effects of calcination temperature of a mesoporous zinc vanadate anode material on the performance of Na-ion batteries
Rasu Muruganantham, Irish Valerie Maggay, Lyn-Marie Z. De Juan, Tetsu Yonezawa, Mai Thanh Nguyen, Yan-Gu Lin, Chia-Her Lin, Wei-Ren Liu
Inorganic Chemistry Frontiers, in press, Jun. 2019, [Peer-reviewed]
Nowadays, transition metal oxides are being rapidly developed for application as Na-ion storage anode materials, which provide a relatively high theoretical capacity compared to the graphitic anode; however, the evaluation of enhanced electrochemical performance of SIBs via various approaches, such as coating or doping, is an ongoing process. Hence, in this study, a mesoporus ZnV2O4 anode material with a spinel structure was successfully synthesized via a solvothermal technique followed by calcination at different temperatures; moreover, the impact of the calcination temperature on the Na-ion storage performance of this anode material was thoroughly investigated for the first time. The initial discharge capacities of 178, 251, and 296 mA h g−1 were obtained for the cacination temperatures of 500, 600, and 700 °C, respectively; after 250 cycles, the ZVO-700 electrode retained the discharge capacity of 166 mA h g−1 at 200 mA g−1 with the high coulombic efficiency of 99%. Furthermore, ZVO-500 and ZVO-600 retained 55 mA h g−1 and 99 mA h g−1 with a ∼27% and ∼42% retention rate, respectively. The electrochemical Na-ion storage performance is predicted by the conversion reaction of ZnV2O4. Moreover, the ZVO-700 sample showed higher surface area and pore volume, which led to remarkable electrochemical performance, than the ZVO-500 and ZVO-600 samples.

Porous ZnV2O4 Nanowire for Stable and High-rate Lithium Ion Battery Anodes
Lyn Marie, Z. De Juan-Corpuz, Mai Thanh Nguyen, Ryan D. Corpuz, Tetsu Yonezawa, Nataly Carolina Rosero-Navarro, Kiyoharu Tadanaga, Tomoharu Tokunaga, Soorathep Kheawhom
ACS Applied Nano Materials, 2, 7, 4247, 4256, Jun. 2019, [Peer-reviewed]
English, Scientific journal, Porous ZnV2O4 nanowires (NWs) were successfully prepared by hydrothermal reaction followed by calcination. Despite the porous structure, these porous ZnV2O4 NWs are single crystal with {220} facets and a wire direction along the c-axis. On the basis of an electrochemical test, these porous ZnV2O4 NWs have better cycling stability and higher specific capacity (i.e., 460 mA h g–1 after 100 cycles and 149 mA h g–1 after 1000 cycles using 1 and 5 A g–1 current densities, respectively) compared to other morphologies (i.e., spherical and coral-like morphologies). As a ternary transition metal oxide, the produced porous ZnV2O4 NWs undergo phase transformation without compromising the resulting capacity. On the other hand, the CV curves at different scan rates indicate a pseudocapacitive electrochemical behavior of the porous ZnV2O4.

Synthesis of Sn/Ag–Sn nanoparticles via room temperature galvanic reaction and diffusion
Min Jia Saw, Mai Thanh Nguyen, Shilei Zhu, Yongming Wang, Tetsu Yonezawa
RSC Advances, 9, 38, 21786, 21792, Apr. 2019, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Tin (Sn) has a low melting temperature, i.e., 231.9 °C for the bulk, and the capability to form compounds with many metals. The galvanic reaction between Sn nanoparticles (NPs) as the core and silver nitrate at room temperature under argon gas in an organic solvent without any reducing power, was employed for the first time to coat an Ag–Sn intermetallic shell, i.e., Ag3Sn and/or Ag4Sn, on Sn NPs. For spherical Sn NPs, the NPs retained a spherical shape after coating. Uniform and Janus structures consisting of a β-Sn core with Ag–Sn shell were observed in the resulting NPs and their population related to the input molar ratios of the metal precursors. The observation of the intermetallic shell is general for both spherical and rod-shape Sn NPs. The formation of the intermetallic shell indicated that two reactions occurred sequentially, first reduction of Ag ions to Ag atoms by the Sn core, followed by interdiffusion of Ag and Sn to form the Ag–Sn intermetallic shell.

Size-controlled Preparation of Alkylamine-stabilized Copper Fine Particles from Cupric Oxide (CuO) Micro-particles
Tetsu Yonezawa, Jiajia Shi, Hiroki Tsukamoto, Mai Thanh Nguyen
MRS Advances, 4, 7, 413, 418, Springer Science and Business Media LLC, Feb. 2019, [Peer-reviewed], [Lead author, Corresponding author]
English, Scientific journal

Monitor the Growth and Oxidation of Cu-nanoparticles in PEG after Sputtering
Yuen-ting Rachel Chau, Lianlian Deng, Mai Thanh Nguyen, Tetsu Yonezawa
MRS Advances, 4, 5-6, 305, 309, Springer Science and Business Media LLC, Jan. 2019, [Last author, Corresponding author]
Scientific journal

Ethanol as an electrolyte additive for alkaline zinc-air flow batteries
Soraya Hosseini, Siow Jing Han, Amornchai Arponwichanop, Tetsu Yonezawa, Soorathep Kheawhom
Scientific Reports, 8, 1, Nature Publishing Group, 01 Dec. 2018
English, Scientific journal, Zinc-air flow batteries exhibit high energy density and offer several appealing advantages. However, their low efficiency of zinc utilization resulted from passivation and corrosion of the zinc anodes has limited their broad application. In this work, ethanol, which is considered as an environmentally friendly solvent, is examined as an electrolyte additive to potassium hydroxide (KOH) aqueous electrolyte to improve electrochemical performance of the batteries. Besides, the effects of adding different percentages of ethanol (0–50% v/v) to 8 M KOH aqueous electrolyte were investigated and discussed. Cyclic voltammograms revealed that the presence of 5–10% v/v ethanol is attributed to the enhancement of zinc dissolution and the hindrance of zinc anode passivation. Also, potentiodynamic polarization and electrochemical impedance spectroscopy confirmed that adding 5–10% v/v ethanol could effectively suppress the formation of passivating layers on the active surface of the zinc anodes. Though the addition of ethanol increased solution resistance and hence slightly decreased the discharge potential of the batteries, a significant enhancement of discharge capacity and energy density could be sought. Also, galvanostatic discharge results indicated that the battery using 10% v/v ethanol electrolyte exhibited the highest electrochemical performance with 30% increase in discharge capacity and 16% increase in specific energy over that of KOH electrolyte without ethanol.

Electrochemical properties of novel FeV2O4 as an anode for Na-ion batteries
Irish Valerie B. Maggay, Lyn Marie Z. De Juan, Jeng-Shin Lu, Mai Thanh Nguyen, Tetsu Yonezawa, Ting-Shan Chan, Wei-Ren Liu
Scientific Reports, 8, 1, Nature Publishing Group, 01 Dec. 2018, [Peer-reviewed]
English, Scientific journal, Spinel based transition metal oxide - FeV2O4 is applied as a novel anode for sodium-ion battery. The electrochemical tests indicate that FeV2O4 is generally controlled by pseudo-capacitive process. Using cost-effective and eco-friendly aqueous based binders, Sodium-Carboxymethylcellulose/Styrene butadiene rubber, a highly stable capacity of ~97 mAhg-1 is obtained after 200 cycles. This is attributed to the strong hydrogen bonding of carboxyl and hydroxyl groups indicating superior binding with the active material and current collector which is confirmed by the ex-situ cross-section images of the electrode. Meanwhile, only ~27 mAhg-1 is provided by the electrode using poly(vinylidene difluoride) due to severe detachment of the electrode material from the Cu foil after 200 cycles. The obtained results provide an insight into the possible applications of FeV2O4 as an anode material and the use of water-based binders to obtain highly stable electrochemical tests for sodium-ion battery.

Yttrium (III) Recovery with D2EHPA in Pseudo-Emulsion Hollow Fiber Strip Dispersion System
Teerapon Pirom, Amornchai Arponwichanop, Ura Pancharoen, Tetsu Yonezawa, Soorathep Kheawhom
Scientific Reports, 8, 1, Nature Publishing Group, 01 Dec. 2018, [Peer-reviewed]
English, Scientific journal, Yttrium (Y) is an essential lanthanide rare earth element and can be effectively extracted and purified using a hollow fiber supported liquid membrane (HFSLM) system. However, the stability of HFSLM system is a significant challenge. Pseudoemulsion-hollow fiber strip dispersion (PEHFSD) system, providing excellent stability, is attracting research attention. In this work, the recovery of Y(III) by PEHFSD system using di(2-ethylhexyl)phosphoric acid (D2EHPA) as a carrier was investigated. The effects of several operating parameters, including the initial concentration of Y(III) in the feed phase, the flow rate of feed, the stirring speed and the volumetric ratio of feed to strip on Y(III) separation were studied. The Y(III) transport was analyzed on the concentration ratio of Y(III) ions, percent extraction, percent stripping and overall mass transfer coefficient (K p ). The PEHFSD system outperformed HFSLM system regarding separation performance and stability. K p of HFSLM system decreased after the second run, but K p of PEHFSD system remained constant even at the fifth run. The dispersed droplets in the strip dispersion phase in the PEHFSD system enhanced separation performance and stability of the membrane module.

Microwave-Induced Plasma-In-Liquid Process for Nanoparticle Production
Tetsu Yonezawa, David Čempel, Mai Thanh Nguyen
Bulletin of the Chemical Society of Japan, 91, 12, 1781, 1798, The Chemical Society of Japan, Dec. 2018, [Peer-reviewed], [Invited]
English, Scientific journal, In the past decades, various nanomaterials have been intensively developed because of their unique electrical, optical, magnetic as well as catalytic properties. In this review, we discuss the plasma-in-liquid process, especially the microwave-induced plasma-in-liquid process (MWPLP), for metal and metal oxide nanoparticle production. Various types of plasma systems have been employed to produce metal, alloy, and metal oxide nanoparticles. Nanoparticle production by plasma processes usually requires fewer chemical additives compared to other chemical processes. After discussing the bottom-up approach and the plasma-in-liquid process for nanoparticle synthesis, we have focused on MWPLP. Various apparatus systems and detailed mechanisms of MWPLP will be discussed and preparation of metal and metal oxide nanoparticles by MWPLP will be introduced in detail. The surface-coated-electrode system, which is a unique system for MWPLP, is also discussed in this review. This system prevents sample contamination due to the metal components, which are usually ejected into the surrounding liquid after plasma ignition during the production of nanoparticles.

Sputtering onto a liquid: interesting physical preparation method for multi-metallic nanoparticles
Mai Thanh Nguyen, Tetsu Yonezawa
Science and Technology of Advanced Materials, 19, 1, 883, 898, Oct. 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, The young history of sputtering onto a liquid features great achievements in the green production of various metal and metal oxide nanoparticles (NPs) and nanoclusters (NCs). Studies on how the sputtering parameters affect the properties of NPs and NCs have elucidated their formation mechanism and marked a crucial role of liquid matrix in the nucleation and growth of particles, controlling their various properties. Current research has been devoted to making alloy bi- and trimetallic NPs with a high level of control over the NP structure, composition, and size via well-designed target systems, sputtering steps, and liquid matrix materials. In this minireview, we discuss the recent advances in the use of various types of targets to prepare different bi- and trimetallic NPs. In single target sputtering, systems with alternative configurations of metals, alloy targets, monometallic targets in sequence, and a combination of sputtering and chemical reactions have been developed. On the other hand, a double head system was introduced to widen the range of controllable sputtering parameters yielding more versatility in particle composition and fine structure. The synergistic and tuneable properties exhibited by the multi-metallic components in small NPs and NCs for their use in catalysis and optical applications are discussed.

Enhancements of X-ray emission from solution film of gold nano-colloidal suspension under double-pulse excitation
Wei-Hung Hsu, Frances Camille, P. Masim, Armandas Balcytis, Hsin-Hui Huang, Tetsu Yonezawa, Aleksandr A. Kuchmizhak, Saulius Juodkazis, Koji Hatanaka
Beilstein Journal of Nanotechnology, 9, 2609, 2617, Oct. 2018, [Peer-reviewed]
English, Scientific journal, Enhancement of X-ray emission was observed from a micro-jet of a nano-colloidal gold suspension in air under double-pulse excitation of ultrashort (40 fs) near-IR laser pulses. Temporal and spatial overlaps between the pre-pulse and the main pulse were optimized for the highest X-ray emission. The maximum X-ray intensity was obtained at a 1–7 ns delay of the main pulse irradiation after the pre-pulse irradiation with the micro-jet position shifted along the laser beam propagation. It was revealed that the volume around gold nanoparticles where the permittivity is near zero, ε ≈ 0, accounts for the strongest absorption, which leads to the effective enhancements of X-ray emission.

Discharge Performance of Zinc-Air Flow Batteries Under the Effects of Sodium Dodecyl Sulfate and Pluronic F-127
Soraya Hosseini, Woranunt Lao-atiman, Siow Jing Han, Amornchai Arpornwichanop, Tetsu Yonezawa, Soorathep Kheawhom
Scientific Reports, 8, 14909, Oct. 2018, [Peer-reviewed]
English, Scientific journal, Zinc-air batteries are a promising technology for large-scale electricity storage. However, their practical deployment has been hindered by some issues related to corrosion and passivation of the zinc anode in an alkaline electrolyte. In this work, anionic surfactant sodium dodecyl sulfate (SDS) and nonionic surfactant Pluronic F-127 (P127) are examined their applicability to enhance the battery performances. Pristine zinc granules in 7 M KOH, pristine zinc granules in 0–8 mM SDS/7 M KOH, pristine zinc granules in 0–1000 ppm P127/7 M KOH, and SDS coated zinc granules in 7 M KOH were examined. Cyclic voltammograms, potentiodynamic polarization, and electrochemical impedance spectroscopy confirmed that using 0.2 mM SDS or 100 ppm P127 effectively suppressed the anode corrosion and passivation. Nevertheless, direct coating SDS on the zinc anode showed adverse effects because the thick layer of SDS coating acted as a passivating film and blocked the removal of the anode oxidation product from the zinc surface. Furthermore, the performances of the zinc-air flow batteries were studied. Galvanostatic discharge results indicated that the improvement of discharge capacity and energy density could be sought by the introduction of the surfactants to the KOH electrolyte. The enhancement of specific discharge capacity for 30% and 24% was observed in the electrolyte containing 100 ppm P127 and 0.2 mM SDS, respectively.

Copper ion production using zeolite and application to MALDI MS of small molecules
Megumi Sakurai, Mengrui Yang, Jiawei Xu, Mai Thanh Nguyen, Tetsu Yonezawa, Kenro Hashimoto, Tatsuya Fujino
International Journal of Mass Spectroscopy, 434, 179, 184, Elsevier BV, Sep. 2018, [Peer-reviewed]
English, Scientific journal, CuO nanoparticles (CuO) loaded on zeolite (CuO/HM20) and zeolite whose active sites are substituted by copper (CuM20) have been developed as matrices for laser desorption ionization. CuO/HM20 showed efficient Cu+ production upon laser irradiation. By several spectroscopic results, it was found that CuO interacts with hydroxyl groups in zeolite and the lifetime of electron hole pair becomes long owing to the presence of the zeolite support. In addition, it was also found that water molecules surrounding the CuO play an important role in the Cu2++e → Cu+ reaction on the CuO surface. For CuM20, on the other hand, Cu+ production was not effective, probable because strong binding of Cu2+ with water molecules hindered the desorption of copper ions. These two matrices were applied to the desorption ionization of small molecules (arginine, tyrosine, heptacosan, melamine and creatinine). It was found that CuO/HM20 ionized analyte efficiently and CuM20 had selectivity for Cu+ adduction ionization.

Kinetics of Cationic-Ligand-Exchange Reactions in Au-25 Nanoclusters
Huang Zhong, Ishida Yohei, Narita Kunihiro, Yonezawa Tetsu
JOURNAL OF PHYSICAL CHEMISTRY C, 122, 31, 18142, 18150, 09 Aug. 2018, [Peer-reviewed], [Last author, Corresponding author]

Sn Nanoparticles Confined in Porous Silica Spheres for Enhanced Thermal Cyclic Stability
Zhu Shilei, Mai Thanh Nguyen, Fumoto Koji, Kanie Kiyoshi, Muramatsu Atsushi, Yonezawa Tetsu
ACS APPLIED NANO MATERIALS, 1, 8, 4073, 4082, AMER CHEMICAL SOC, Aug. 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, We report a facile method for preparing a silica (SiO2)-based material containing Sn nanoparticles (NPs) distributed inside for enhancing the thermal cyclic stability of the inserted Sn NPs. Absorption of a Sn precursor (i.e., an aqueous SnCl2 solution) into a mesoporous SiO2 matrix resulted in confinement of the Sn precursor in a mesoporous SiO2 matrix. Hydrogen thermal reduction of the above composite yielded Sn nanoparticles with a diameter of ca. 30 nm uniformly distributed inside porous SiO2 (p-SiO2) spheres: Sn NPs@p-SiO2. Our investigation of the transformation ofthe porous SiO2 structure to hold Sn NPs revealed that the process was closely related to the transformation of the amorphous hydrolyzed Sn precursor into Sn oxides followed by, probably, the rearrangement of the SiO2 matrix via its interaction with the melting Sn. This led to the formation of stable Sn NPs@p-SiO2. The SiO2 matrix effectively prevented the coalescence of the Sn NPs, and the obtained product exhibited negligible changes in melting behavior during the second to 100th cycle of a freeze melt cycle test.

Ultra-rapid Cationization of Gold Nanoparticles via a Single-step Ligand Exchange Reaction
Yohei Ishida, Jun Suzuki, Ikumi Akita, Tetsu Yonezawa
Langmuir, 34, 36, 10668, 10672, Aug. 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, We propose a novel method for the ultra-rapid cationization of gold nanoparticles with diameters ranging from several to a hundred nanometers via a single-step ligand exchange reaction of citrate-protected anionic gold nanoparticles with cationic thiol ligand. This reaction was performed only in an aqueous medium via a single step from citrate to cationic thiol, therefore enables a rapid preparation of cationic Au NPs without a contamination of organic solvent or lipid-soluble molecules. The cationization was successfully completed within 20 min without changes in the core diameter and optical characteristic.

β-Sn Nanorods with Active (001) Tip Induced LiF-Rich SEI Layer for Stable Anode Material in Lithium Ion Battery
Lyn Marie Z. De Juan, Irish Valerie B. Maggay, Mai Thanh Nguyen, Wei-Ren Liu, Tetsu Yonezawa
ACS Applied Nano Materials, 1, 7, 3509, 3519, American Chemical Society ({ACS}), 27 Jul. 2018, [Peer-reviewed]
English, Scientific journal

ZnV2O4: A potential anode material for sodium-ion batteries
Irish Valerie Buiser Maggay, Lyn Marie Z. De Juan, Mai Thanh Nguyen, Tetsu Yonezawa, B. K. Chang, T. S. Chan, Wei-Ren Liu
Journal of the Taiwan Institute of Chemical Engineers, 88, 161, 168, Taiwan Institute of Chemical Engineers, 01 Jul. 2018, [Peer-reviewed]
English, Scientific journal, A template-free solvothermal method was employed to successfully obtain ZnV2O4 spinel oxide and its electrochemical properties as anode materials for sodium ion battery system were investigated for the first time. The structural, morphological, elemental composition, electrochemical properties and theoretical calculations of the as-prepared ZnV2O4 were carried out. XRD revealed the presence of ZnO and VO2 impurities when synthesized for 1 day, while complete formation of ZnV2O4 was attained when the synthesis procedure was increased to 3 days. When cycled at 50 mA/g, it delivered an initial capacity of as high as 537 mAh/g at a potential window of 0.01–3.0 V. Meanwhile, a reversible capacity of ∼ 113 mAh/g was obtained when cycled at 100 mA/g for 30 cycles. These results indicate the potential applications of ZnV2O4 as anode materials for sodium ion battery systems.

Surface Design and Functional Prediction of Inorganic Nanoparticles for Electronic Material Applications
Tetsu Yonezawa, Masaki Matsubara
Journal of the Society of Powder Technology, Japan, 55, 6, 325, 333, The Society of Powder Technology, Japan, 10 Jun. 2018
Scientific journal

Sputter Deposition toward Short Cationic Thiolated Fluorescent Gold Nanoclusters: Investigation of Their Unique Structural and Photophysical Characteristics Using High-Performance Liquid Chromatography.
Yohei Ishida, Akihiro Morita, Tomoharu Tokunaga, Tetsu Yonezawa
Langmuir : the ACS journal of surfaces and colloids, 34, 13, 4024, 4030, 03 Apr. 2018, [Peer-reviewed], [Last author, Corresponding author], [International Magazine]
English, We herein present the preparation of short, bulky cationic thiolate (thiocholine)-protected fluorescent Au nanoclusters via sputter deposition over a liquid polymer matrix. The obtained Au nanoclusters showed near-infrared fluorescence and had an average core diameter of 1.7 ± 0.6 nm, which is too large compared to that of the reported fluorescent Au nanoclusters prepared via chemical means. We revealed the mechanism of formation of this unique material using single-particle electron microscopy, optical measurements, X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography fractionations. The noncrystallized image was observed via single-particle high-angle annular dark-field scanning transmission electron microscopy observations and compared with chemically synthesized crystalline Au nanoparticle with the same diameter, which demonstrated the unique structural characteristic speculated via XPS. The size fractionation and size-dependent fluorescence measurement, together with other observations, indicated that the nanoclusters most probably contained a mixture of very small fluorescent species in their aggregated form and were derived from the sputtering process itself and not from the interaction between thiol ligands.

Sub-2 nm Single-Crystal Pt Nanoparticles via Sputtering onto a Liquid Polymer
Lianlian Deng, Mai Thanh Nguyen, Tetsu Yonezawa
Langmuir, 34, 8, 2876, 2881, American Chemical Society, 27 Feb. 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Matrix sputtering with the use of a low vapor pressure liquid as its matrix becomes a green technique to prepare nanoparticles dispersed in liquid. In the present study, we proposed using this method with polyethylene glycol (PEG, molecular weight = 600) as the liquid matrix to produce highly uniform Pt nanoparticles with a small size (below 2.0 nm) and a narrow size distribution. The results indicated that particle sizes were tailorable from 0.9 ± 0.3 to 1.4 ± 0.3 nm by varying the sputtering current (5-50 mA) with negligible particle aggregation that occurred in PEG during sputtering. The slight growth of the particle size observed after sputtering was attributed to the addition of free Pt atoms to the existing Pt nanoparticles. All samples formed stable dispersion in PEG for 5 month storage. This result suggested an advantage of using a liquid matrix to produce and stabilize nanoparticles.

Desorption and ionization of amino acids by surface-assisted laser desorption/ionization mass spectrometry (Saldi-MS) using titanium oxide nanoparticles in positive ion mode
Takashi Asano, Tetsu Yonezawa
Nano Biomedicine, 10, 2, 83, 90, National Institute of Informatics, 2018
English, Scientific journal, Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) with inorganic nanoparticles as desorption/ionization (DI) assisting materials, has been reported in order to decrease the background noises including matrix ions or matrix degradation products, especially in the region of <
500 Da. In this mass region, we can detect the existence of medical material components, drugs, and bio-related organic compounds. However, the mechanism of desorption/ ionization of SALDI-MS is not clear. Therefore, in order to understand the correlation of desorption/ ionization efficiency with molecular structures of analytes, the efficiencies of 20 common amino acids in SALDI-MS with TiO2 nanoparticles are collected in positive ion mode. SALDI-MS with TiO2 nanoparticles gives sodium ion adducted mass peaks. The ion intensity of amino acids is mainly determined by the same factors regardless of the desorption/ionization method in both MALDI and proton adducted SALDI but poorer linear correlation between the ion yield and the sodium ion affinity was found in our system.

Ligand free green plasma-in-liquid synthesis of Au/Ag alloy nanoparticles
David Čempel, Mai Thanh Nguyen, Yohei Ishida, Tomoharu Tokunaga, Tetsu Yonezawa
New Journal of Chemistry, 42, 8, 5680, 5687, Royal Society of Chemistry, 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Au/Ag alloy nanoparticles (NPs) were successfully prepared by a one step synthesis using HAuCl4 and [Ag(NH3)2]+ as the corresponding precursors in a microwave-induced plasma in liquid process (MWPLP) without the addition of any organic protecting or reducing agents. The time dependent reduction and particle formation during the 140 min plasma discharge were studied with TEM, UV-vis extinction spectra, and ICP-OES. After 140 min, the HAADF-STEM and EDX results indicated that the obtained Au/Ag NPs were alloy NPs. Varying the input molar ratios of the metal precursors allowed for control of the composition of the Au/Ag alloy NPs.

Preparation of Ag nanoparticles using hydrogen peroxide as a reducing agent　　　　　　　　　　　　　　　
M. Nishimoto, S. Abe, T. Yonezawa
New J. Chemistry, 42, 14493, 14501, 2018, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal

L-arginine-stabilized highly uniform Ag nanoparticles prepared in a microwave-induced plasma-in-liquid process (MWPLP)
David Čempel, Mai Thanh Nguyen, Yohei Ishida, Tetsu Yonezawa
Bulletin of the Chemical Society of Japan, 91, 3, 362, 367, Chemical Society of Japan, 2018, [Peer-reviewed]
English, Scientific journal, Microwave induced plasma in liquid has become a green and effective method for preparation of metallic nanoparticles (NPs). In our research, we have introduced yttrium oxide (Y2O3) coated stainless steel electrodes to address impurity problems of resulting NPs due to the loss of electrode materials. We have proposed using [Ag(NH3)2]+ complex as an alternative precursor and L-arginine as the stabilizing agent to synthesize highly uniform Ag NPs with an average diameter of around 5nm. [Ag(NH3)2]+ complex was chosen as it can allow the reaction proceed at high pH for higher reaction yield compared with using AgNO3 whereas L-arginine can stabilize Ag NPs to attain highly uniform and small sizes. The influence of the selection of initial precursor on the reduction of metal precursor during the plasma irradiation, the particle size and size distribution of Ag NPs, and influence of the amount of L-arginine, were investigated.

Real-Space Investigation of Energy Transfer through Electron Tomography
Yohei Ishida, Ikumi Akita, Thomas Pons, Tetsu Yonezawa, Niko Hildebrandt
Journal of Physical Chemistry C, 121, 51, 28395, 28402, American Chemical Society, 28 Dec. 2017, [Peer-reviewed]
English, Scientific journal, We herein report the first real-space investigation of Förster resonance energy transfer (FRET) in two different types of quantum dot (QD) supramolecular assemblies by observing their three-dimensional (3D) configurations through high-resolution electron tomography. Owing to its critical role in photosynthesis, artificial light-harvesting antennas, and investigation of protein-protein interactions, the mechanism of FRET has been intensively studied by monitoring its excited-state dynamics via various spectroscopic techniques. The utilized electron tomography technique allowed the direct localization of 3D coordinates of individual QDs in self-assembled nanostructures and theoretical estimation of the FRET efficiency of a single fluorophore, domain, or supramolecular assembly. Moreover, the experimental value of the FRET efficiency determined by fluorescence spectroscopy was in good agreement with the magnitude obtained via electron tomography. We believe that the described strategy can be used in single-molecule FRET studies and will help to create a new bridge between material science and molecular/supramolecular photochemistry.

Matrix Sputtering Method: A Novel Physical Approach for Photoluminescent Noble Metal Nanoclusters
Yohei Ishida, Ryan D. Corpuz, Tetsu Yonezawa
ACCOUNTS OF CHEMICAL RESEARCH, 50, 12, 2986, 2995, AMER CHEMICAL SOC, Dec. 2017, [Peer-reviewed], [Invited]
English, Scientific journal, Noble metal nanoclusters are believed to be the transition between single metal atoms, which show distinct optical properties, and metal nanoparticles, which show characteristic plasmon absorbance. The interesting properties of these materials emerge when the particle size is well below 2 nm, such as photoluminescence, which has potential application particularly in biomedical fields. These photoluminescent ultrasmall nanoclusters are typically produced by chemical reduction, which limits their practical application because of the inherent toxicity of the reagents used in this method. Thus, alternative strategies are sought, particularly in terms of physical approaches, which are known as "greener alternatives," to produce high purity materials at high yields. Thus, a new approach using the sputtering technique was developed. This method was initially used to produce thin films using solid substrates; now it can be applied even with liquid substrates such as ionic liquids or polyethylene glycol as long as these liquids have a low vapor pressure. This revolutionary development has opened up new areas of research, particularly for the synthesis of colloidal nanoparticles with dimensions below 10 nm. We are among the first to apply the sputtering technique to the physical synthesis of photoluminescent noble metal nanoclusters. Although typical sputtering systems have relied on the effect of surface composition and viscosity of the liquid matrix on controlling particle diameters, which only resulted in diameters ca. 3-10 nm, that were all plasmonic, our new approach introduced thiol molecules as stabilizers inspired from chemical methods. In the chemical syntheses of metal nanoparticles, controlling the concentration ratio between metal ions and stabilizing reagents is a possible means of systematic size, control. However, it was not clear whether this would be applicable in a sputtering system. Our latest results showed that we were able to generically produce a variety of photoluminescent monometallic nanoclusters of Au, Ag, and Cu, all of which showed stable emission in both solution and solid form via our matrix sputtering method with the induction of cationic-, neutral-, and anionic-charged thiol ligands. We also succeeded in synthesizing photoluminescent bimetallic Au-Ag nanoclusters that showed tunable emission within the UV-NIR region by controlling the composition of the atomic ratio by a double-target sputtering technique. Most importantly, we have revealed the formation mechanism of these unique photoluminescent nanoclusters by sputtering, which had relatively larger diameters (ca. 1-3 nm) as determined using TEM and stronger emission quantum yield (max. 16.1%) as compared to typical photoluminescent nanoclusters prepared by chemical means. We believe the high tunability of sputtering systems presented here has significant advantages for creating novel photoluminescent nanoclusters as a complementary strategy to common chemical methods. This Account highlights our journey toward understanding the photophysical properties and formation mechanism of photoluminescent noble metal nanoclusters via the sputtering method, a novel strategy that will contribute widely to the body of scientific knowledge of metal nanoparticles and nanoclusters.

Au/Cu Bimetallic Nanoparticles via Double-Target Sputtering onto a Liquid Polymer
Mai Thanh Nguyen, Hong Zhang, Lianlian Deng, Tomoharu Tokunaga, Tetsu Yonezawa
LANGMUIR, 33, 43, 12389, 12397, AMER CHEMICAL SOC, Oct. 2017, [Peer-reviewed]
English, Scientific journal, Alloy nanoparticles (NPs) of a bimetal system, Au/Cu, that form intermetallic compounds in a bulk state have been successfully produced using a double-target sputtering technique onto a low-cost and biocompatible liquid polymer (polyethylene glycol, PEG). The formation of an Au/Cu solid solution alloy in individual NPs was revealed by scanning transmission electron microscopy-energy-dispersive X-ray elemental mapping analysis. Altering the sputter currents for Au and Cu targets resulted in a tailored NP composition, but the particle sizes did not significantly vary. We found similar structures, sizes, and optical properties of Au/Cu NPs obtained by double-head sputtering on carbon-coated transmission electron microscopy grids or PEG and by Au/Cu alloy target sputtering. Random alloy formation occurred in matrix sputtering using double-target heads. This method is advantageous for manipulating the alloy composition through highly independent control of sputter parameters for each metal target.

Structural Control Parameters for Formation of Single-Crystalline ss-Sn Nanorods in Organic Phase
Lyn Marie Z. De Juan, Mai Thanh Nguyen, Tetsu Yonezawa, Tomoharu Tokunaga, Hiroki Tsukamoto, Yohei Ishida
CRYSTAL GROWTH & DESIGN, 17, 9, 4554, 4562, AMER CHEMICAL SOC, Sep. 2017, [Peer-reviewed]
English, Scientific journal, For the first time, investigation on the effect of lowering the synthesis temperature below room temperature (10 to -10 degrees C) and increasing the viscosity of the reaction solution at certain temperatures has been used to trigger the formation of single-crystalline ss-Sn nanorods (NRs) in a chemical synthesis using an organic solvent. These two parameters govern the energy of the particles in the solution, thereby mediating the selective attachment to the nuclei and the preferential growth of Sn along the c-axis. The length and aspect ratio of the NRs were inversely proportional to the synthesis temperature and directly proportional to the viscosity of the reaction solution. In addition, we found that poly(vinylpyrrolidone) with a high molecular weight aided the formation of longer and higher aspect ratio NRs via the bridge flocculation effect.

Effects of Additives on the Preparation of Ag Nanoparticles Using the Microwave-Induced Plasma in Liquid Process
Masamu Nishimoto, Hiroki Tsukamoto, Mai Thanh Nguyen, Tetsu Yonezawa
CHEMISTRYSELECT, 2, 26, 7873, 7879, WILEY-V C H VERLAG GMBH, Sep. 2017, [Peer-reviewed]
English, Scientific journal, The effect of additives, i.e., H2O2 and pH adjustors, on the preparation of Ag nanoparticles (NPs) fabricated using the microwave-induced plasma in liquid process (MWPLP) has been investigated. When both aqueous ammonia and NaOH were used as pH adjustors, the rate of the reduction of silver ions decreased with lower concentrations of H2O2 or at higher pH values. Under these conditions, the aggregation of generated nuclei during the early stages of the reduction was suppressed, and the sizes of the obtained Ag NPs decreased. The amount of H2O2 and the pH of the reduction solutions are therefore highly important parameters for the preparation of well-dispersed Ag NPs using the MWPLP.

Synthesis of Positively Charged Photoluminescent Bimetallic Au-Ag Nanoclusters by Double-Target Sputtering Method on a Biocompatible Polymer Matrix
Ryan D. Corpuz, Yohei Ishida, Mai Thanh Nguyen, Tetsu Yonezawa
LANGMUIR, 33, 36, 9144, 9150, AMER CHEMICAL SOC, Sep. 2017, [Peer-reviewed]
English, Scientific journal, Herein, we report a novel positively charged photoluminescent Au-Ag bimetallic nanocluster synthesized using 11-mercaptoundecyl-N,N,N-trimethylammonium bromide as the capping ligand by means of green double-target sputtering method on a biocompatible polymer matrix. The photoluminescent Au-Ag bimetallic cluster showed emission tunability from blue to near infrared (NIR) regions with respect to change in the composition.

Small Nanosized Oxygen-Deficient Tungsten Oxide Particles: Mechanistic Investigation with Controlled Plasma Generation in Water for Their Preparation.
Yohei Ishida, Shingo Motono, Wataru Doshin, Tomoharu Tokunaga, Hiroki Tsukamoto, Tetsu Yonezawa
ACS omega, 2, 8, 5104, 5110, 31 Aug. 2017, [Peer-reviewed], [International Magazine]
English, Scientific journal, Production of oxygen-deficient tungsten oxide nanoparticles with a diameter of around 10 nm have been successfully developed using a microwave-induced plasma in liquid technique. The prepared blue-green nanoparticles exhibit strong absorption in the visible region; thus, these could be efficient visible-light photocatalysts. The high-angle annular dark-field images revealed the dislocation of tungsten, which causes oxygen deficiencies.

Photoacoustic signal enhancements from gold nano-colloidal suspensions excited by a pair of time-delayed femtosecond pulses
Frances Camille P. Masim, Wei-Hung Hsu, Hao-Li Liu, Tetsu Yonezawa, Armandas Balcytis, Saulius Juodkazis, Koji Hatanaka
OPTICS EXPRESS, 25, 16, 19497, 19507, OPTICAL SOC AMER, Aug. 2017, [Peer-reviewed]
English, Scientific journal, Photoacoustic signal enhancements were observed with a pair of time-delayed femtosecond pulses upon excitation of gold nanosphere colloidal suspension. A systematic experimental investigation of photoacoustic intensity within the delay time, Delta t = 0 to 15 ns, was carried out. The results revealed a significant enhancement factor of similar to 2 when the pre-pulse energy is 20-30% of the total energy. Pre-pulse and main pulse energy ratios, E-p((1)) :E-s((2)) were varied to determine the optimal ratio that yields to maximum photoacoustic signal enhancement. This enhancement was ascribed to the initial stage of thermalization and bubble generation in the nanosecond time scale. Pre-pulse scattering intensity measurements and numerical finite-difference time-domain calculations were performed to reveal dynamics and light field enchancement, respectively. (C) 2017 Optical Society of America

Particle size tuning in scalable synthesis of anti-oxidized copper fine particles by polypeptide molecular weights
Tetsu Yonezawa, Hiroki Tsukamoto, Mai Thanh Nguyen
ADVANCED POWDER TECHNOLOGY, 28, 8, 1966, 1971, ELSEVIER SCIENCE BV, Aug. 2017, [Peer-reviewed]
English, Scientific journal, Size tuning of metallic copper fine particles is highly important for their application to conductive pastes. Uniformly sized metallic copper fine particles could be successfully obtained by a chemical reduction of CuO micro powders using hydrazine in the presence of polypeptides as the stabilizing regent. Easy tuning of their particle sizes was successfully achieved via controlling the molecular weight of polypeptides. The obtained particles were covered by polypeptide capsules which were approximately 2 wt% of total mass. They are highly stable even under ambient conditions. (C) 2017 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

Synthesis of cationically charged photoluminescent coinage metal nanoclusters by sputtering over a liquid polymer matrix
Ryan D. Corpuz, Yohei Ishida, Tetsu Yonezawa
NEW JOURNAL OF CHEMISTRY, 41, 14, 6828, 6833, ROYAL SOC CHEMISTRY, Jul. 2017, [Peer-reviewed]
English, Scientific journal, This study demonstrates a novel synthesis of cationically charged photoluminescent noble metal nanoclusters of Au, Ag, and Cu; these are known plasmonic elements utilizing 11-mercaptoundecyl-N,N,N-trimethyl ammonium bromide as a stabilizing and capping ligand via sputtering deposition over a liquid polymer matrix.

TiO2 nanotube array with "multi-layer" walled structure and its vulnerability to water
Chaorui Xue, Shengliang Hu, Wei Liu, Qing Chang, Tetsu Yonezawa, Jinlong Yang
FUNCTIONAL MATERIALS LETTERS, 10, 3, WORLD SCIENTIFIC PUBL CO PTE LTD, Jun. 2017, [Peer-reviewed]
English, Scientific journal, "Multi-layer" walled TiO2 nanotube array has been prepared by anodization with post-treatment of ethanol. Two post-treatment methods, which were ethanol and water treatment respectively, exerted a marked and different effect on the structure of nanotube. With ethanol immersion, the " multi-layer" walled nanotube can be obtained, while water treatment cannot produce the "multi-layer" walled structure. The main reason could be the uptake of carbon and fluoride during anodization process. Compared with "single-layer" walled TiO2 nanotube, "multi-layer" walled TiO2 nanotube demonstrated higher photocatalytic activity.

Effect of H2O2 on Au nanoparticle preparation using microwave-induced plasma in liquid
Masamu Nishimoto, Tetsu Yonezawa, David Cempel, Mai Thanh Nguyen, Yohei Ishida, Hiroki Tsukamoto
MATERIALS CHEMISTRY AND PHYSICS, 193, 7, 12, ELSEVIER SCIENCE SA, Jun. 2017, [Peer-reviewed]
English, Scientific journal, The microwave-induced plasma in liquid process (MWPLP) has been attractive as a unique preparation method of metal nanoparticles. In this study, we investigated the effect of H2O2 on gold nanoparticles prepared using the MWPLP. Au nanoparticles were obtained without aggregation when the Au and H2O2 concentrations in the reaction solution were 0.3 mM and 0.03 mM, respectively. When the H2O2 concentration was lower or higher than the optimum range, aggregated particles were obtained. The results show that the addition of H2O2 had a great influence on the reduction rate and the dispersibility, and that Au nanoparticles prepared under optimum conditions were not aggregated and exhibited a high dispersibility. (C) 2017 Elsevier B.V. All rights reserved.

Charge Neutralization Strategy: A Novel Synthetic Approach to Fully Cationized Thiolate-Protected Au-25(SR+)(18) Clusters with Atomic Precision
Yohei Ishida, Yu-Ling Huang, Tetsu Yonezawa, Kunihiro Narita
CHEMNANOMAT, 3, 5, 298, 302, WILEY-V C H VERLAG GMBH, May 2017, [Peer-reviewed]
English, Scientific journal, Many thiolate-protected molecular Au clusters, of different cluster sizes and with varying neutral or anionic thiolate ligands, have been reported over the past two decades. Despite this abundance of information, to date there has been no report of atomically pure cationized molecular Au clusters that are protected with cationic thiolates. We herein present a novel, facile and high-yield synthetic approach towards producing a new series of thiolate- protected molecular Au clusters: a fully cationized Au-25(SR+)(18) cluster with atomic precision. The simple "charge neutralization strategy" presented enables treatment of the cationic thiols as neutral thiols, thus the well-established method for preparing Au-25 clusters with neutral thiolates can be adopted for cationic Au-25 clusters at a very high synthetic yield. We believe that this report will widen the spectrum of gold cluster chemistry and also help in the further development of cationized molecular clusters with various metals, core sizes, and ligand structures.

Water-dispersible fluorescent silver nanoparticles via sputtering deposition over liquid polymer using a very short thiol ligand
Yohei Ishida, Ryota Nakabayashi, Ryan D. Corpuz, Tetsu Yonezawa
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 518, 25, 29, ELSEVIER SCIENCE BV, Apr. 2017, [Peer-reviewed]
English, Scientific journal, We have developed a novel physical approach for size-controlled synthesis of metal nanoparticles via sputtering deposition over liquid matrix. Here we report a novel water-dispersible, negatively charged fluorescent silver nanoparticles through this method with a very short anionic thiolate ligand. Our previous result showed that multiple hydrogen bonds between carboxylic groups in surface ligands resulted in a very poor dispersilibity of formed nanoparticles, however neutralized sodium 3-mercaptopropionate used in this work could overcome this limitation. We successfully obtained NIR fluorescent, water-dispersible silver nanoparticles for the first time among physical-based approach. Results presented here therefore will widen the spectrum of novel and environmental-friendly strategy for functionalized metal nanoparticles or fluorescent clusters. (C) 2017 Elsevier B.V. All rights reserved.

Preparation of Au/Pd Bimetallic Nanoparticles by a Microwave-Induced Plasma in Liquid Process
Hiroaki Shirai, Mai Thanh Nguyen, David Cempel, Hiroki Tsukamoto, Tomoharu Tokunaga, Ying-Chih Liao, Tetsu Yonezawa
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 90, 3, 279, 285, CHEMICAL SOC JAPAN, Mar. 2017, [Peer-reviewed]
English, Scientific journal, Au/Pd alloy nanoparticles (NPs) were successfully synthesized using HAuCl4, H2PdCl4, and alpha-thioglycerol as precursors and a stabilizer, respectively, by microwave-induced plasma in liquid process (MWPLP). After only several minutes of microwave irradiation, metallic NPs were obtained in aqueous environment without any reducing agent. The reduction mechanism of metal ions was confirmed by UV-vis spectral changes. The results from HAADF-STEM and EDS indicated that synthesized NPs were bimetallic Au/Pd. Moreover, XRD patterns of synthesized NPs implied that the composition of bimetallic NPs could be controlled by changing the initial ratio of metal precursors.

Effect of decomposition and organic residues on resistivity of copper films fabricated via low-temperature sintering of complex particle mixed dispersions.
Yingqiong Yong, Mai Thanh Nguyen, Hiroki Tsukamoto, Masaki Matsubara, Ying-Chih Liao, Tetsu Yonezawa
SCIENTIFIC REPORTS, 7, 45150, NATURE PUBLISHING GROUP, Mar. 2017, [Peer-reviewed]
English, Scientific journal, Mixtures of a copper complex and copper fine particles as copper-based metal-organic decomposition (MOD) dispersions have been demonstrated to be effective for low-temperature sintering of conductive copper film. However, the copper particle size effect on decomposition process of the dispersion during heating and the effect of organic residues on the resistivity have not been studied. In this study, the decomposition process of dispersions containing mixtures of a copper complex and copper particles with various sizes was studied. The effect of organic residues on the resistivity was also studied using thermogravimetric analysis. In addition, the choice of copper salts in the copper complex was also discussed. In this work, a low-resistivity sintered copper film (7 x 10(-6) Omega center dot m) at a temperature as low as 100 degrees C was achieved without using any reductive gas.

Stabilization of the thermal decomposition process of self-reducible copper ion ink for direct printed conductive patterns
Kuan-Ming Huang, Hiroki Tsukamoto, Yingqiong Yong, Hsien-Lung Chiu, Mai Thanh Nguyen, Tetsu Yonezawa, Ying-Chih Liao
RSC ADVANCES, 7, 40, 25095, 25100, ROYAL SOC CHEMISTRY, 2017, [Peer-reviewed]
English, Scientific journal, In this study, a thermally triggered self-reducible copper ink is developed to print conductive patterns on flexible substrates. Inks containing only copper formate (CuF) and monoisopropanol amine (MIPA) generated large bubbles in the CuF decomposing process, and thus the surface morphologies of prepared thin films were largely disturbed. With the addition of octylamine (OA), the bubbling disturbance was relieved due to the lower surface tension and the film uniformity was greatly improved. A low resistivity of 2 x 10(-7) Omega m (8.5% of bulk copper) can be reached by heating the ink at 140 degrees C for 5 minutes under a nitrogen environment. XRD results showed the synthesized copper films were comprised of pure metallic copper crystalline. The copper films were composed of closely packed spherical grains of 50 to 500 nm in diameter. After the addition of 1 wt% polyvinylpyrrolidone (PVP) in the ink, the synthesized copper thin films showed great adhesion on glass substrates, and sustained the same conductivity after repeated tape tests. The ink can also be printed on flexible substrates, such as polyethylene terephthalate (PET) or polyimide (PI) thin films, to create highly-conductive tracks with a strong mechanical stability. Finally, various conductive patterns were printed on flexible substrates to show the great potential of this ink for various printed electronic applications.

Use of decomposable polymer-coated submicron Cu particles with effective additive for production of highly conductive Cu films at low sintering temperature
Y. Yong, M. T. Nguyen, T. Yonezawa, T. Asano, M. Matsubara, H. Tsukamoto, Y. Liao, T. Zhang, S. Isobe, Y. Nakagawa
Journal of Materials Chemistry C, 5, 5, 1033, 1041, Royal Society of Chemistry, 2017, [Peer-reviewed], [Corresponding author]
English, A method for producing Cu films with low resistivity, based on low temperature sintering, is demonstrated. The Cu inks for preparing conductive Cu films consisted of Cu particles that were coated with a decomposable polymer (poly(propylenecarbonate), PPC) as well as a self-reducible copper formate/1-amino-2- propanol (CuF-IPA) complex as an additive. The sintering temperature used in this study was as low as 100 degrees C. Following sintering at a temperature of 100 degrees C, the lowest reported resistivity (8.8 x 10(-7) Omega m) was achieved through the use of Cu-based metal-organic decomposition (MOD) inks. This was due to the dual promotional effects of the aminolysis of PPC with IPA and the pyrolysis of the CuF-IPA complex.

Au Nanoplasma as Efficient Hard X-ray Emission Source
Frances Camille P. Masim, Matteo Porta, Wei-Hung Hsu, Mai Thanh Nguyen, Tetsu Yonezawa, Armandas Balcytis, Saulius Juodkazis, Koji Hatanaka
ACS PHOTONICS, 3, 11, 2184, 2190, AMER CHEMICAL SOC, Nov. 2016, [Peer-reviewed]
English, Scientific journal, Hard X-ray generation up to 15 keV (similar to 1 angstrom) from Au nanoparticle suspensions was systematically investigated for different particle diameters ranging from 10 to 100 nm with a narrow size distribution of +/- 2%. Scaling law of X-ray generation is close to a 6-photon process before the onset of saturation for excitation by 40 fs laser pulses with central wavelength of 800 nm. This is consistent with bulk plasmon excitation at lambda(bulk)(p) similar or equal to 138 nm. The longitudinal E-field component due to nanoparticle focusing is responsible for the excitation of the longitudinal bulk plasmon. The proposed analysis also explains X-ray emission from water breakdown via an electron solvation mechanism at similar to 6.2 eV. The most efficient emission of X-rays was observed for 40 +/- 1 nm diameter nanoparticles which also had the strongest UV extinction. X-ray emission was the most efficient when induced by prechirped 370 +/- 20 fs laser pulses and exhibited the highest intensity at a negative chirp.

Matrix Sputtering into Liquid Mercaptan: From Blue-Emitting Copper Nanoclusters to Red-Emitting Copper Sulfide Nanoclusters
Matteo Porta, Mai Thanh Nguyen, Tomoharu Tokunaga, Yohei Ishida, Wei-Ren Liu, Tetsu Yonezawa
LANGMUIR, 32, 46, 12159, 12165, AMER CHEMICAL SOC, Nov. 2016, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, A modified magnetron sputtering technique using pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) as a stabilizing agent and liquid dispersion medium was developed to generate photoluminescent copper nanoclusters. The results reveal that, over time, the as-prepared blue emitting copper nanoclusters were converted to red-emitting copper sulfide nanoclusters. The formation of copper oxide as an intermediate during the conversion of copper to copper sulfide nanoclusters was demonstrated. Furthermore, based on the mechanism of formation of copper sulfide, the kinetics of the conversion process could be controlled via ultraviolet (UV) irradiation of the as-synthesized dispersion. These findings shed light on the formation and conversion of nanoclusters obtained via sputtering into liquid, demonstrating that the method is highly versatile for producing metal nanoclusters and compounds with tailorable composition and optical properties.

Preparation of Water-Dispersible Palladium Nanoparticles Stabilized by Carbon-Palladium Bonds and Application to Suzuki-Miyaura Coupling in Water
Tetsu Yonezawa, Koji Kawai, Hayato Kawakami, Takashi Narushima
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 89, 10, 1230, 1232, CHEMICAL SOC JAPAN, Oct. 2016, [Peer-reviewed]
English, Scientific journal, Water-dispersible palladium nanoparticle catalysts have been prepared using palladium-carbon covalent bonds. They worked as an excellent catalyst for Suzuki-Miyaura coupling reaction in water. Even though the particle size of Pd nano particles was much larger than the previously reported ones, they showed a very good catalytic activity for the coupling reaction.

Fully Cationized Gold Clusters: Synthesis of Au-25(SR+)(18)
Yohei Ishida, Kunihiro Narita, Tetsu Yonezawa, Robert L. Whetten
JOURNAL OF PHYSICAL CHEMISTRY LETTERS, 7, 19, 3718, 3722, AMER CHEMICAL SOC, Oct. 2016, [Peer-reviewed]
English, Scientific journal, Although many thiolate-protected Au clusters with different numbers of Au atoms and a variety of thiolate ligands have been synthesized, to date there has been no report of a fully cationized Au cluster protected with cationic thiolates. Herein, we report the synthesis of the first member of a new series of thiolate-protected Au cluster molecules: a fully cationized Au-25(SR+)(18) cluster.

Femtosecond laser-induced hard X-ray generation in air from a solution flow of Au nano-sphere suspension using an automatic positioning system
Wei-Hung Hsu, Frances Camille P. Masim, Matteo Porta, Mai Thanh Nguyen, Tetsu Yonezawa, Armandas Balocytis, Xuewen Wang, Lorenzo Rosa, Saulius Juodkazis, Koji Hatanakai
OPTICS EXPRESS, 24, 18, 19994, 20001, OPTICAL SOC AMER, Sep. 2016, [Peer-reviewed]
English, Scientific journal, Femtosecond laser-induced hard X-ray generation in air from a 100-mu m-thick solution film of distilled water or Au nano-sphere suspension was carried out by using a newly-developed automatic positioning system with 1-mu m precision. By positioning the solution film for the highest X-ray intensity, the optimum position shifted upstream as the laser power increased due to breakdown. Optimized positioning allowed us to control X-ray intensity with high fidelity. X-ray generation from Au nano-sphere suspension and distilled water showed different power scaling. Linear and nonlinear absorption mechanism are analyzed together with numerical modeling of light delivery. (C) 2016 Optical Society of America

Understanding the primary and secondary aggregation states of sputtered silver nanoparticles in thiolate matrix and their immobilization in resin
Yohei Ishida, Satoshi Udagawa, Tetsu Yonezawa
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 504, 437, 441, ELSEVIER SCIENCE BV, Sep. 2016, [Peer-reviewed]
English, Scientific journal, We report detailed aggregation mechanisms of sputtered silver nanoparticles in a viscous thiolate liquid matrix. Fluorescent silver nanoparticles were prepared by the sputtering deposition over pentaerythritol tetrakis(3-mercaptopropionate) (PEMP). The dependences of extinction, fluorescence and particle size on time were discussed in terms of two possible aggregation mechanisms. The main aggregation process was secondary aggregation, with primary aggregation (core coalescence) making a small contribution. The four thiol groups in the PEMP structure are the driving force determining the predominance of secondary aggregation. Finally, we successfully prepared a thiourethane resin by the polymerization of a thiolate matrix, and complete immobilization of nanoparticles in the resin resulted in no observable degradation of the photophysical properties. The demonstrations presented here will be beneficial in understanding the detailed aggregation mechanism and optical properties of nanoparticles. (C) 2016 Elsevier B.V. All rights reserved.

Ligand Effect on the Formation of Gold Nanoparticles via Sputtering Deposition over a Liquid Matrix
Ikumi Akita, Yohei Ishida, Tetsu Yonezawa
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 89, 9, 1054, 1056, CHEMICAL SOC JAPAN, Sep. 2016, [Peer-reviewed]
English, Scientific journal, Sputtering deposition of gold over a liquid matrix containing different ligands with thiolate, amine, or carboxy groups resulted in the formation of spherical gold nanoparticles (Au NPs) in the range of 2.1 to 6.7 nm, and the diameters gradually decreased as the affinity of the ligands for Au increases.

Au Nanoparticles Prepared Using a Coated Electrode in Plasma-in-Liquid Process: Effect of the Solution pH
David Cempel, Mai Thanh Nguyen, Yohei Ishida, Hiroki Tsukamoto, Hiroaki Shirai, Yongming Wang, Kevin C. -W. Wu, Tetsu Yonezwa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 16, 9, 9257, 9262, AMER SCIENTIFIC PUBLISHERS, Sep. 2016, [Peer-reviewed]
English, Scientific journal, Plasma-in-liquid process (PLP) has become a hot topic in green synthesis of metal nanoparticles (NPs). In order to overcome one of the current challenges associated with the impurity produced from metal electrodes, this study utilized a ceramic-coated electrode to prepare pure Au NPs stabilized by L-arginine. Using this electrode, the reduction of Au ions during the plasma irradiation, the formation of Au NPs, their size and size distribution as a function of the pH were investigated. Our results show that a bimodal NP size distribution was obtained at pH 3.5-12.0. The fraction of small sized Au NPs becomes significant at pH 6.0 and 12.0 while that of big sized Au NPs is dominant at pH 3.5. The results in the present study suggested that this change in the size distribution of Au NPs was governed by the reduction rate of gold ion at different pH under plasma generated in water.

MHz-ultrasound generation by chirped femtosecond laser pulses from gold nano-colloidal suspensions
Frances Camille P. Masim, Wei-Hung Hsu, Chih-Hung Tsai, Hao-Li Liu, Matteo Porta, Mai Thanh Nguyen, Tetsu Yonezawa, Armandas Balcytis, Xuewen Wang, Saulius Juodkazis, Koji Hatanaka
OPTICS EXPRESS, 24, 15, 17050, 17059, OPTICAL SOC AMER, Jul. 2016, [Peer-reviewed]
English, Scientific journal, Strong absorption of femtosecond laser pulses in Au nano-colloidal suspensions was used to generate coherent ultrasound signals at 1-20 MHz frequency range. The most efficient ultrasound generation was observed at negative chirp values and was proportional to the pulse duration. Maximization of a dimensionless factor A equivalent to alpha c(0)t(p) defined as the ratio of pulse duration t(p) and the time required for sound at speed c(0) to cross the optical energy deposition length (an inverse of the absorption coefficient alpha) given by 1/(alpha c(0)). Chirp controlled pulse duration allows effective enhancement of ultrasound generation at higher frequencies (shorter wavelengths) and is promising for a high spatial resolution acoustic imaging. (C) 2016 Optical Society of America

Thiolate-Protected Gold Nanoparticles Via Physical Approach: Unusual Structural and Photophysical Characteristics.
Ishida Y, Akita I, Sumi T, Matsubara M, Yonezawa T
Scientific reports, 6, 29928, 29928, Nature Publishing Group, Jul. 2016, [Peer-reviewed]
English, Here we report a novel physical approach for thiolate-protected fluorescent gold nanoparticles with a controlled size of the order of a few nanometers. This approach is based on a sputtering of gold into a liquid matrix containing thiolate ligand as a stabilizer at various concentrations, thus no reductant was used. The size of the gold nanoparticles was successfully controlled to range from 1.6 to 7.4 nm by adjusting the thiol concentrations. Surface plasmon absorption was observed in larger nanoparticles, but it was not observed in smaller ones. Such smaller nanoparticles fluoresced at around 670 nm with a small spectral shift according to their size, however, the diameter (1.6-2.7 nm) was very strange to show such red emission compared with photophysical characteristics of reported gold cluster or nanoparticles synthesized by chemical method. By detailed investigations using TEM, HAADF-STEM, XPS, and TGA, and size fractionation by size exclusion chromatography, we finally arrived at the plausible mechanism for the origin of unusual fluorescence property; the obtained gold nanoparticles are not single-crystal and are composed of aggregates of very small components such as multinuclear gold clusters or complexes.

Enhanced photoacoustics from gold nano-colloidal suspensions under femtosecond laser excitation
Frances Camille P. Masim, Hao-Li Liu, Matteo Porta, Tetsu Yonezawa, Armandas Balcytis, Saulius Juodkazis, Wei-Hung Hsu, Koji Hatanaka
OPTICS EXPRESS, 24, 13, 14781, 14792, OPTICAL SOC AMER, Jun. 2016, [Peer-reviewed]
English, Scientific journal, Enhanced photoacoustic (PA) intensity from gold nanosphere and nanorod colloidal suspensions in water under tightly-focused femtosecond pulsed laser irradiation was systematically investigated. PA signal amplitudes were measured by ultrasound transducers at frequencies of 5, 10, and 25 MHz. The experimental results revealed a linear-dependence of the relative photoacoustic amplitude on the laser power and the mechanism was attributed to non-radiative relaxation dynamics of surface plasmon oscillations. When gold nanorod with longitudinal absorption/extinction peak at 800 nm coincides with the wavelength of femtosecond laser pulses, the most efficient PA signal is generated. Laser excitation was kept within a thermal stability region of gold nanoparticles, i.e., colloidal suspension can be continuously reused for PA generation. (C) 2016 Optical Society of America

Growth of sputtered silver nanoparticles on a liquid mercaptan matrix with controlled viscosity and sputter rate
Yohei Ishida, Satoshi Udagawa, Tetsu Yonezawa
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS, 498, 106, 111, ELSEVIER SCIENCE BV, Jun. 2016, [Peer-reviewed]
English, Scientific journal, A sputtering deposition of metals over liquid matrixes has been investigated as a novel and environmentally friendly method to generate stable colloidal metal nanoparticles. We have expanded this method by using the liquid monomers with mercapto groups in order to prepare more stable, uniform and size controllable nanoparticles. Here we report the systematic investigation on the growth mechanism of silver nanoparticles on pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) matrix under the varied viscosities controlled by temperature. The diameter of obtained nanoparticles increased from 1.8 to 2.3 nm as the viscosity of the liquid matrix increased, and at higher viscosity region we obtained a thin deposited film on the liquid surface but no nanoparticles formed. The effect of viscosity on the particle diameter was much smaller than previous works using ionic liquids or polyethylene glycol, and then the phenomenon was understood by the structure of these matrixes where PEMP has four mercapto groups however ionic liquids or polyethylene glycol does not have any functional groups that introduce strong interaction with metals. These demonstrations suggest that the sputtering over mercaptan liquid matrix is a more favorable method for the stable preparation of uniform very small nanoparticles. (C) 2016 Elsevier B.V. All rights reserved.

Double target sputtering into liquid: A new approach for preparation of Ag-Au alloy nanoparticles
Mai Thanh Nguyen, Tetsu Yonezawa, Yuan Wang, Tomoharu Tokunaga
MATERIALS LETTERS, 171, 75, 78, ELSEVIER, May 2016, [Peer-reviewed]
English, Scientific journal, A new approach using double target sputtering into liquid is proposed to synthesize Ag-Au alloy nanoparticles (NPs). The results reveal the formation of Ag-Au solid solution alloy as individual NPs. Variation of the applied target current allows fine tuning of the NP composition, and, therefore, variation of optical properties of the alloy NPs. The method offers highly independent control of sputter parameters for each metal target, thereby allowing manipulation of the NP composition, size and optical properties. (C) 2016 Elsevier B.V. All rights reserved.

Assessment of Size and Morphological Effects of Ceramics Nanoparticles on Their Biocompatibility
Satoshi Tsuchiya, Shigeaki Abe, Yuko Era, Yukari Nakagawa, Shuichi Yamagata, Mariko Nakamura, Teruo Kusaka, Yasuhiro Yoshida, Tetsu Yonezawa, Junichiro Iida
Nanoscience and Nanotechnology Letters, 8, 4, 329, 334, AMER SCIENTIFIC PUBLISHERS, Apr. 2016, [Peer-reviewed]
English, Scientific journal, In this study, we investigated the effects of the topological properties of ceramics nanoparticles (NPs) (i.e., TiO2, Fe2O3, and CuO) on their biocompatibility. In the case of particle size, cell viability was not affected by the size of TiO2 particles even when the size was varied from 30 to 250 nm. Although the cytocompatibilities of TiO2 NPs with different morphologies were compared, no substantial difference was observed. In the case of Fe2O3, the viability decreased slightly with increasing particle concentration without a particle-size effect. In contrast, the viability upon exposure to CuO NPs decreased drastically with increasing NP concentration. Furthermore, the viability improved when CuO NPs size was increased from the nano-regime to micro-regime. Interestingly, greater viability was exhibited by gelatin-coated Cu NPs than by CuO NPs. These results suggest that the cytocompatibility of ceramics NPs is more strongly affected by chemical species than by particle size and, morphology.

Controlling an electrostatic repulsion by oppositely charged surfactants towards positively charged fluorescent gold nanoclusters
Ryan D. Corpuz, Yohei Ishida, Tetsu Yonezawa
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 18, 13, 8773, 8776, ROYAL SOC CHEMISTRY, Apr. 2016, [Peer-reviewed]
English, Scientific journal, A novel positively charged fluorescent gold nanocluster was successfully synthesized using the shortest cationic thiol, thiocholine. Effective control of electrostatic repulsion by the introduction of an anionic surfactant afforded a nanocluster that showed blue fluorescence emission.

Surface-Assisted Laser Desorption Ionization Mass Spectrometry (SALDI-MS) of Low-Molecular-Weight Medicines and Toxic Materials Using Commercial TiO2 Nanoparticles
Tetsu Yonezawa, Takashi Asano, Masaki Matsubara
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 89, 3, 346, 353, CHEMICAL SOC JAPAN, Mar. 2016, [Peer-reviewed], [Lead author, Corresponding author]
English, Scientific journal, The ability of surface-assisted laser desorption/ionization mass spectroscopy (SALDI-MS) of low-molecular-weight compounds using six types of commercially available TiO2 nanoparticles (NPs) was examined. In all cases, TiO2 NPs gave strong Na+-adduct sample ion peaks. Some chemicals, which rarely show proton-adduct sample ion peaks by MALDI-MS, such as aspirin and barbital, could be easily detected by using TiO2 NPs. The key factors determining the SALDI ability of TiO2 NPs are their purity, ratio of rutile, and particle size.

Estimation of Biocompatibility of Nano-Sized Ceramic Particles with Osteoblasts, Osteosarcomas and Hepatocytes by Static and Time-Lapse Observation
Shigeaki Abe, Eri Seitoku, Nobuki Lwadera, Yusuke Hamba, Shuichi Yamagata, Tsukasa Akasaka, Teruo Kusaka, Satoshi Lnoue, Yasutaka Yawaka, Junichiro Lida, Hidehiko Sano, Tetsu Yonezawa, Yasuhiro Yoshida
JOURNAL OF BIOMEDICAL NANOTECHNOLOGY, 12, 3, 472, 480, AMER SCIENTIFIC PUBLISHERS, Mar. 2016, [Peer-reviewed]
English, Scientific journal, We assessed the biocompatibility of nano-sized ceramic particles with several cells types. Though these particles have less than 100 nm in diameter, they act as submicron-sized particles in saline by aggregation that was estimated using laser diffraction particle size analysis (LDS). they act as submicro-sized particles in saline by aggregation based on laser diffraction particle size analysis (LDS). Several types of cells (osteoblasts, osteosarcoma and hepatocyte cells) were exposed to these particles and their cytocompatibility was estimated. Not only the cytotoxic assay but also their static and dynamic morphology under nanoparticles exposure were investigated. The intercellular uptake of particles was determined using a confocal fluorescence microscope. The particles used in this study did not inhibit cellular activity or growth even when their concentrations were high. Only copper oxide particles caused acute cytotoxicity depending on the particle size. The cytotoxicity assay, dynamic behavior of the nanoparticle-exposed cells and their examination under a confocal fluorescence microscope suggests that the irritative reaction was induced by contact between the cells and particles, whereas eluted copper ions are not dominant factor. These results indicate that nano-sized particles used in this study have excellent biocompatibility except copper oxide ones.

Hard-templating synthesis of macroporous platinum microballs (MPtM)
Hiroaki Shirai, Yu-Yuan Huang, Tetsu Yonezawa, Tomoharu Tokunaga, Wei-Chen Chang, Saad M. Alshehri, Bo Jiang, Yusuke Yamauchi, Kevin C. -W. Wu
MATERIALS LETTERS, 164, 488, 492, ELSEVIER, Feb. 2016, [Peer-reviewed], [Corresponding author]
English, Scientific journal, Platinum (Pt) is widely applied for electrochemical catalysis, thus creating porosity in Pt-based materials would enhance their catalytic efficacy. This study demonstrates a new route to synthesize a Pt material with macropores and spherical morphology by the combination of evaporation induced self-assembly of a hard template (i.e., silica nanoparticles) and infiltration/reduction of Pt species in micro-emulsion systems. The synthesized macroporous Pt microballs (denoted as MPtM) are characterized with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and it is found that MPtM exhibits uniform macropores (diameter of 300 nm) and Pt crystalline framework, which would be potential for enhanced catalytic reactions. (C) 2015 Elsevier B.V. All rights reserved.

DeNovo Synthesis of Gold-Nanoparticle-Embedded, Nitrogen-Doped Nanoporous Carbon Nanoparticles (Au@NC) with Enhanced Reduction Ability
Yu-Te Liao, Jeffrey E. Chen, Yohei Isida, Tetsu Yonezawa, Wei-Chen Chang, Saad M. Alshehri, Yusuke Yamauchi, Kevin C. -W. Wu
CHEMCATCHEM, 8, 3, 502, 509, WILEY-V C H VERLAG GMBH, Feb. 2016, [Peer-reviewed]
English, Scientific journal, A denovo synthesis of gold-nanoparticle-embedded, nitrogen-doped nanoporous carbon nanoparticles (Au@NC) was investigated in this work. Chloroauroic acid was encapsulated inside zeolitic imidazolate framework-8 (ZIF-8) nanoparticles during the synthesis and later reduced into gold nanoparticles. The as-synthesized gold-nanoparticle-embedded ZIF-8 (Au@ZIF-8) was then carbonized into Au@NC to enhance the stability of the nanoporous support. The results show that Au@NC exhibits a porous structure containing 3wt% of gold. 2-Methylimidazole provided an abundant amount of nitrogen (19wt%) on the carbon matrix, which resulted in a hydrophilic and positively charged surface that is useful for the reduction of 4-nitrophenol. The results of the catalytic reaction indicate that synthesized Au@NC could act as an effective catalyst with a turnover frequency (TOF) of 1185g(-1)s(-1), which is higher than that of conventional naked Au nanoparticles (TOF: 339g(-1)s(-1)) and that of Au nanoparticles on activated carbon (TOF: 89g(-1)s(-1)). We propose that the enhanced performance of Au@NC resulted from homogeneous distribution of Au nanoparticles along with the hydrophilic and positively charged nitrogen-doped carbon surface.

Highly stable and blue-emitting copper nanocluster dispersion prepared by magnetron sputtering over liquid polymer matrix
Matteo Porta, Mai Thanh Nguyen, Yohei Ishida, Tetsu Yonezawa
RSC ADVANCES, 6, 107, 105030, 105034, ROYAL SOC CHEMISTRY, 2016, [Peer-reviewed]
English, Scientific journal, For the first time, magnetron sputtering of copper onto liquid was investigated for the preparation of stable blue-fluorescent copper nanoclusters. The fluorescent intensity increased linearly with an increase of mercaptan. Our finding casts light on the formation mechanism of metal photoluminescent nanoclusters via sputtering onto liquid.

Photochemical Reaction in Two Dimensional Assemblies of Functional Dyes on Inorganic Nanosheets
Yohei Ishida, Tetsu Yonezawa
KOBUNSHI RONBUNSHU, 73, 1, 12, 18, SOC POLYMER SCIENCE JAPAN, 2016, [Peer-reviewed]
Japanese, Scientific journal, In recent years, it has been revealed that light-harvesting systems (LHSs) are composed of beautifully aligned chlorophyll molecules; the regulated alignment of chlorophylls is responsible for the efficient and selective light-harvesting energy transfer processes in purple bacteria. This finding led to the construction of regularly arranged assemblies of functional dyes as a step toward fabricating artificial LHSs. While most researchers use molecular interactions such as covalent, coordination, and hydrogen bonds to produce dye assemblies, our approach involves guest-host interactions using an inorganic nanosheet as a host material. This short review presents the construction of a 2D dye assembly and its effective utilization in artificial light-harvesting applications. Owing to the highly stable and uniform 2D alignment of functional dyes on inorganic nanosheets, nearly 100% singlet-singlet energy transfer and efficient light-harvesting were achieved.

Titanium oxide nanoparticle dispersions in a liquid monomer and solid polymer resins prepared by sputtering
Matteo Porta, Mai Thanh Nguyen, Tetsu Yonezawa, Tomoharu Tokunaga, Yohei Ishida, Hiroki Tsukamoto, Yuichi Shishino, Yoshikiyo Hatakeyama
NEW JOURNAL OF CHEMISTRY, 40, 11, 9337, 9343, ROYAL SOC CHEMISTRY, 2016
English, Scientific journal, A transparent resin containing titanium oxide nanoparticles ( NPs) was prepared using a molten matrix sputtering ( MMS) technique. The low vapour pressure of the liquid, pentaerythritol ethoxylate ( PEEL) substrate permits the use of this vacuum technique directly with liquid PEEL under stirring conditions in order to obtain uniform dispersions of NPs. We found that it is possible to synthesize titanium oxide, TiOx, NPs with diameters of less than 5 nm with a controlled composition by simply adjusting the sputtering atmosphere. Furthermore, as the electronic structure of the TiOx NPs changes depending on the particle size, crystallinity and degree of oxidation, we were able to modify the optical properties of PEEL and the resin by embedding TiOx NPs in the matrix. The enhancement of the refractive index of a resin containing TiO2 NPs was also demonstrated. This synthetic method is promising for the advanced preparation of high purity TiOx NPs without using a reducing agent and leaving by-products for various applications in optical devices, energy conversion, and light harvesting in the UV visible region.

Reproducible shape control of single-crystal SnO micro particles
Mai Thanh Nguyen, Hiroaki Shirai, Chondanai Tiankanon, Hiroki Tsukamoto, Yohei Ishida, Tetsu Yonezawa
RSC ADVANCES, 6, 32, 26725, 26733, ROYAL SOC CHEMISTRY, 2016, [Peer-reviewed]
English, Scientific journal, A straightforward method for synthesizing single-crystalline SnO micro particles in an organic medium using tin acetylacetonate as the precursor and oleylamine as the capping ligand is proposed. For the first time, well-defined four-petal starfish-like SnO sheets were obtained in the organic medium. In addition, the shape of the particles could be reproducibly tuned such that their structures varied from cubes to squares and then to starfish-like sheets by simply changing the concentration of oleylamine. The underlying mechanism of this process was found to be closely related to the interaction of the stabilizing agent with the SnO crystal planes. Changing the concentration of the stabilizing agent could modify this interaction, leading to the preferential growth of certain crystal planes of SnO particles which determined the particle shape. This synthesis approach is advantageous in terms of allowing control over the particle shape as well as for its simplicity and short reaction time. Our results yield crucial insights regarding the shape evolution of SnO particles.

Low temperature sintering process of copper fine particles under nitrogen gas flow with Cu2+-alkanolamine metallacycle compounds for electrically conductive layer formation
Tetsu Yonezawa, Hiroki Tsukamoto, Yingqiong Yong, Mai Thanh Nguyen, Masaki Matsubara
RSC ADVANCES, 6, 15, 12048, 12052, ROYAL SOC CHEMISTRY, 2016, [Peer-reviewed]
English, Scientific journal, A novel low cost sintering process of copper fine particles to a copper conductive layer was demonstrated at as low as 100 degrees C without reductive gas flow. Sintering of a mixture of copper particles and copper-based metal-organic-decomposition (MOD) ink gave a copper film with high packing density and low resistivity (9 x 10(-6) Omega m). This novel process may open a new strategy in the field of printed electronics.

A new approach for additive-free room temperature sintering of conductive patterns using polymer-stabilized Sn nanoparticles
Hiroaki Shirai, Mai Thanh Nguyen, Yohei Ishida, Tetsu Yonezawa
JOURNAL OF MATERIALS CHEMISTRY C, 4, 11, 2228, 2234, ROYAL SOC CHEMISTRY, 2016, [Peer-reviewed]
English, Scientific journal, Tin nanoparticles (Sn NPs) are of considerable interest for conductive printing because of their low melting temperature and low cost. In the present study, polyvinylpyrrolidone (PVP) stabilized metallic Sn NPs were synthesized by a polyol process and the size of Sn NPs was controlled from 15 to 89 nm by adjusting the amount of PVP. For the first time, we demonstrated that conductive patterns fabricated from the inks of metallic Sn NPs were achieved readily at room temperature under N-2 without reducing gases or additives. The lowest obtained resistivity was 1.1 x 10 (3) Omega cm, which was 100 times higher than that of bulk Sn. The size of Sn NPs, the amount of the stabilizing agent, and the low melting temperature of Sn NPs were found to be the main factors controlling the conductivity of the obtained Sn pattern in room temperature sintering. This study offers a new approach for the room temperature fabrication of conductive electronics using the printing technique.

Mesoporous Europium-Doped Titania Nanoparticles (Eu-MTNs) for Luminescence-Based Intracellular Bio-Imaging
Kuan-Chou Chen, Saikat Dutta, Yusuke Yamauchi, Saad M. Alshehri, Mai Thanh Nguyen, Tetsu Yonezawa, Kun-Hung Shen, Kevin C. -W. Wu
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 15, 12, 9802, 9806, AMER SCIENTIFIC PUBLISHERS, Dec. 2015, [Peer-reviewed]
English, Scientific journal, Monodisperse and mesoporous europium (Eu)-doped titania nanoparticles (denoted as Eu-MTNs) were prepared by a co-synthesis method with the presence of a cationic surfactant (i.e., CTAB). A maximum loading amount of 8 mol% of Eu could be successfully incorporated into the framework of MTNs. The synthesized Eu-MTNs samples were characterized with X-ray diffraction (XRD) and scanning electron microscopy (SEM), with their luminescent property examined by photoluminescence (PL). Under ultraviolet irradiation, the Eu-MTNs samples exhibit several characteristic luminescence corresponding to D-5(0)-F-7(j) for Eu+3 ions, which can be attributed to the energy transfer from titania nanocrystallite to Eu3+ ions dispersed in amorphous mesoporous titania region. The potential intracellular bio-imaging application of the synthesized Eu-MTN nanoparticles was demonstrated with a breast cancer cell line (i.e., BT-20). High biocompatibility and strong luminescence of the Eu-MTNs show great potential in biomedical applications.

Effect of Glass Transition Temperature of Stabilizing Polymer of Air-Stable Gelatin-Stabilized Copper Fine Particles during Redox Two-Step Low-Temperature Sintering Process
Masaki Matsubara, Tetsu Yonezawa, Hiroki Tsukamoto
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 88, 12, 1755, 1759, CHEMICAL SOC JAPAN, Dec. 2015, [Peer-reviewed]
English, Scientific journal, It has been found in this study that the glass transition temperatures can be considered as the lowest temperature for sintering metal fine particles to obtain electro-conductive metallic layers from the differential scanning calorimetry measurement of the fine particles. Gelatin-stabilized copper fine particles could be sintered to form an electrically conductive copper layer with a resistivity of 1.9 x 10(-5) Omega cm at as low as 150 degrees C using oxidation-reduction two-step sintering.

Scanning Electron Microscope Observation of Carbon Nanotubes with Room Temperature Ionic Liquids: Effect of Their Hydrophilicities
Atsushi Hyono, Shigeaki Abe, Koji Kawai, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 15, 11, 9272, 9274, AMER SCIENTIFIC PUBLISHERS, Nov. 2015, [Peer-reviewed]
English, Scientific journal, In this study, we succeeded in acquiring scanning electron microscope (SEM) images of carbon nanotube (CNT) derivatives with different surface properties based on an electro-conductive pretreatment using a room temperature ionic liquid (IL). The quality of the obtained SEM images depended on their surface properties and the hydrophilicities of IL used. When the hydrophilicities of both the sample surface and the IL were close, the obtained SEM images had a high resolution. In contrast, SEM imges of samples pretreated with an IL, which had different hydrophilicities from the sample, was observed with low resolution and low quality. This result suggests that the relationship between both hydrophilicities is the dominant factor for this visualization method.

Black TiO2 Nanoparticles by a Microwave-induced Plasma over Titanium Complex Aqueous Solution
Yohei Ishida, Wataru Doshin, Hiroki Tsukamoto, Tetsu Yonezawa
CHEMISTRY LETTERS, 44, 10, 1327, 1329, CHEMICAL SOC JAPAN, Oct. 2015, [Peer-reviewed]
English, Scientific journal, We herein report a novel synthesis of black TiO2 nanoparticles by using a microwave-induced plasma over Ti complex aqueous solution. The resultant TiO2 nanoparticles showed very strong reflectance over the whole visible light region. Detailed HAADF-STEM analysis of the obtained particles revealed that this plasma method enables doping of W ions inside the TiO2 crystal structure.

Enhanced Terahertz Emission from CuxO/Metal Thin Film Deposited on Columnar-Structured Porous Silicon
Xu Lu, Yohei Ishida, Tomobumi Mishina, Mai Thanh Nguyen, Tetsu Yonezawa
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 88, 10, 1385, 1387, CHEMICAL SOC JAPAN, Oct. 2015, [Peer-reviewed]
English, Scientific journal, We propose a novel method to enhance the THz emission from CuOx/metal nano thin film by using columnar-structured microsized porous silicon (MS-PSi) as the substrate. THz emission was improved several times higher than that from the planar substrate due to the decreased optical reflectance and enlarged surface area.

A Novel Physical Approach for Cationic-Thiolate Protected Fluorescent Gold Nanoparticles
Yohei Ishida, Chaiyathat Lee, Tetsu Yonezawa
SCIENTIFIC REPORTS, 5, 15382, NATURE PUBLISHING GROUP, Oct. 2015, [Peer-reviewed]
English, Scientific journal, Knowledge on the synthesis of cationically charged fluorescent gold nanoparticles (Au NPs) is limited because the electrostatic repulsion between cationic ligands on the surface of NP hinders the formation of small Au NPs (usually less than ca. 2 nm) during nucleation in solvents. We herein propose a novel methodology for a synthesis of water-dispersible, cationic-thiolate protected fluorescent Au NPs by the sputtering of Au into liquid matrix containing thiolate ligands. By controlling mercaptan concentration the size and photophysical characteristics of Au NPs were directly controlled, resulting in near IR fluorescence with a 0.9% of absolute quantum yield. Cationically charged fluorescent metal NPs are promising, especially in biological fields, and this work provides a novel methodology towards the synthesis of a new series of functional metal NPs.

Reduction of carbon dioxide using a visible-light-induced electron transfer system with colloidal metal nanoparticle catalysts: evidence for production of methane　　　　　　　　　　　　　　　
責任著者, 平川 和貴, 共著者]Kazutaka Hirakawa, Yumi Yamaji, Tetsu Yonezawa, Naoki Toshima
Current Topics in Catalysis, 11, (num), 55, 63, May 2015, [Peer-reviewed]

Formation and Optical Properties of Fluorescent Gold Nanoparticles Obtained by Matrix Sputtering Method with Volatile Mercaptan Molecules in the Vacuum Chamber and Consideration of Their Structures
Taiki Sumi, Shingo Motono, Yohei Ishida, Naoto Shirahata, Tetsu Yonezawa
LANGMUIR, 31, 14, 4323, 4329, AMER CHEMICAL SOC, Apr. 2015, [Peer-reviewed]
English, Scientific journal, This paper proposes a novel methodology to synthesize highly fluorescent gold nanoparticles (NPs) with a maximum quantum yield of 16%, in the near-infrared (IR) region. This work discusses the results of using our (previously developed) matrix sputtering method to introduce mercaptan molecules, alpha-thioglycerol, inside the vacuum sputtering chamber, during the synthesis of metal NPs. The evaporation of alpha-thioglycerol inside the chamber enables to coordinate to the nucleation stage very small gold nanoclusters in the gas phase, thus retaining their photophysical characteristics. As observed through transmission electron microscopy, the size of the Au NPs obtained with the addition of alpha-thioglycerol varied from approximately 23 nm to approximately 5 nm. Plasmon absorption varied with the size of the resultant nanoparticles. Thus, plasmon absorption was observed at 2.4 eV in the larger NPs. However, it was not observed, and instead a new peak was found at approximately 3.4 eV, in the smaller NPs that resulted from the introduction of alpha-thioglycerol. The Au NPs stabilized by the alpha-thioglycerol fluoresced at approximately 1.8 eV, and the maximum wavelength shifted toward the red, in accordance with the size of the NPs. A maximum fluorescent quantum yield of 16% was realized under the optimum conditions, and this value is extremely high compared to values previously reported on gold NPs and clusters (generally similar to 1%). To our knowledge, however, Au NPs of size >2 nm usually do not show strong fluorescence. By comparison with results reported in previous literature, it was concluded that these highly fluorescent Au NPs consist of goldmercaptan complexes. The novel method presented in this paper therefore opens a new door for the effective control of size, photophysical characteristics, and structure of metal NPs. It is hoped that this research contributes significantly to the science in this field.

Cladding Layer on Well-Defined Double-Wall TiO2 Nanotubes
Chaorui Xue, Tetsu Yonezawa, Mai Thanh Nguyen, Xu Lu
LANGMUIR, 31, 4, 1575, 1580, AMER CHEMICAL SOC, Feb. 2015, [Peer-reviewed]
English, Scientific journal, Highly ordered double-wall TiO2 nanotube arrays were obtained by a two-step anodization method in a fluoride-containing glycerol based electrolyte. The low water and fluoride content and high viscosity of the electrolyte support a partly undissolved fluoride-rich layer, and its hydrolyzed products remain on the tube walls. The double-wall structure and a cladding layer originating from the fluoride-rich layer were clearly observed after annealing. The morphology and crystal structure of the cladding layer were investigated. The study of the cladding layer gives a fundamental insight into the wall structure design of the anodic TiO2 nanotubes in the glycerol-based electrolyte.

Synthesis of binary solid solution Cu-Pd nanoparticles by DMF reduction for enhanced photoluminescence properties
Masashi Chiba, Mai Nguyen Thanh, Yasuchika Hasegawa, Yasushi Obora, Hideya Kawasaki, Tetsu Yonezawa
JOURNAL OF MATERIALS CHEMISTRY C, 3, 3, 514, 520, ROYAL SOC CHEMISTRY, 2015
English, Scientific journal, We report the use of a DMF reduction method for straightforward synthesis of binary solid solution Cu-Pd nanoparticles (NPs) over the entire range of composition. The resulting NPs were uniform in size (less than 2.5 nm), tunable in composition, and exhibited photoluminescence properties that were nonlinear in composition. These binary solid solution NPs showed enhanced photoluminescence intensity and quantum yield compared to those of the single-metal NPs and their mixtures. The highest quantum yield of 3.10% for Cu-Pd alloy NPs synthesized using equimolar feeding ratio versus 2.75% for Cu and 0.71% for Pd NPs was obtained. These enhancements make the alloy NPs promising materials for optical applications.

Selective and reactive hydration of nitriles to amides in water using silver nanoparticles stabilized by organic ligands
Koji Kawai, Hayato Kawakami, Takashi Narushima, Tetsu Yonezawa
JOURNAL OF NANOPARTICLE RESEARCH, 17, 2, 1, 9, SPRINGER, Jan. 2015, [Peer-reviewed]
English, Scientific journal, Water-dispersible silver nanoparticles stabilized by silver-carbon covalent bonds were prepared. They exhibited high catalytic activities for the selective hydration of nitriles to amides in water. The activation of a nitrile group by the functional groups of the substrates and the hydrophobic layer on the nanoparticles influenced the catalyzed reaction were confirmed. Alkyl nitriles could also be selectively hydrated.

Electroconductive pretreatment of several types of non-conductive wet biological samples for SEM using a room temperature ionic liquid: simple and rapid conductive preparation
Mami Mutoh, Shigeaki Abe, Atsushi Hyono, Hiroshi Matsuura, Ko Nakanishi, Koji Kawai, Mariko Nakamura, Satoshi Inoue, Yasuhiro Yoshida, Junichiro Iida, Tetsu Yonezawa
Nano Biomedicine, 7, 2, 80, 2015, [Peer-reviewed]

Proton-assisted low-temperature sintering of Cu fine particles stabilized by a proton-initiating degradable polymer
Masaki Matsubara, Tetsu Yonezawa, Takato Minoshima, Hiroki Tsukamoto, Yingqiong Yong, Yohei Ishida, Mai Thanh Nguyen, Hiroki Tanaka, Kazuki Okamoto, Takuya Osaka
RSC ADVANCES, 5, 124, 102904, 102910, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, Metallic copper fine particles were prepared by chemical reduction of CuO in the presence of thermally degradable poly-1,4-butanediol-divinylether (BDVE). Because a BDVE thin layer formed on the particle surfaces, the obtained copper particles were stable and did not undergo obvious oxidation under ambient conditions. The ether groups of BDVE were hydrolyzed with protons, and this generated small fragment molecules. The BDVE-stabilized copper fine particles and their pastes can be therefore sintered at 150 degrees C in the presence of protons. Electro-conductive films with a relatively low resistivity of 8.5 x 10(-5) Omega cm were obtained on a alumina substrate in the presence of formic acid, and hot pressed conductive pellets with a resistivity of 2.9 x 10(-5) Omega cm were also obtained without any pre-oxidative annealing in the presence of proton generator molecules at very low temperatures. The hot pressed pellets show a high anti-oxidative ability and their corrosion tests revealed their good anti-corrosion property.

X-ray diffraction and high-resolution TEM observations of biopolymer nanoskin-covered metallic copper fine particles: preparative conditions and surface oxidation states
Tetsu Yonezawa, Yoshiki Uchida, Hiroki Tsukamoto
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 17, 48, 32511, 32516, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, Metallic copper fine particles used for electro conductive pastes were prepared by the chemical reduction of cupric oxide microparticles in the presence of gelatin. After reduction, the fine particles were collected by decantation with pH control and washing, followed by drying at a moderate temperature. The surface oxidation state of the obtained copper fine particles could be considerably varied by altering the pH of the particle dispersion, as shown by X-ray diffraction and high-resolution transmission electron microscopy. Our results strongly indicate that decantation under a nitrogen atmosphere can prevent the oxidation of copper fine particles but a slight oxidation was found.

One-pot preparation of cationic charged Pt nanoparticles by the autocatalytic hydrolysis of acetylthiocholine
Yohei Ishida, Thatchanont Jirasupangkul, Tetsu Yonezawa
NEW JOURNAL OF CHEMISTRY, 39, 6, 4214, 4217, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, We propose a novel synthetic approach for cationic charged platinum nanoparticles via the autocatalytic hydrolysis of acetylthiocholine. This method can be extended to the platinum group of metals.

Sputtering synthesis and optical investigation of octadecanethiol-protected fluorescent Au nanoparticles
Yohei Ishida, Taiki Sumi, Tetsu Yonezawa
NEW JOURNAL OF CHEMISTRY, 39, 8, 5895, 5897, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, Herein we report for the first time the synthesis of octadecanethiol-capped gold nanoparticles (Au NPs) by sputtering of Au over a liquid matrix (silicone oil). Au NPs prepared in silicone oil showed plasmon absorption; however, those prepared in the presence of 1-octadecanethiol did not show plasmon absorption but fluoresced in the near IR region.

Synthesis and fluorescence properties of a nanoisland-structured SiOx/CuxO composite
Xu Lu, Yohei Ishida, Mai Thanh Nguyen, Tetsu Yonezawa
JOURNAL OF MATERIALS CHEMISTRY C, 3, 32, 8358, 8363, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, A nanoisland-structured SiOx (x <= 2)/CuxO (x <= 2) composite was prepared from a Cu-deposited Si wafer by electrochemical anodization in a hydrofluoric acid (HF) and ferric nitrate (Fe(NO3)3) electrolyte. The surface of the nanoisland comprised Cu, Cu oxides, Si nanoparticles and Si oxides. The distribution of elemental Cu on the surface was uniform. Cracks and native Cu-oxides in the deposited Cu layer are the two main factors for the formation of the nanoisland-structured surface. Different from the single red photoluminescence (PL) band emitted from the electrochemical anodized bare Si wafer, a dualvisible PL band with comparable intensities at red and blue ranges was observed. The red PL quenching did not occur in this Cu-ion-doped nanostructured Si due to the different distribution areas of Cu+ and the red PL centre. The red PL originates due to oxygen defects in the band gap of Si nanoparticles/Si oxides; the blue PL is the consequence of the band-to-band transitions between 3d(10) and 3d(9)4s(1) of Cu+ ions and the intra d -> d band transition of Cu2+ ions in the interstitial vacancies of Si oxides. Compared with the electrochemical anodized bare Si sample with a single PL band, the nanoisland-structured SiOx/CuxO composite emitting a dual-PL-band is more promising for fabricating white light emitters.

Low-temperature nanoredox two-step sintering of gelatin nanoskin-stabilized submicrometer-sized copper fine particles for preparing highly conductive layers
Tetsu Yonezawa, Hiroki Tsukamoto, Masaki Matsubara
RSC ADVANCES, 5, 75, 61290, 61297, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, A conductive paste was prepared with submicrometer-sized copper fine particles that were coated by a gelatin nanoskin. The average particle size was ca. 130 nm. After drying, an oxidation-reduction two-step sintering process was proposed for these submicrometer-sized copper fine particles to obtain low-resistivity layers at a very low temperature. The optimized conditions gave a low resistivity of 8.2 x 10(-6) Omega cm, even when the particles were covered by a common polymer. Our results suggest that the formation of the small copper oxide prominences on the surface of the copper fine particles could be reduced at low temperatures, forming connected submicrometer-sized metallic copper particles.

Plasma induced tungsten doping of TiO2 particles for enhancement of photocatalysis under visible light
Yohei Ishida, Yasutomo Motokane, Tomoharu Tokunaga, Tetsu Yonezawa
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 17, 38, 24556, 24559, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, Here we report a novel method for modifying commercially available TiO2 nanoparticles by a microwave-induced plasma technique. After the plasma treatment TiO2 nanoparticles showed enhanced visible absorption due to the doped W atoms, and the photocatalytic methylene blue degradation above 440 nm was successfully improved.

Synthesis of magnetic mesoporous titania colloidal crystals through evaporation induced self-assembly in emulsion as effective and recyclable photocatalysts
Jeffrey E. Chen, Hong-Yuan Lian, Saikat Dutta, Saad M. Alshehri, Yusuke Yamauchi, Mai Thanh Nguyen, Tetsu Yonezawa, Kevin C. -W. Wu
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 17, 41, 27653, 27657, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, This study illustrates the directed self-assembly of mesoporous TiO2 with magnetic properties due to its colloidal crystal structure with Fe3O4. The Fe3O4 nanoparticles were synthesized using co-precipitation techniques to a size of 28.2 nm and a magnetic saturation of 66.9 emu g(-1). Meanwhile, mesoporous titania nanoparticles (MTNs) with a particle diameter of 373 nm, a specific surface area of 236.3 m(2) g(-1), and a pore size of 2.8 nm were prepared by controlling the rate of hydrolysis. Magnetic colloidal crystals (a diameter of 10.2 mm) were formed by the aggregation of Fe3O4 and MTNs caused by the interface phenomena during solvent evaporation in emulsion. Even the anatase octahedrite produced from the colloidal crystal after a hydrothermal reaction retained a magnetic saturation of 2.8 emu g(-1). This study also investigates the photodegradation activity of our synthesized material as a photocatalyst, while utilizing its capability for magnetic separation to prove its usefulness in catalyst recycling.

The mechanism of alkylamine-stabilized copper fine particles towards improving the electrical conductivity of copper films at low sintering temperature
Yingqiong Yong, Tetsu Yonezawa, Masaki Matsubara, Hiroki Tsukamoto
JOURNAL OF MATERIALS CHEMISTRY C, 3, 23, 5890, 5895, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, To facilitate sintering of copper particles at low temperatures and achieve excellent electrical conductivity of copper films, reducing particle size is a common method. However, strong reducing agents which are usually used for reducing the size of particles limit their application. Here we report a novel approach to obtain highly conductive copper films. Firstly, copper fine particles were prepared by a one-pot reduction reaction utilizing D-isoascorbic acid as a mild reductant. Secondly, tight connection facilitating the sintering of particles was formed by generating convex surfaces, nanorods or nanoparticles during the oxidation procedure. The mechanism of the oxidative preheating process and its effects on the conductivity were clarified. High conductivity of copper films at low temperatures can be achieved due to the critical role of the oxidative preheating process.

Silver sputtering into a liquid matrix containing mercaptans: the systematic size control of silver nanoparticles in single nanometer-orders
Yohei Ishida, Ryota Nakabayashi, Masaki Matsubara, Tetsu Yonezawa
NEW JOURNAL OF CHEMISTRY, 39, 6, 4227, 4230, ROYAL SOC CHEMISTRY, 2015, [Peer-reviewed]
English, Scientific journal, We herein propose a novel methodology to synthesize silver nano-particles with precisely controlled diameters in single nano-meter orders by sputtering into a liquid matrix (polyethylene glycol) containing mercaptans (11-mercaptoundecanoic acid) as an environmental friendly preparation without reductants.

Double-wall TiO2 nanotube arrays: enhanced photocatalytic activity and in situ TEM observations at high temperature.
Chaorui Xue, Takashi Narushima, Yohei Ishida, Tomoharu Tokunaga, Tetsu Yonezawa
ACS applied materials & interfaces, 6, 22, 19924, 32, 26 Nov. 2014, [Peer-reviewed], [International Magazine]
English, Scientific journal, By decreasing the water content in an NH4F and glycerol-water electrolyte, the transition from single-wall to double-wall TiO2 nanotube arrays was successfully achieved using an anodization method. The double-wall TiO2 nanotube structures exhibited better photocatalytic activity than the typical single-wall structures. After modification with platinum nanoparticles, the photocatalytic activity of both the single- and double-wall TiO2 nanotubes was improved further. In situ observations at the annealing temperature of the TiO2 nanotubes were performed using a transmission electron microscopy (TEM) system. A slower structural failure of the nanotubes was obtained with the introduction of oxygen gas into the TEM column compared with the structural changes observed under high-vacuum conditions without the introduction of oxygen gas. These behaviors suggest that oxygen injection is an important factor in stabilizing the TiO2 nanotubes during the in situ TEM annealing process. The high-magnification TEM images of the double-wall TiO2 nanotubes revealed that the sintering of the inner wall can draw a clear distinction between the inner and outer walls.

Influence of Surface Properties on SEM Observation for Carbon Nanotubes with Pretreatment Using Room Temperature Ionic Liquids
Shigeaki Abe, Atsushi Hyono, Tetsu Yonezawa
JOURNAL OF SOLUTION CHEMISTRY, 43, 9-10, 1645, 1654, SPRINGER/PLENUM PUBLISHERS, Oct. 2014, [Peer-reviewed]
English, Scientific journal, In this study, we observed hydrophobic or hydrophilic carbon nanotubes (CNTs) by scanning electron microscopy (SEM); the samples were pretreated with room temperature ionic liquids (RTILs) to impart electrical conductivity to their surfaces. When the amount of RTIL on the sample surface and the affinity between the RTIL and sample surface were tuned, suitable electroconductive thin layers were formed on the sample surfaces. The presence of these layers allowed high-quality SEM images to be observed at the nano level. Suitable pretreatments for CNT were achieved using dilute RTIL/ethanol solutions. By optimizing these conditions, we acquired SEM images that were similar in quality to those of samples subjected to the conventional pretreatment of metal sputtering. The highest resolution of the SEM images was less than 30 nm.

Copper film prepared from copper fine particle paste by laser sintering at room temperature: Influences of sintering atmosphere on the morphology and resistivity
Gang Qin, Akira Watanabe, Hiroki Tsukamoto, Tetsu Yonezawa
JAPANESE JOURNAL OF APPLIED PHYSICS, 53, 9, 印刷中, IOP PUBLISHING LTD, Sep. 2014, [Peer-reviewed]
English, Scientific journal, Laser sintering method was applied for copper fine particle paste to generate electrically conductive copper film. The one-step sintering of the copper fine particle coating films at room temperature was carried out by scanning irradiation of a line-shaped laser beam under various atmospheric conditions. The laser sintering of the copper fine particle coating film under a hydrogen/argon (4/96) gas mixture flow gave a copper film with a low resistivity of 1.05 x 10(-5) Omega cm. The scanning electron microscope (SEM) image of the laser sintered film showed the necking among copper fine particles. The film laser-sintered in air was insulator which showed the Raman band assigned to Cu2O. The laser sintering of the copper fine particle coating film under argon gas flow gave also copper films with resistivities of the order of 10(-5) Omega cm, which depended on the flow rate of argon gas. On the other hand, the film sintered by conventional heat treatment at 300 degrees C under argon gas flow showed a high resistivity. The formation of a copper wiring with several micrometers resolution was achieved by laser direct writing using copper fine particle with the size larger than 100 nm. The advantages of the laser sintering in the preparation of a conductive film from copper fine particle paste were demonstrated. (C) 2014 The Japan Society of Applied Physics

In Situ Transmission Electron Microscopic Observation of Double-wall TiO2 Nanotube Arrays at High Temperature
Chaorui Xue, Takashi Narushima, Yohei Ishida, Tomoharu Tokunaga, Tetsu Yonezawa
CHEMISTRY LETTERS, 43, 9, 1514, 1516, CHEMICAL SOC JAPAN, Sep. 2014, [Peer-reviewed]
English, Scientific journal, Double-wall TiO2 nanotube arrays were prepared using an anodization method in a glycerol-containing electrolyte. In situ TEM observation of these samples at high temperature was carried out with and without oxygen injections. With oxygen injection, an improved thermal stability of the nanotubes at high temperature was observed. It may provide more detailed information about the calcination process of TiO2 nanotubes and assist its morphology and structure modulation.

Wet Preparation of Organic-Stabilizer-Free Urchin Structured Nickel Fine Particles and Their In Situ TEM Observation at High Temperatures
Takashi Narushima, Ren Lu, Tetsu Yonezawa
MATERIALS TRANSACTIONS, 55, 9, 1474, 1478, JAPAN INST METALS, Sep. 2014, [Peer-reviewed]
English, Scientific journal, Urchin structured nickel fine particles were successfully obtained by the hydrazine reduction of NiCl2 center dot 6H(2)O in ethanol. The particle structures, particularly the aspect ratios of the nickel nanoneedles on the surface, were controlled by changing the sequence of the addition of hydrazine and sodium hydroxide. These particles were not stabilized by organic compounds. In situ TEM observations at high temperatures revealed that the obtained fine particles began to deform at 350 degrees C.

Formation Process of Metallic Copper Fine Particles from Cupric Oxide Microparticles at Room Temperature
Tetsu Yonezawa, Yoshiki Uchida, Yuki Abe
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 14, 7, 5402, 5407, AMER SCIENTIFIC PUBLISHERS, Jul. 2014, [Peer-reviewed]
English, Scientific journal, Copper (Cu) fine particles were prepared by room-temperature hydrazine reduction of Cu oxide microparticles. In this study, to reveal the formation process of metallic Cu homogeneous fine particles from cupric oxide (CuO) microparticles, hydrazine was added to a CuO slurry at room temperature. The morphological changes in the product during the reduction with and without ammonia were observed by using scanning electron microscopy (SEM). The SEM images indicated that not only did the Cu2+ dissolve in water by complex formation with ammonia or hydrazine, but also that Cu2+ ions on the surface of CuO microparticles were reduced by hydrazine to form metallic Cu fine particles. Tuning the sizes of Cu particles by the stabilizing reagent is also discussed.

Simple and Rapid Conductive Preparation of Wet Biological Samples for SEM Observation: Use of an Asymmetrical Choline-like Room Temperature Ionic Liquid as a Visualizing Agent
ABE SHIGEAKI, HYONO ATSUSHI, KAWAI KOJI, NAKAMURA KOICHI, YAWAKA YASUTAKA, YOSHIDA YASUHIRO, YONEZAWA TETSU
Nano Biomed, 6, 1, 41, 46, 30 Jun. 2014
English

イオン液体を用いたバイオマテリアルのSEM新規観察法の開発
兵野 篤, 米澤 徹, 阿部 薫明, 赤坂 司, 亘理 文夫
北海道外科雑誌, 59, 1, 91, 92, 北海道外科学会, Jun. 2014
Japanese

SEM observation of the live morphology of human red blood cells under high vacuum conditions using a novel RTIL
Atsushi Hyono, Tetsu Yonezawa, Koji Kawai, Shigeaki Abe, Mitsuhiro Fujihara, Hiroshi Azuma, Shinobu Wakamoto
SURFACE AND INTERFACE ANALYSIS, 46, 6, 425, 428, WILEY-BLACKWELL, Jun. 2014, [Peer-reviewed]
English, Scientific journal, In this study, we succeed in visualizing a living' morphology of red blood cells (RBCs) by a rapid and simple scanning electron microscope (SEM) pretreatment using a hydrophilic room temperature ionic liquid (RTIL) with asymmetrical structure. The conventional pretreatment induces size shrinkage of the cells, and the diameter observed in an SEM (less than 6 mu m) was smaller than that in an optical microscope (8 mu m). Though RBCs are well-known to be easily deformed with the environmental conditions, the cells did not show the deformation when they were pretreated with our RTILs. Since the chemical structure of our RTIL resembles a choline', which is a typical bioactive material, and has biocompatibilities, they may make it avoid from the deformation of RBCs. In fact, only immersing RBCs, our novel RTIL can provide a clear SEM image without size shrinkage and deformation. Interestingly, the obtained SEM image shows 8 mu m in the diameter, almost same size as that in optical microscope. Therefore, this method is expected for novel SEM pretreatment for various biological samples observation as living' matter. Copyright (c) 2014 John Wiley & Sons, Ltd.

Responses of RAW264.7 macrophages to water-dispersible gold and silver nanoparticles stabilized by metal-carbon sigma-bonds
Masanori Hashimoto, Hirokazu Toshima, Tetsu Yonezawa, Koji Kawai, Takashi Narushima, Masayuki Kaga, Kazuhiko Endo
JOURNAL OF BIOMEDICAL MATERIALS RESEARCH PART A, 102, 6, 1838, 1849, WILEY-BLACKWELL, Jun. 2014, [Peer-reviewed]
English, Scientific journal, Nanometals are currently receiving considerable attention for industrial and biomedical applications, but their potentially hazardous and toxic effects have not been extensively studied. This study evaluated the biological responses of novel water-dispersible gold (Au-NPs) and silver nanoparticles (Ag-NPs) stabilized by Au-C or Ag-C sigma-bonds in cultured macrophages (RAW264.7), via analysis of the cell viability, the integrity of the plasma membrane, and the inflammatory and morphological properties. The cultured RAW264.7 was exposed to metal-NPs at various concentrations. The Ag-NPs showed cytotoxicity at high NP concentrations, but the cytotoxic effects of the Au-NPs were smaller than those of the Ag-NPs. For the microscopic analysis, both types of particles were internalized into cells, the morphological changes in the cells which manifested as an expansion of the vesicles' volume, were smaller for the Au-NPs compared with the Ag-NPs. For the Ag-NPs, the endocytosis abilities of the macrophages might have induced harmful effects, because of the expansion of the cell vesicles. Although an inflammatory response was observed for both the Au- and Ag-NPs, the harmful effects of the Au-NPs were smaller than those of the Ag-NPs, with minor morphological changes observed even after internalization of the NPs into the cells. (c) 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 102A: 1838-1849, 2014.

Alignment of Needle TiO_2_ Nanoparticles in Water
Atsushi Hasegawa, Masamitsu Yoshiki, Tsuguhito Nakano, Susumu Sato, Tetsu Yonezawa
International Journal of Theoretical and Applied Nanotechnology, 2, 1, 18, 23, 31 Mar. 2014, [Peer-reviewed]
English, Scientific journal, Alignment of needle-like nanoparticles in solution because of migration due to an electric field is observed using Rayleigh-Mie scattering. This is confirmed by the change in the signal form as a function of the scattering angle. It is clearly observed that the signal profiles between the aligned and non-aligned situations are different. The theoretical calculation of Rayleigh-Mie scattering based on a single spherical particle is used for analyzing the experimental data. The theoretical analysis is in good agreement with the result of experiment.

Visualizing Preparation Using Asymmetrical Choline-Like Ionic Liquids for Scanning Electron Microscope Observation of Non-Conductive Biological Samples
Shigeaki Abe, Atsushi Hyono, Koji Kawai, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 14, 3, 2620, 2623, AMER SCIENTIFIC PUBLISHERS, Mar. 2014, [Peer-reviewed]
English, Scientific journal, In this study, we investigated conductivity preparation for scanning electron microscope (SEM) observation that used novel asymmetrical choline-type room temperature ionic liquids (RTIL). By immersion in only an RTIL solution, clear SEM images of several types of biological samples were successfully observed. In addition, we could visualize protozoans using RTILs without any dilution. These results suggested that the asymmetrical choline-type RTILs used in this study are suitable for visualizing of biological samples by SEM. Treatment without the need for dilution can obviate the need for adjusting the RTIL concentration and provide for a rapid and easy conductivity treatment for insulating samples.

Wet Preparation of Organic Stabilizer Free Urchin Structured Nickel Fine Particles and Their In-Situ TEM Observation at High Temperature
Takashi Narushima, Ren Lu, Tetsu Yonezawa
JOURNAL OF THE JAPAN INSTITUTE OF METALS, 78, 2, 98, 102, JAPAN INST METALS, Feb. 2014, [Peer-reviewed]
Japanese, Scientific journal, Urchin structured nickel fine particles have been successfully obtained by the hydrazine reduction of NiC12.6H20 in ethanol. Changing the time of the addition of hydrazine and sodium hydroxide can control the particle structures, especially the aspect ratio of the Ni nanoneedles. These particles were not stabilized by organic compounds. In-situ TEM observation at high temperature revealed the deformation of the obtained fine particles began at 350 degrees C.

Evaluation of Silver Nanoparticle Toxicity to RAW264.7 Cells in a Three-Dimensional Cell Culture
Masanori Hashimoto, Hirokazu Toshima, Tetsu Yonezawa, Koji Kawai, Masahiro Iijima, Kazuhiko Endo
JOURNAL OF BIOMATERIALS AND TISSUE ENGINEERING, 4, 1, 51, 58, AMER SCIENTIFIC PUBLISHERS, Jan. 2014, [Peer-reviewed]
English, Scientific journal, Clinically relevant in vitro models are required to rapidly evaluate the cytotoxicity of nanoparticles. Recently, numerous three-dimensional cell culture systems (3D) have been manufactured to mimic the properties of tissue in vivo. Spheroid culture models play an invaluable role in understanding tumor biology and in performing the screening of drugs and biomaterials. Nanoparticles (NPs) are currently receiving considerable attention for industrial and biomedical applications, yet their hazardous and potential toxic effects have not been studied extensively. The purpose of this study was to evaluate the biological effects of polyvinylpyrrolidone-coated silver nanoparticles (AgNPs) in murine macrophages (RAW264.7 cells) cultured in traditional two-dimensional (2D) and novel 3D systems. Biological assays and a micromorphological analysis was performed. Microscopic imaging revealed that the particles were internalized into cells and receptor-mediated endocytosis occurred. However, cells exposed to AgNPs exhibited minor morphological changes compared with cells no exposed. AgNPs displayed greater cytotoxicity in the 2D culture versus in the 3D. Moreover, in the 3D culture the AgNP cytotoxicity decreased over time, which did not occur in the 2D culture.

Salmon milt DNA as a template for the mass production of Ag nanoparticles
Tomomi Takeshima, Ling Sun, Yanqing Wang, Yoshihisa Yamada, Norio Nishi, Tetsu Yonezawa, Bunshi Fugetsu
POLYMER JOURNAL, 46, 1, 36, 41, NATURE PUBLISHING GROUP, Jan. 2014, [Peer-reviewed]
English, Scientific journal, A wet-chemical approach using DNA extracted from salmon milt as a template to mass produce Ag nanoparticles was developed. Spherical Ag nanoparticles with a main diameter of less than 10 nm were obtained. The concentration of Ag nanoparticles in the as-produced colloidal suspension was as high as 5.3 x 10(-2) mol I-1. This simple and effective procedure should offer an alternative route to the mass production of Ag nanoparticles for practical applications.

Overlook of Gold Nanoparticles and Other Metal Nanoparticles Containing Gold
YONEZAWA Tetsu
Oleoscience, 14, 1, 11, 15, Japan Oil Chemists' Society, 2014
Japanese,

Gold nanoparticles have been widely used as a good inorganic red pigment which show dark wine red color. Gold nanoparticles are considered as a long life pigment. Red stained glasses often used in old churches are old glasses containing gold nanoparticles. They are very clear and show dark red color. The history of the chemistry of gold nanoparticles is very long, and began in 1857. Faraday firstly reported the preparation of red gold hydrosol^{1, 2)}. Gold itself is a highly precious materials and show brilliant gold luster. However, gold nanoparticles show considerably different color. Gold has attracted much interest not only from scientists. Such gold nanoparticles can be prepared quite readily by chemical reduction of the corresponding salts, which also support their intensive scientific studies. Recently, Brust et al. reported the preparation of single nanometer-sized gold nanoparticles by NaBH₄ reduction³⁾. This pioneering report introduced explosive expansion of nanoparticle researches. Gold nanoclusters and gold nanocatalysts which are also invented quite recently still continue to attract the peoples' interest. In this section, I would like to overlook the studies of gold nanoparticles.

Terahertz Emission from CuxO/Au Thin Film
Xu Lu, Tetsu Yonezawa
2014 INTERNATIONAL TOPICAL MEETING ON MICROWAVE PHOTONICS (MWP) AND THE 2014 9TH ASIA-PACIFIC MICROWAVE PHOTONICS CONFERENCE (APMP), 164, 165, IEEE, 2014, [Peer-reviewed]
English, International conference proceedings, Terahertz (THz) emission from copper oxides/gold interface was detected on silicon substrates. The unexpected THz emission was attributed to Schokkty barrier at the interface. Degree of oxidation of the copper layer significantly affected the THz emission amplitude by the difference of electronic structures between cuprous oxide and cupric oxide.

Cyclodextrin-supported organic matrix for application of MALDI-MS for forensics. Soft-ionization to obtain protonated molecules of low molecular weight compounds
Tetsu Yonezawa, Takashi Asano, Tatsuya Fujino, Hiroshi Nishihara
CHEMICAL PHYSICS, 419, 17, 22, ELSEVIER SCIENCE BV, Jun. 2013, [Peer-reviewed]
English, Scientific journal, A mass measurement technique for detecting low-molecular-weight drugs with a cyclodextrin-supported organic matrix was investigated. By using cyclodextrin-supported 2,4,6-trihydroxyacetophenone (THAP), the matrix-related peaks of drugs were suppressed. The peaks of protonated molecules of the sample and THAP were mainly observed, and small fragments were detected in a few cases. Despite the Na+ and K+ peaks were observed in the spectrum, Na+ or K+ adduct sample molecules were undetected, owing to the sugar units of cyclodextrin. The advantages of MALDI-MS with cyclodextrin-supported matrices as an analytical tool for forensic samples are discussed. The suppression of alkali adducted molecules and desorption process are also discussed. (C) 2012 Elsevier B.V. All rights reserved.

In-Plane Orientation Control of 2,7-Diphenyl[1]benzothieno[3,2-b][1]benzothiophene Monolayer on Bismuth-Terminated Si(111) Vicinal Surfaces with Wettability Optimization
Manabu Ohtomo, Yuya Tsuchida, Naoki Muraya, Takashi Yanase, Seiji Sakai, Tetsu Yonezawa, Taro Nagahama, Tetsuya Hasegawa, Toshihiro Shimada
JOURNAL OF PHYSICAL CHEMISTRY C, 117, 22, 11555, 11561, AMER CHEMICAL SOC, Jun. 2013, [Peer-reviewed]
English, Scientific journal, We report the in-plane orientation control of a high-mobility organic semiconductor: 2,7-diphenyl[1]benzothieno[3,2-b][1]benzothiophene (DPh-BTBT). As previously reported for the monolayer pentacene, it was revealed that bunched steps on the vicinal Si(111) with a bismuth termination break the surface 3-fold symmetry and reduce the multiple orientation of the DPh-BTBT grains into a quasi-single orientation. Interestingly, the critical step height necessary for the orientation control was higher than that of pentacene. We examined several mechanisms of orientation control and concluded that the facet nanostructure fabricated by step bunching works as an anisotropic template for the nucleation. We also show the wettability optimization of the bismuth-terminated silicon surface and show that the growth mode of DPh-BTBT is dependent on the surface nanostructure of Bi-Si.

Surfactant Free-solution Synthesis of Copper Nanoparticles for Low Temperature Sintering and Conductive Paste
KAWASAKI Hideya, OBORA Yasushi, YONEZAWA Toru, ARAKAWA Ryuichi
Journal of The Adhesion Society of Japan, 49, 5, 171, 176, The Adhesion Society of Japan, 01 May 2013
Japanese

Suitability of GaP nanoparticles as a surface-assisted laser desorption/ionization mass spectroscopy
T. Yonezawa, H. Tsukamoto, S, Hayashi Y, Myojin H. Kawasaki, R.Arakawa
Analyst, 138, 995-999, May 2013
2013/5/

Structure Consideration of Platinum Nanoparticles Constructing Nanostructures Obtained by Electrochemical Dealloying of a Cu-Pt Alloy
Kazuki Maruya, Ryoji Yamauchi, Takashi Narushima, Seiji Miura, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 13, 4, 2999, 3003, AMER SCIENTIFIC PUBLISHERS, Apr. 2013, [Peer-reviewed]
English, Scientific journal, Many nanoporous metals have been applied for catalysis and show active properties. In this study, nanoporous platinum was successfully prepared from a Cu-Pt (50/50 w/w) alloy plate by electrochemical dealloying. In order to reveal their detailed structures in nanometer order, TEM observation of the surface area of the alloy plate was performed by using focused ion beam (FIB) for sample preparation. Peeling off the surface platinum nanoparticles could be also successfully preformed by using ultra sonification and their TEM observation revealed the units of the platinum nanoporous. structures.

Simple pretreatment of non-conductive small hydrous bio-samples with choline-type ionic liquid and membrane filter for microsample mounting
Koji Kawai, Kotaro Kaneko, Hayato Kawakami, Takashi Narushima, Tetsu Yonezawa
COLLOIDS AND SURFACES B-BIOINTERFACES, 102, 9, 12, ELSEVIER SCIENCE BV, Feb. 2013, [Peer-reviewed]
English, Scientific journal, Choline-type ionic liquids (CILs), which have a molecular structure resembling that of the vitamin-like active substance choline, have high water solubility, high osmotic pressure, and high cell membrane permeability. Their physical properties make them a very useful pretreatment agent for scanning electron microscopy (SEM) observation of hydrous samples because they can replace water in the samples, causing them to retain their shapes. SEM images of pollen without dissolution of cell membranes, damage, or deformation were obtained by a simple visualization process using CILs. We also identified an easy pretreatment protocol for SEM observation of hydrous microsamples that uses a membrane filter as a sample stage to ensure correct sample placement. Bacteria were successfully observed by using this protocol. (c) 2012 Elsevier B.V. All rights reserved.

Use of a bio-polymer as protective reagent for the metal particles for electronic parts
Tetsu Yonezawa
Kobunshi Ronbunshu, 70, 12, 684, 692, Society of Polymer Science, 2013, [Peer-reviewed]
Japanese, Scientific journal, The application of a bio-polymer, gelatin, as a material for copper fine particles, used for electronics parts, is described. Gelatin is well-known as a good stabilizer of metal nano- and fine particles. However, gelatin has not been frequently applied to such materials. According to the properties of surface coatings by gelatin, these copper fine particles are not easily oxidized. They could also be applied as the material for the inner electrodes of ceramic condensers. Such applications of bio-polymers can be one good example for reaching a sustainable society. ©2013, The Society of Polymer Science,.

Micromorphological cellular responses of MC3T3-E1 and RAW264.7 after exposure to water-dispersible silver nanoparticles stabilized by metal-carbon σ-bonds
Masanori Hashimoto, Hirokazu Toshima, Tetsu Yonezawa, Koji Kawai, Takashi Narushima, Masayuki Kaga, Kazuhiko Endo
Dental Materials Journal, 32, 5, 725, 733, 2013, [Peer-reviewed]
English, Scientific journal, With the continuous progress in nanomaterial development for biomedicine, the potential cytotoxicity of nanoparticles is drawing more attention and concern for clinical applications. The purpose of this study was to evaluate biological responses of new water-dispersible silver nanoparticles (Ag-NPs) stabilized by Ag-C σ-bonds in cultured murine macrophages (RAW264.7) and osteoblast-like cells (MC3T3-E1) using cell viability and morphological analyses. For RAW264.7, Ag-NPs seemed to induce cytotoxicity that was dependent on the Ag-NP concentration. However, no cytotoxic effects were observed in the MC3T3-E1 cell line. In microscopic analysis, Ag-NPs were taken up by MC3T3-E1 cells with only minor cell morphological changes, in contrast to RAW264.7 cells, in which particles aggregated in the cytoplasm and vesicles. The ability of endocytosis of macrophages may induce harmful effects due to expansion of cell vesicles compared to osteoblast-like cells with their lower uptake of Ag-NPs.

Scanning Electron Microscope Observation of Nano Carbon Materials with Imidazolium-Type Room Temperature Ionic Liquids
Shigeaki Abe, Atsushi Hyono, Katsutoshi Nakayama, Tomoya Takada, Tetsu Yonezawa
JAPANESE JOURNAL OF APPLIED PHYSICS, 52, 1, IOP PUBLISHING LTD, Jan. 2013, [Peer-reviewed]
English, Scientific journal, A novel pre-treatment method for scanning electron microscopy (SEM) observation using room temperature ionic liquids (ILs) was used for several carbon nano materials. After the ILs pre-treatment, the quality of the SEM images obtained was almost the same as that obtained with conventional platinum/palladium (Pt/Pd) spattering pre-treatment. The highest resolution in this study was under 30 nm. This result means that the pre-treatment with IL can form ultrathin layer on the sample surface at several molecules level. Therefore, the ILs pre-treatment is a simple and easy tool for SEM observation of nano materials on insulating substrates. (C) 2013 The Japan Society of Applied Physics

Preparation of Copper Nanoparticles in Liquid by Matrix Sputtering Process
Ko Nakagawa, Takashi Narushima, Satoshi Udagawa, Tetsu Yonezawa
15TH INTERNATIONAL CONFERENCE ON THIN FILMS (ICTF-15), 417, IOP PUBLISHING LTD, 2013, [Peer-reviewed]
English, International conference proceedings, As a new method for nanoparticles preparation, magnetron sputtering of metal atoms and clusters into organic liquids has been intensively used recently. In this study, metallic copper nanoparticles dispersed in pentaerythritol ethoxylate were prepared by this process. Their size control was achieved by controlling the sputtering current. Specific absorption at ca. 580 nm was detected by UV-Vis measurement which is attributed to the specific plasmon absorption of metallic copper. TEM observation also revealed the formation of metallic nanoparticles.

Direct SEM Observation of Non-electroconductive TiOF2 Nanotube Arrays Prepared by Anodization Using an Ionic Liquid as a Visualizing Reagent
Chaorui Xue, Takashi Narushima, Tetsu Yonezawa
JOURNAL OF INORGANIC AND ORGANOMETALLIC POLYMERS AND MATERIALS, 23, 1, 239, 242, SPRINGER, Jan. 2013, [Peer-reviewed]
English, Scientific journal, Arrays of TiOF2 nanotubes of the diameters ca. 100 nm were successfully prepared by the anodization of a titanium foil in an aqueous electrolyte containing fluoride anion. Scanning electron microscope observation of the surface of TiOF2 arrays was performed, but the surface was charged, so no clear image was obtained. Meanwhile, when the specimen was pretreated with an ionic liquid, a clear surface image could be observed, and the degree of clarity corresponded to its ion conductivity. This result indicates that the advantage of using an ionic liquid for visualizing nanomaterials.

Biocompatibility and biodistribution of several nano-sized ceramics particles
Shigeaki Abe, Yusaku Hamba, Nobuki Iwadera, Tsukasa Akasaka, Shuichi Yamagata, Yasutaka Yawaka, Junichiro Iida, Motohiro Uo, Tetsu Yonezawa, Fumio Watari
BIOCERAMICS 24, 529-530, 625, +, TRANS TECH PUBLICATIONS LTD, 2013, [Peer-reviewed]
English, International conference proceedings, We succeeded in determination the biodistribution of several nano-sized particles administered to mice through the tail vein. After administration, these particles were observed in the lung, liver and spleen. The distribution behaviors depend upon not only chemical species but also the particles size. To estimate their cytocompatibility, these particles were exposed to osteoblastic cell at several concentrations. When the concentration reached at 10 ppm, their viability remained at 80% or more even nano-sized particle contained rare earth element. Only CuO particles indicated the viability decrease. The effect depended on the particle size. These results suggested that the chemical species played a dominant key in the biodistribution and biocompatibility of nanoparticles compared with the size-effect.

Near-infrared photoluminescence from molecular crystals containing tellurium
Hong Tao Sun, Yoshio Sakka, Naoto Shirahata, Minoru Fujii, Tetsu Yonezawa
Journal of Materials Chemistry, 22, 47, 24792, 24797, 21 Dec. 2012, [Peer-reviewed]
English, Scientific journal, We report the observation of near-infrared photoluminescence from Te 4(Ga2Cl7)2 and Te 4(Al2Cl7)2 molecular crystals containing Te42+ polycations. The experimental and theoretical results clearly revealed that the Te42+ polycation is a smart near-infrared emitter with characteristic emission peaks at 1252 and 1258 nm for Te4(Ga2Cl7)2 and Te4(Al2Cl7)2 crystals, respectively, resulting from the intrinsic electronic transitions of Te 42+. Furthermore, it was also found that the emissions strongly depend on the excitation wavelengths for both Te4(Ga 2Cl7)2 and Te4(Al2Cl 7)2 samples, most possibly due to the co-existence of other Te-related optically active centers. This research not only enriches the species of luminescent charged p-block element polyhedra and deepens the understanding of Te-related photophysical behaviors, but also may stimulate efforts for designing novel material systems using such active centers. It is also greatly expected that these sub-nanometer optically active species could exist in other systems such as glasses, polymers, and bulk optical crystals, and the stabilization of these centers in widely used hosts will pave the way for their practical applications. © The Royal Society of Chemistry 2012.

Temperature distributions of electron beam-irradiated samples by scanning electron microscopy
T. Tokunaga, T. Narushima, T. Yonezawa, T. Sudo, S. Okubo, S. Komatsubara, K. Sasaki, Takahisa Yamamoto
JOURNAL OF MICROSCOPY, 248, 3, 228, 233, WILEY-BLACKWELL, Dec. 2012, [Peer-reviewed]
English, Scientific journal, An electron beam (EB) generated by a scanning electron microscope (SEM) was used to irradiate two samples having different thermal conductivities, and the resulting temperatures of the EB-irradiated areas as well as the temperature distributions within the samples were then measured using a thermal camera. These measurements showed overall increases in sample temperatures, as well as revealed temperature rises at the EB-irradiated areas that had little difference with one of the theoretical predictions. Differences between the actual and the predicted temperature measurements were analysed in terms of the accuracy with which parameters could be estimated. The temperature distributions of the samples were measured and, On the basis of the results, it was hypothesized that the temperature differential over an irradiated sample will be inversely correlated with its thermal conductivity.

Synthesis and antibacterial properties of water-dispersible silver nanoparticles stabilized by metal-carbon sigma-bonds
Koji Kawai, Takashi Narushima, Kotaro Kaneko, Hayato Kawakami, Miyuki Matsumoto, Atsushi Hyono, Hiroshi Nishihara, Tetsu Yonezawa
APPLIED SURFACE SCIENCE, 262, 76, 80, ELSEVIER SCIENCE BV, Dec. 2012, [Peer-reviewed]
English, Scientific journal, The synthesis of 4-diazoniumcarboxylbenzene fluoroborate, a new water-soluble stabilizer for metal nanoparticles (NPs), is described. A stable dispersion of Ag NPs in water was successfully produced by a simultaneous aqueous reduction of this diazonium salt and silver nitrate by NaBH4. UV-vis spectra, TEM images, XRD patterns, and XPS spectra of the obtained Ag NPs revealed that they were stabilized by Ag-C sigma-bonds. These NPs showed excellent antimicrobial properties against Staphylococcus aureus. (c) 2012 Elsevier B.V. All rights reserved.

Fabrication of ZnO Nanorods by Atmospheric-Pressure Solid-Source CVD Using Ethanol-Assisted Low-Temperature Vaporization
Sawako Miyamoto, Tetsuya Hasegawa, Hiroyuki Takahashi, Tetsu Yonezawa, Hajime Kiyono, Takashi Yanase, Taro Nagahama, Toshihiro Shimada
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 85, 12, 1287, 1292, CHEMICAL SOC JAPAN, Dec. 2012, [Peer-reviewed]
English, Scientific journal, We report a method to produce vapor species from ZnO powder for the fabrication of ZnO nanorods. Mixing ethanol vapor with the inert carrier gas substantially lowered the gasification temperature of ZnO. c Axis-aligned ZnO nanorods were obtained by dispersing gold nanoparticles on Si substrates. The growth was identified as a vapor-solid (VS) mechanism. Choice of the substrate materials and their surface morphology were both critically important to control the shapes and orientation of grown ZnO.

High temperature oxidation event of gelatin nanoskin-coated copper fine particles observed by in situ TEM
Takashi Narushima, Hiroki Tsukamoto, Tetsu Yonezawa
AIP ADVANCES, 2, 4, AMER INST PHYSICS, Dec. 2012, [Peer-reviewed]
English, Scientific journal, Metallic copper fine particles were prepared using CuO slurry by hydrazine reduction in the presence of gelatin. To observe a behavior of these particles at high temperature, in situ heating TEM observations were carried out. Oxygen gas was introduced and the pressure of the TEM column was kept at 10(-3) Pa, corresponding the pressure around the sample at 10(-1) Pa. The gelatin, which acts as a protective nanoskin on the particle surface was gradually decomposed. Around approximately 140 degrees C, it was observed that Cu2O dots formed on the surface of the copper particle. This result is well consistent with the behavior of the TG-DTA curve of the copper fine particles under ambient conditions, and provides key information of oxidative behavior of copper fine particles. Copyright 2012 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported license.[http://dx.doi.org/10.1063/1.4759498]

Self-assembly of gold nanoparticles on a single crystalline sapphire substrate
Hiroyuki Takahashi, Naoto Shirahata, Takashi Narushima, Tetsu Yonezawa
APPLIED SURFACE SCIENCE, 262, 129, 133, ELSEVIER SCIENCE BV, Dec. 2012, [Peer-reviewed]
English, Scientific journal, Single crystalline sapphire is an atomically flat substrate with a high transparency in a wide wavelength region. However, its surface is chemically stable so that the modification by a self-assembled monolayer is somewhat difficult. We have used a H2O2 treatment at 70 degrees C to activate the surface and modified with a silan coupling reagent. The modification of the surface is discussed with the water contact angle. Immobilization of citrate-stabilized anionic gold nanoparticles on a cationically modified sapphire surface was carried out. (c) 2012 Elsevier B.V. All rights reserved.

Ultra-broad near-infrared photoluminescence from crystalline (K-crypt) 2Bi2 containing [Bi2]^2- dimers
Hong Tao Sun, Tetsu Yonezawa, Miriam M. Gillett-Kunnath, Yoshio Sakka, Naoto Shirahata, Sa Chu Rong Gui, Minoru Fujii, Slavi C. Sevov
Journal of Materials Chemistry, 22, 38, 20175, 20178, 14 Oct. 2012, [Peer-reviewed]
English, Scientific journal, For the first time, we report that a single crystal of (K-crypt) 2Bi2 containing [Bi2]2- displays ultra-broad near-infrared photoluminescence (PL) peaking at around 1190 nm and having a full width at the half maximum of 212 nm, stemming from the inherent electronic transitions of [Bi2]2-. The results not only add to the number of charged Bi species with luminescence, but also deepen the understanding of Bi-related near-infrared emission behavior and lead to the reconsideration of the fundamentally important issue of Bi-related PL mechanisms in some material systems such as bulk glasses, fibers, and conventional optical crystals. © 2012 The Royal Society of Chemistry.

In-Situ Heating TEM Observation of Microscopic Structural Changes of Size-Controlled Metallic Copper/Gelatin Composite
Takashi Narushima, Atsushi Hyono, Naoki Nishida, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 12, 10, 7764, 7776, AMER SCIENTIFIC PUBLISHERS, Oct. 2012, [Peer-reviewed]
English, Scientific journal, Copper/gelatin composite particles with controlled sizes were prepared at room temperature from cupric sulfate pentahydrate in the presence of gelatin as a protective reagent by using hydrazine monohydrate as a reducing agent. The formed particles with the size between 190-940 nm were secondary aggregated particles which were composed of smaller nanosized particles ("particle-in-particle"), the presence of which was established by XRD patterns and a cross-sectional TEM image. The sintering behavior of these copper/gelatin composite particles was demonstrated by in-situ heating TEM under a high vacuum (similar to 10(-5) Pa) and separately with the oxygen partial pressure controlled at the 10(-4) Pa level. It was established that the particles began to sinter at about 330 degrees C with the oxygen and that they sublimate above 450 degrees C both in the vacuum and oxygen conditions. This result shows that the introduction of an adequate amount of oxygen was effective to remove the gelatin surrounding the particles. It can also be concluded that the sintering of the copper/gelatin composite particles occurred even in the absence of a reducing agent such as hydrogen gas.

Photoluminescence from Bi 5(GaCl 4) 3 molecular crystal
Hong Tao Sun, Beibei Xu, Tetsu Yonezawa, Yoshio Sakka, Naoto Shirahata, Minoru Fujii, Jianrong Qiu, Hong Gao
Dalton Transactions, 41, 36, 11055, 11061, 36, 28 Sep. 2012, [Peer-reviewed]
Scientific journal, Bi 5(GaCl 4) 3 sample has been synthesized through the oxidation of Bi metal by gallium chloride (GaCl 3) salt. Powder X-ray diffraction as well as micro-Raman scattering results revealed that, in addition to crystalline Bi 5(GaCl 4) 3 in the product, an amorphous phase containing [GaCl 4] - and [Ga 2Cl 7] - units also exists. The thorough comparison of steady-state and time-resolved photoluminescent behaviors between the Bi 5(GaCl 4) 3 product and Bi 5(AlCl 4) 3 crystal leads us to conclude that Bi 53+ is the dominant emitter in the product, which gives rise to the ultrabroad emission ranging from 1 to 2.7 μm. Detailed quantum chemistry calculation helps us assign the observed excitations to some electronic transitions of the Bi 53+ polycation, especially at shorter wavelengths. It is believed that our work shown here is not only helpful to solve the confusions on the luminescent origin of bismuth in other material systems, but also serves to develop novel broadband tunable laser materials. © 2012 The Royal Society of Chemistry.

金属が再び未来を照らす 第三の蛍光材料:構造制御された金属ナノクラスター
米澤徹
化学, 67, 8, 64-65, Aug. 2012, [Invited]
Japanese, Scientific journal

A method for accurate temperature measurement using infrared thermal camera
Tomoharu Tokunaga, Takashi Narushima, Tetsu Yonezawa, Takayuki Sudo, Shuichi Okubo, Shigeyuki Komatsubara, Katsuhiro Sasaki, Takahisa Yamamoto
JOURNAL OF ELECTRON MICROSCOPY, 61, 4, 223, 227, OXFORD UNIV PRESS, Aug. 2012, [Peer-reviewed]
English, Scientific journal, The temperature distribution on a centre-holed thin foil of molybdenum, used as a sample and heated using a sample-heating holder for electron microscopy, was measured using an infrared thermal camera. The temperature on the heated foil area located near the heating stage of the heating holder is almost equal to the temperature on the heating stage. However, during the measurement of the temperature at the edge of the hole of the foil located farthest from the heating stage, a drop in temperature should be taken into consideration; however, so far, no method has been developed to locally measure the temperature distribution on the heated sample. In this study, a method for the accurate measurement of temperature distribution on heated samples for electron microscopy is discussed.

高度ナノ粒子の製法と応用 低温基材用ナノインクに向けたシングルナノサイズの銅ナノ粒子の製造法
川崎英也, 米澤徹, 荒川隆一
ケミカルエンジニヤリング, 57, 7, 538-542, 542, 化学工業社, Jul. 2012, [Invited]
Japanese, Scientific journal

Preparation of naked silver nanoparticles in a TEM column and direct in situ observation of their structural changes at high temperature
Tetsu Yonezawa, Shigeo Arai, Hironori Takeuchi, Takeo Kamino, Kotaro Kuroda
CHEMICAL PHYSICS LETTERS, 537, 65, 68, ELSEVIER SCIENCE BV, Jun. 2012, [Peer-reviewed]
English, Scientific journal, Naked silver nanoparticles supported on SiO2 were prepared in a TEM chamber in order to be directly observed in situ their structural changes at high temperature. Without exposing the samples in air, this method give a possibility to understand the behavior of metal itself without any contamination or oxidation. Melting temperature depression according to the particle size could be observed. (C) 2012 Elsevier B.V. All rights reserved.

Preparation of Copper Particles by Microwave Induced Plasma in Liquid Process
Takashi Narushima, Takayuki Yoshioka, Hideki Miyazaki, Ikumasa Suga, Susumu Sato, Tetsu Yonezawa
JOURNAL OF THE JAPAN INSTITUTE OF METALS, 76, 4, 229, 233, JAPAN INST METALS, Apr. 2012, [Peer-reviewed]
Japanese, Scientific journal, Non-oxidized metallic copper particles were prepared by plasma irradiation into aqueous solution of cupric sulfate in the presence of gelatin as a protective agent using home-made microwave induced plasma equipment. Then, two different steric structures of ascorbic acid, L-ascorbic acid and isoascorbic acid, were added as reducing auxiliaries. In the case of isoascorbic acid addition, metallic copper particles were obtained by plasma irradiation within about 5 minute. This result suggests that the reduction of copper ion from Cu2+ to metallic Cu can be succeeded by hydrogen radical generated by plasma in water combination with isoascorbic acid, and without toxic chemical agent such as hydrazine. Additionally, the diameter of copper particles can be controlled by the mount of CuSO4 center dot 5H(2)O and gelatin. These results were indicated that the plasma in liquid process has possibilities for high-speed and low environmental load process to prepare metallic copper particles.

Comparison of biodistribution and biocompatibility of gelatin-coated copper nanoparticles and naked copper oxide nanoparticles
Shigeaki Abe, Nobuki Iwadera, Takashi Narushima, Yoshiki Uchida, Motohiro Uo, Tsukasa Akasaka, Yasutaka Yawaka, Fumio Watari, Tetsu Yonezawa
e-Journal of Surface Science and Nanotechnology, 10, 33, 37, 17 Mar. 2012, [Peer-reviewed]
English, International conference proceedings, In this study, we investigated the biocompatibility of gelatin-coated copper nanoparticles. To estimate their cytotoxicity, the coated copper nanoparticles were exposed to osteoblastic cells. The cell proliferation remained above 80% even when the particles concentration increased. When uncoated copper oxide nanoparticles were exposed to the cells, the proliferation ratio rapidly decreased with the concentration reaching 20% under the same conditions. To determine their biodistribution, the nanoparticles were administered to mice through their tail veins. The particles were subsequently found in some organs using an energy-dispersed X-ray spectrometer and inductively coupled plasma-atomic emission spectroscopy. The polymer-coated nanoparticles were observed in the lung, liver and spleen. They were also detected in the urine at higher concentrations than the copper oxide nanoparticles. Thus, the polymer coating is expected to improve biocompatibility by virtue of the excellent cytocompatibility and acceleration of the excretion process. © 2012 The Surface Science Society of Japan.

Observation of Microstructural Changes in Polymer-Coated Kompeito-Type Platinum Particles by In Situ Heating TEM
Takashi Narushima, Takuya Makino, Tomoharu Tokunaga, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 12, 3, 2612, 2616, AMER SCIENTIFIC PUBLISHERS, Mar. 2012, [Peer-reviewed]
English, Scientific journal, We have successfully prepared Kompeito-like platinum particles by hydrogen reduction of Pt4+ in the presence of sodium polyacrylate. We performed in situ TEM observation of these platinum particles at high temperatures. At 300 degrees C, a thin carbon layer due to polyacrylate formed on the particle surface. The detailed structure of the particles did not change with temperatures up to 700 degrees C. Continuous heating up to 800 degrees C blunted the particles' edges and also sintering of the particles was observed. This result strongly indicates that the shape change and sintering of platinum particles are exclusively controlled by the carbon layer, which is generated from a surface stabilizer polymer.

Change in the Morphology of the Terrace Edges on Graphite Surfaces by Electrochemical Reduction
Shosei Kubota, Tetsu Yonezawa, Taro Nagahama, Toshihiro Shimada
CHEMISTRY LETTERS, 41, 2, 187, 188, CHEMICAL SOC JAPAN, Feb. 2012, [Peer-reviewed]
English, Scientific journal, We found that graphite surfaces can be etched by electrochemical reduction in sulfuric acid. Terraces with straight edges crossing with 60 degrees-multiple angles were found on surfaces by AFM observation. It suggests that crystallographic edges can be formed at room temperature in a controlled manner. Layer-by-layer etching of graphene sheets was possible by tuning the etching condition.

Conductivity preparation by choline lactate ethanol solution for SEM observation: Both hard and soft tissues in living matter　　　　　　　　　　　　　　　
Shigeaki Abe, Atsushi Hyono, Yuri Machida, Fumio Watari, Tetsu Yonezawa
Nano Biomedicine, 4, 1, 18, 23, National Institute of Informatics, 2012
English, Scientific journal, In this study, we investigated a conductivity preparation for scanning electron microscope (SEM) observation that uses a solution containing the room temperature ionic liquid (RTIL) choline lactate, which is a natural product - based tertaammonium salt. By only immersion in the choline solution, clear SEM images of biological matter were successfully observed. In addition, we also succeeded in applying the RTIL preparation to energy-dispersed fluorescent X-ray spectroscopy (EDS) and elemental distribution mapping (SEM-EDS). This is the first time that RTIL preparation has been applied to SEM-EDS measurement instead of conventional pretreatment such as carbon sputtering. These results suggested that simple and rapid conductivity preparation using the RTIL solution can be widely applied not only SEM observation but also to SEM-EDS of a variety of living mater.

Surfactant-free single-nano-sized colloidal Cu nanoparticles for use as an active catalyst in Ullmann-coupling reaction
Yuto Isomura, Takashi Narushima, Hideya Kawasaki, Tetsu Yonezawa, Yasushi Obora
CHEMICAL COMMUNICATIONS, 48, 31, 3784, 3786, ROYAL SOC CHEMISTRY, 2012, [Peer-reviewed]
English, Scientific journal, Surfactant-free, single-nano-sized copper nanoparticles (Cu NPs) (size: about 2 nm) were prepared by the DMF reduction method. The Cu NPs showed high catalytic activity (with a turnover number (TON) of up to 2.2 X 10(4)) in Ullmann-type cross-coupling of aryl halides with phenols under ligand-free conditions.

Behavior of Cu nanoparticles ink under reductive calcination for fabrication of Cu conductive film
Kiyonobu Ida, Masanori Tomonari, Yasuyuki Sugiyama, Yuki Chujyo, Tomoharu Tokunaga, Tetsu Yonezawa, Kotaro Kuroda, Katsuhiro Sasaki
THIN SOLID FILMS, 520, 7, 2789, 2793, ELSEVIER SCIENCE SA, Jan. 2012, [Peer-reviewed]
English, Scientific journal, Cu nanoparticle ink was prepared from Cu nanoparticles that were coated with a gelatin layer at an average diameter of 46 nm. The Cu nanoparticle ink was applied on the polyimide substrate. Conductive films were fabricated using the Cu nanoparticle ink with a two-step annealing process consisting of oxidative pre-heating at 200 degrees C under 10 ppm O-2-N-2 mixed gas flow and reductive calcination at 250 degrees C under 3 vol.% H-2-N-2 mixed gas flow showed a low resistivity of 5 mu Omega cm. The hydrolysis of the remaining gelatin layer by H2O vapor, which was formed during the reduction of the Cu oxide by 3 vol.% H-2-N-2 mixed gas, was suggested. The results suggest the possibility of the removal of the gelatin layer without oxidative pre-heating and simultaneous sintering of Cu nanoparticles in reductive calcination. (C) 2011 Elsevier B.V. All rights reserved.

Internal diffusion of biocompatible polymer-coated inorganic nanoparticles in mice
Shigeaki Abe, Akiko Sakaki, Takashi Narushima, Yoshiki Uchida, Tsukasa Akasaka, Motohiro Uo, Tetsu Yonezawa, Fumio Watari
Key Engineering Materials, 493-494, 752, 756, 2012
English, International conference proceedings, In this study, we succeeded in preparation and characterization of two types of biocompatible polymer-coated inorganic nanoparticles (cupper and silicone oxide). As a biocompatible polymer, gelatin and poly(lactic acid) were used. For determination of their biodistribution, the obtained particles were administered to mice through the tail vein. After administration, the particles in some organs were determined with energy-dispersed X-ray spectrometer. The cupper nanoparticles were observed in the lung and kidney, while the silica particles were in the lung, liver and spleen. The distribution behaviors were quite different from non-polymer coated nanoparticles. © (2012) Trans Tech Publications.

Experimental and theoretical studies of photoluminescence from Bi-8(2+) and Bi-5(3+) stabilized by [AlCl4](-) in molecular crystals
Hong-Tao Sun, Yoshio Sakka, Naoto Shirahata, Hong Gao, Tetsu Yonezawa
JOURNAL OF MATERIALS CHEMISTRY, 22, 25, 12837, 12841, ROYAL SOC CHEMISTRY, 2012, [Peer-reviewed]
English, Scientific journal, The photophysical properties of Bi-8(2+) and Bi-5(3+) polycations stabilized by [AlCl4](-) have been studied experimentally and theoretically. The obtained product was thoroughly evaluated by powder X-ray diffraction and photoluminescence spectroscopy, making it clear that both Bi-8(2+) and Bi-5(3+) contribute to the observed broad near-infrared emission. Furthermore, it was revealed that the Bi-8(2+) polycation shows emission peaking at ca. 1180 nm, while Bi-5(3+) shows the longer-wavelength emission. The following quantum chemistry calculation on the Bi-8(2+) polycation helps us attribute some of the observed excitation bands in the visible spectral range to specific electronic transitions of bismuth polycations. It is believed that systematic investigation of structural and luminescent properties as well as detailed quantum chemistry calculation of molecular crystals containing such kinds of bismuth units allows us to obtain a clearer picture of bismuth-related photophysical behaviors, which not only serve to solve the confusions on the luminescence origin of bismuth in other material systems such as bulk glasses, glass fibers and conventional crystals, but also is helpful to develop novel applicable broadband tunable laser mediums.

Synthesis of nanoparticles of silver and platinum by microwave-induced plasma in liquid
Susumu Sato, Kunihiko Mori, Osamu Ariyada, Hyono Atsushi, Tetsu Yonezawa
SURFACE & COATINGS TECHNOLOGY, 206, 5, 955, 958, ELSEVIER SCIENCE SA, Nov. 2011, [Peer-reviewed]
English, Scientific journal, We have conducted a basic study of microwave plasma in liquid at atmospheric pressure. Plasma could be successfully induced by radiated microwave from pointed and ring tungsten electrodes. The tungsten electrode showed a long lifetime of 70 h. Melting and chemical etching of the electrode's top limited the lifetime. Silver cations from silver nitrates could be rapidly and completely reduced to generate metallic silver nanoparticles using this plasma source without any addition of reducing chemical reagents. Optimization of electric conductivity of the reaction solution was not needed. When the material of the electrode was changed to platinum from tungsten, platinum nanoparticles were produced by vaporization into pure water. Both these preparation processes can be expected to produce lower contamination than chemical synthesis. (C) 2011 Elsevier B.V. All rights reserved.

Size of Elementary Clusters and Process Period in Silver Nanoparticle Formation
Masafumi Takesue, Takuya Tomura, Mitsuru Yamada, Katsuhiko Hata, Shigeo Kuwamoto, Tetsu Yonezawa
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 36, 14164, 14167, AMER CHEMICAL SOC, Sep. 2011, [Peer-reviewed]
English, Scientific journal, The time dependence of small-angle X-ray scattering (SAXS) curves for silver nanoparticle formation was followed in situ at a time resolution of 0.18 ms, which is 3 orders of magnitude higher than that used in previous reports (ca. 100 ms). The starting materials were silver nitrate solutions that were reacted with reducing solutions containing trisodium citrate. The SAXS analyses showed that silver nanoparticles were formed in three distinct periods from a peak diameter of ca. 0.7 nm (corresponding to the size of a Ago cluster) during the nucleation and the early growth period. The Ago clusters are most likely elementary clusters that agglomerate to form silver nanoparticles.

Bioinspired Choline-like Ionic Liquids: Their Penetration Ability through Cell Membranes and Application to SEM Visualization of Hydrous Samples
Koji Kawai, Kotaro Kaneko, Hayato Kawakami, Tetsu Yonezawa
LANGMUIR, 27, 16, 9671, 9675, AMER CHEMICAL SOC, Aug. 2011, [Peer-reviewed]
English, Scientific journal, This letter proposes the use of choline-like hydrophilic ionic liquids (ILs) to visualize hydrous samples (e.g., seaweed and other biological or food samples) for scanning electron microscopy (SEM) observation. Some of the water in the samples was successfully replaced with these ILs, which penetrated the cell membranes. The treated samples did not contract much even after drying. The ILs' ionic conductivity decreased the charging of sample surfaces, and good SEM images were obtained.

Hydrophilic Quaternary Ammonium Type Ionic Liquids. Systematic Study of the Relationship among Molecular Structures, Osmotic Pressures, and Water-Solubility
Koji Kawai, Kotaro Kaneko, Tetsu Yonezawa
LANGMUIR, 27, 12, 7353, 7356, AMER CHEMICAL SOC, Jun. 2011, [Peer-reviewed]
English, Scientific journal, This Letter examines the relationship between the structures of ionic liquids and their water-solubility or osmotic pressure with a number of synthesized quaternary ammonium type ionic liquids and organic salts containing a hydroxyl group as hydrophilic substituted groups on ammonium group cations, and bromide or methylsulfonate as anions. The study found a linear relation between the amount and osmotic pressure of the water-soluble ionic liquids synthesized here, strongly indicating that these water-soluble ionic liquids are perfectly ionized in water like inorganic salts with small diameter ions.

Reversible On/Off Conductance Switching of Single Diarylethene Immobilized on a Silicon Surface
Kazuki Uchida, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 24, 9239, 9241, AMER CHEMICAL SOC, Jun. 2011, [Peer-reviewed]
English, Scientific journal, The chemical functionalization of hydrogen-terminated silicon(111) surfaces with photochromic diarylethene using an ethylene anchoring group was achieved. Conductive atomic force microscopy measurements showed the current changes on modified silicon electrodes caused by light-induced isomerization of the diarylethene between an open form and a closed form.

Observation of a 3D network nano-structure of carbon nanotubes scaffold for cultivation
Shigeaki Abe, Kosuke Ishikawa, Atsushi Hyono, Hirohisa Kobayashi, Takayuki Kiba, Tsukasa Akasaka, Motohiro Uo, Yasutaka Yawaka, Shin-Ichiro Sato, Tetsu Yonezawa, Fumio Watari
e-Journal of Surface Science and Nanotechnology, 9, 80, 84, 05 Mar. 2011, [Peer-reviewed]
English, International conference proceedings, Development of scaffolds consisting of micro-/nano-sized materials have attracted a great deal of attention for their potential use in tissue engineering tools. We prepared a cell culture scaffold of carbon nanotubes, which is a typical bio-inert nanomaterial, and then investigated the surface morphology and properties. A three-dimensional nano-level network structure was observed using a scanning electron microscope and an atomic force microscope. The scaffold also exhibited excellent protein absorption. In order to apply the obtained scaffold to the cultivation of osteoblast cells, the cytocompatibility was comparable to that of a conventional cell culture dish. © 2011 The Surface Science Society of Japan.

In-situ TEM Observation of Crystal Structural Change in Metal Nanoparticles(Growth and Novel Functions of Nanocrystals)
Yonezawa Tetsu, Hyono Atsushi
Journal of the Japanese Association of Crystal Growth, 37, 4, 291, 296, 日本結晶成長学会, Jan. 2011, [Invited]
Japanese, Scientific journal, Metal nanoparticles are have special properties depending their size such as melting point suppression and Localized Surface Plasmon Resonance. Therefore, the application of them to some electronic components is attractive because of their easiness for processing. In-situ TEM observation is useful for observation of their crystal structural changes in nanoparticles. Some study have already proposed abut the melting suppression, the crystal formation from amorphous and the sintering process of metal particles.

Preparation of Optical Resins Containing Dispersed Gold Nanoparticles by the Matrix Sputtering Method
Yuichi Shishino, Tetsu Yonezawa, Satoshi Udagawa, Kaname Hase, Hiroshi Nishihara
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50, 3, 703, 705, WILEY-V C H VERLAG GMBH, 2011, [Peer-reviewed]
English, Scientific journal

Microwave-assisted polyol synthesis of copper nanocrystals without using additional protective agents
Hideya Kawasaki, Yuka Kosaka, Yuki Myoujin, Takashi Narushima, Tetsu Yonezawa, Ryuichi Arakawa
CHEMICAL COMMUNICATIONS, 47, 27, 7740, 7742, ROYAL SOC CHEMISTRY, 2011, [Peer-reviewed]
English, Scientific journal, We report the synthesis of 2 nm copper nanocrystals (Cu NCs) via a microwave-assisted polyol method without using additional protective and reducing agents. The Cu NCs are oxidation resistant and exhibit photoluminescence and highly stable properties in a colloidal dispersion.

Non-oxidative copper nano and fine particles for electroconductive materials
Tetsu Yonezawa, Hiroki Tsukamoto, Takashi Narushima
Proceedings of the IEEE Conference on Nanotechnology, 1588, 1591, 2011, [Peer-reviewed]
English, International conference proceedings, Metallic copper nano and fine particles have been successfully prepared by a wet process using a biopolymer as an anti-oxidation reagent. Copper oxide (CuO) and copper sulfate (CuSO 4) were the metal sauces used in this study. Hydrazine was used as the reducing reagent in order to obtain copper metal atoms. Uniform sized metallic copper particles were obtained by this process. Detailed TEM observation revealed that the obtained copper nanoparticles were covered by a continuous thin gelatin layer with the thickness of a couple of nanometers, which prevented oxidation of the obtained metallic copper particles for months. On submicron-sized fine particles, the gelatin layers were very condensed and showed a smooth surface. These organic layers show a sharp gray amorphous contrast in the TEM image. On the other hand, room temperature reduction of Cu 2+ surprisingly gave very small copper nanoparticles with the size in a single digit nm level, but they form uniform-sized submicron sized secondary aggregations. The obtained particles can be kept non-oxidized for months in an ambient condition (under air). These particles could be successfully dispersed into an organic media to form stable electroconductive pastes, by using several physical dispersing steps and an organic coating polymer. Monodispersed particle pastes were obtained to form a continuous particle thin layer. These particles and pastes can be applied to printable electronics in the near future. © 2011 IEEE.

Efficient fabrication of substrates for surface-assisted laser desorption/ionization mass spectrometry using laser ablation in liquids
Tsuji, Takeshi, Mizuki, Takeshi, Yasutomo, Masato, Tsuji, Masaharu, Kawasaki, Hideya, Yonezawa, Tetsu, Mafuné, Fumitaka
Applied Surface Science, 257, 6, 2046, 2050, Elsevier BV, 2011, [Peer-reviewed]
Scientific journal

Observation of Internal Distribution Behavior of Micro/Nano-Sized Ceramics and Metal Particles in Mice
Shigeaki Abe, Nobuki Iwadera, Mami Mutoh, Chika Koyama, Mitsue Esaki, Tsukasa Akasaka, Motohiro Uo, Manabu Morita, Yoshinori Kuboki, Koichi Haneda, Yasutaka Yawaka, Fumio Uchida, Tetsu Yonezawa, Fumio Watari
Bioceramics Development and Applications, 1, D110134, Jan. 2011, [Peer-reviewed]
English, Scientific journal

Controlled Immobilization of Nanoparticles by Self-Assembling : Techniques with DNA Templates
UDAGAWA Satoshi, YONEZAWA Tetsu
IEEJ Transactions on Sensors and Micromachines, 130, 12, 808, 811, The Institute of Electrical Engineers of Japan, 01 Dec. 2010
Japanese, This article has no abstract.

Detailed investigation of the reduction process of cupric oxide (CuO) to form metallic copper fine particles with a unique diameter
Tetsu Yonezawa, Atsushi Hyono, Naoki Nishida
JOURNAL OF MATERIALS SCIENCE, 45, 23, 6433, 6439, SPRINGER, Dec. 2010, [Peer-reviewed]
English, Scientific journal, Copper fine particles were successfully prepared by hydrazine reduction of cupric oxide (CuO). Changes in the temperature and pH values during the redox reaction of cupric oxide and hydrazine monohydrate were observed in detail. These changes reflected the reaction steps leading to the formation of metallic copper particles. The reduction of cupric oxide proceeded mainly during the part of the process where the pH value changes little or only very slowly. This phenomenon strongly indicates that the reaction and the particle structures can be established by control of the pH during the formation.

マイクロ・ナノ粒子の体内循環挙動の追跡と生体への影響　　　　　　　　　　　　　　　
岩寺 信喜, 石川 紘佑, 伊藤 佐智子, 阿部 薫明, 赤坂 司, 宇尾 基弘, 八若 保孝, 亘理 文夫, 高田 知哉, 米澤 徹
日本バイオマテリアル学会大会予稿集, 32回, 323, 323, 日本バイオマテリアル学会, Nov. 2010
Japanese

Fabrication of Reusable Aluminum Printing Plate with Conducting Polymer
KIKUCHI Tatsuya, SHIMAGUCHI Hiroko, UEDA Mikito, SAKAIRI Masatoshi, YONEZAWA Tetsu, TAKAHASHI Hideaki
Journal of The Surface Finishing Society of Japan, 61, 9, 652, 657, 表面技術協会, Sep. 2010, [Peer-reviewed]
Japanese, Scientific journal, A printing plate for gravure printing consisting of five layers of aluminum alloy / anodic oxide film / nickel / polypyrrole / copper was fabricated by anodizing, electro-less plating, electroplating, and electro-polymerization. Nickel layers were first deposited on anodic oxide film-covered aluminum alloy by electro-less plating and electroplating. The polypyrrole layer was then deposited on the nickel layer by anodic polarization in a pyrrole monomer solution. Many copper fine particles were deposited on the polypyrrole-deposited specimen at the initial stage of electroplating in the CuSO...

ナノ粒子・ナノテクと部会
米澤 徹
化学と工業 = Chemistry and chemical industry, 63, 9, 752, 752, 01 Sep. 2010
Japanese

金属ナノ粒子 (特集 世界で活躍する日本の材料技術)
成島 隆, 米澤 徹
高圧ガス, 47, 8, 632, 635, 高圧ガス保安協会, Aug. 2010, [Invited]
Japanese, Scientific journal

Wet Preparation Process of Metal Nano- and Fine-particles and Their Applications
HYONO Atsushi, YONEZAWA Tetsu
Ceramics Japan, 45, 8, 609, 612, 日本セラミックス協会, Aug. 2010, [Invited]
Japanese, Scientific journal

Corrosion of Al-Sn-Bi alloys in alcohols at high temperatures. Part II: Effect of anodizing on corrosion
Tatsuya Kikuchi, Yasuhito Hara, Masatoshi Sakairi, Tetsu Yonezawa, Akira Yamauchi, Hideaki Takahashi
CORROSION SCIENCE, 52, 8, 2525, 2534, PERGAMON-ELSEVIER SCIENCE LTD, Aug. 2010, [Peer-reviewed]
English, Scientific journal, Nine kinds of Al alloys were anodized to form porous anodic oxide films, and then anodized specimens were immersed in 2-(2-(2-methoxyethoxy)ethoxy)ethanol (MEEE) and 2-(2-(2-butoxyethoxy)ethoxy)ethanol (BEEE) at 415 K. Al-1.0%Sn-1.0%Bi alloy was corroded severely in both BEEE and MEEE, whereas other eight alloys showed no corrosion. The corrosion proceeded under the anodic oxide films through cracks formed in the film. Cathodic polarization in Cu electroplating solution after corrosion suggested that the crack formation during immersion in hot MEEE is due to thermal expansion of the substrate and Sn and Bi containing particles included in the anodic oxide film. (C) 2010 Elsevier Ltd. All rights reserved.

Preparation of Zinc Oxide Nanoparticles by Using Microwave-induced Plasma in Liquid
Tetsu Yonezawa, Atsushi Hyono, Susumu Sato, Osamu Ariyada
CHEMISTRY LETTERS, 39, 7, 783, 785, CHEMICAL SOC JAPAN, Jul. 2010, [Peer-reviewed]
English, Scientific journal, As a rapid and easy liquid process for preparation of ZnO nanoparticles, we propose here a microwave-induced plasma in water. Generation of plasma in liquid has been achieved at atmospheric pressure without external gas bubbling. After only several minutes of microwave irradiation, about 0.3 g of ZnO nanoparticles was obtained from an aqueous solution of zinc(II) acetate under alkaline conditions.

マウスに投与したマイクロ・ナノ無機粒子の生体内分布の追跡と細胞への影響　　　　　　　　　　　　　　　
岩寺 信喜, 阿部 薫明, 石川 紘佑, 赤坂 司, 宇尾 基弘, 大口 郁子, 八若 保孝, 亘理 文夫, 米澤 徹
北海道外科雑誌, 55, 1, 84, 85, 北海道外科学会, Jun. 2010
Japanese

Internal distribution of micro-/nano-sized ceramics and metals particles in mice
Shigeaki Abe, Ikuhiro Kida, Mitsue Esaki, Nobuki Iwadera, Mami Mutoh, Chika Koyama, Tsukasa Akasaka, Motohiro Uo, Yoshinori Kuboki, Manabu Morita, Yoshinori Sato, Koichi Haneda, Tetsu Yonezawa, Balachandran Jeyadevan, Kazuyuki Tohji, Fumio Watari
JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, 118, 1378, 525, 529, CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI, Jun. 2010, [Peer-reviewed]
English, Scientific journal, Internal distribution of several nanoparticles in mice has been investigated using scanning X-ray analytical microscopy, magnetic resonance imaging and inductively coupled plasma atomic emission spectroscopy. According dynamic laser scattering analysis, the actual particle size of obtained metal oxide was similar to that of metal particles. The estimated diameters were ca. one micrometer. After administration through the tail vein of the mice, metal particles quickly reached some organs. The distribution ratio reached a constant value and was then maintained. On the other hand, the metal oxide particles were first localized in the spleen and lung. The concentration in the lung was decreased with post-injection time. This result suggested that the particles were temporally trapped in the lung then removed to other organs. The behaviors between metal and metal oxide were quite different even when those particles had a similar actual particle size. Therefore, the distribution behavior of particles depended on the chemical species. (C) 2010 The Ceramic Society of Japan All rights reserved.

One-pot Preparation of Antioxidized Copper Fine Particles with a Unique Structure by Chemical Reduction at Room Temperature
Tetsu Yonezawa, Naoki Nishida, Atsushi Hyono
CHEMISTRY LETTERS, 39, 6, 548, 549, CHEMICAL SOC JAPAN, Jun. 2010, [Peer-reviewed]
English, Scientific journal, A one-pot and single-step reduction process for producing antioxidized copper fine particles will be described. This process can be carried out at room temperature, and size range is quite wide, from 190 nm to 1 mu m by varying the amount of gelatin, the stabilizing reagent. From SEM images it is revealed that higher loading of gelatin gave larger but relatively uniform particles. However, XRD patterns indicated that the large particles were composed of smaller particles; that is, they had a "particle-in-particle" structure. Cross-sectional TEM image strongly supports this structure and indicates that gelatin is a good antioxidizing coating material which kept 5-nm copper metallic.

Corrosion of Al-Sn-Bi alloys in alcohol at high temperatures. Part I: Effects of the metallurgical structure of the alloys and the metal salt additions to alcohol
Tatsuya Kikuchi, Yasuhito Hara, Masatoshi Sakairi, Tetsu Yonezawa, Akira Yamauchi, Hideaki Takahashi
CORROSION SCIENCE, 52, 4, 1482, 1491, PERGAMON-ELSEVIER SCIENCE LTD, Apr. 2010, [Peer-reviewed]
English, Scientific journal, Corrosion of free machining Al alloys that contain Sn and Bi was investigated at 391-415 K in 2-(2-(2-methoxyethoxy)ethoxy)ethanol (MEEE) and 2-(2-(2-butoxyethoxy)ethoxy)ethanol (BEEE) with/without SnCl(2), Sn(OC(2)H(5))(4), FeCl(3), and CuCl(2). The Al-Sn-Bi alloy displayed severe pitting corrosion in MEEE similar to the Al-Sn alloy in BEEE at 415 K, and Sn and Sn/Bi were enriched on the surface of pits. Immersion tests of pure Al in MEEE containing Sn/Cu-salts at 415 K also showed severe corrosion and the deposition of metallic Sn and Cu on the surface. The corrosion mechanisms are discussed in terms of the electro-catalytic activity of the Sn enriched on the surface. (C) 2009 Elsevier Ltd. All rights reserved.

Analysis of Polymer Layers on Red Blood Cell Surfaces with Soft Particle Models
Atsushi Hyono, Jerome F. L. Duval, Hiroyuki Ohshima, Toshio Mazda, Tetsu Yonezawa
KOBUNSHI RONBUNSHU, 67, 12, 654, 665, SOC POLYMER SCIENCE JAPAN, 2010, [Peer-reviewed], [Invited]
Japanese, Scientific journal, Analysis of human red blood cells surface properties and evaluation of the interactions among red blood cells were done to establish the mechanism of the enzyme method. Electrophoretic mobilities of intact and enzyme-treated red blood cells were analyzed with soft particle theories; one based on the diffuse models could provide further information about the properties of red blood cell surfaces. Therefore, the interaction energies between two red blood cells were evaluated and the closest distances between them were evaluated to decide the agglutinability of cells with a IgG molecule. It was concluded that thinning of the surface layer thickness plays more important role in the enzyme method than reducing the surface layer charge densities.

Platinum Nanaflowers on Scratched Silicon by Galvanic Displacement for an Effective SALDI Substrate
Hideya Kawasaki, Teruyuki Yao, Takashi Suganuma, Kouji Okumura, Yuichi Iwaki, Tetsu Yonezawa, Tatsuya Kikuchi, Ryuichi Arakawa
CHEMISTRY-A EUROPEAN JOURNAL, 16, 35, 10832, 10843, WILEY-V C H VERLAG GMBH, 2010, [Peer-reviewed]
English, Scientific journal, We report a new and facile method for synthesizing 3D platinum nanoflowers (Pt Nfs) on a scratched silicon substrate by electroless galvanic displacement and discuss the applications of the Pt Nfs in surface-assisted laser desorption/ionization-mass spectrometry (SALDI-MS). Surface scratching of n-type silicon is essential to induce Pt Nf growth on a silicon substrate (to obtain a Pt Nf silicon hybrid plate) by the galvanic displacement reaction. The Pt Nf silicon hybrid plate showed excellent SALDI activity in terms of the efficient generation of protonated molecular ions in the absence of a citrate buffer. We propose that the acidity of the Si-OH moieties on silicon increases because of the electron-withdrawing nature of the Pt Nfs; hence, proton transfer from the Si OH groups to the analyte molecules is enhanced, and finally, thermal desorption of the analyte ions from the surface occurs. Signal enhancement was observed for protonated molecular ions produced from a titania nanotube array (TNA) substrate on which Pt nanoparticles had been photochemically deposited. Moreover, surface modification of the Pt Nf silicon hybrid plate by perfluorodecyltrichlorosilane (FDTS) (to obtain an FDTS-Pt Nf silicon hybrid plate) was found to facilitate soft SALDI of labile compounds. More interestingly, the FDTS-Pt Nf silicon hybrid plate acts 1) as a high-affinity substrate for phosphopeptides and 2) as a SALDI substrate. The feasibility of using the FDTS-Pt Nf silicon hybrid plate for SALDI-MS has been demonstrated by using a beta-casein digest and various analytes, including small molecules, peptides, phosphopeptides, phospholipids, carbohydrates, and synthetic polymers. The hybridization of Pt Nfs with a scratched silicon substrate has been found to be important for achieving excellent SALDI activity.

Molten matrix sputtering synthesis of water-soluble luminescent Au nanoparticles with a large Stokes shift
Yuichi Shishino, Tetsu Yonezawa, Koji Kawai, Hiroshi Nishihara
CHEMICAL COMMUNICATIONS, 46, 38, 7211, 7213, ROYAL SOC CHEMISTRY, 2010, [Peer-reviewed]
English, Scientific journal, Water-soluble luminescent AuNPs of 1.3 +/- 0.3 nm in diameter with a large Stokes shift were facilely synthesized by a new molten matrix sputtering (MMS) method.

Sulfonate group-modified FePtCu nanoparticles as a selective probe for LDI-MS analysis of oligopeptides from a peptide mixture and human serum proteins
Hideya Kawasaki, Tarui Akira, Takehiro Watanabe, Kazuyoshi Nozaki, Tetsu Yonezawa, Ryuichi Arakawa
ANALYTICAL AND BIOANALYTICAL CHEMISTRY, 395, 5, 1423, 1431, SPRINGER HEIDELBERG, Nov. 2009, [Peer-reviewed]
English, Scientific journal, Bare FePtCu nanoparticles (NPs) are first prepared for laser desorption/ionization mass spectroscopy (LDI-MS) analysis as affinity probes to selectively trap oppositely charged analytes from a sample solution. Our present results demonstrate bare FePtCu NPs to be a potentially useful matrix for surface-assisted laser desorption/ionization mass spectroscopy (SALDI-MS), for the analysis of small proteins and peptides. The upper detectable mass range of peptides was approximately 5 kDa, and the detection limit for peptides approximately 5 fmol. Sulfonate group-modified FePtCu nanoparticles (FePtCu-SO(3)(-) NPs), with ionization being independent of the solution pH, can interact with a positively charged analyte, and the analyte-bound NPs can be separated from the reaction supernatant by centrifugation or an external magnetic field. An oligopeptide, Gly-Gly-Tyr-Arg (GGYR) from an oligopeptide mixture containing Asp-Asp-Asp-Asp (DDDD), Gly-Gly-Gly-Gly (GGGG) and GGYR, was detected using SALDI-MS with FePtCu-SO(3)(-) NPs employing electrostatic interaction. Furthermore, FePtCuSO(3)(-) NPs can detect lysozyme (Lyz) in human serum through the electrostatic attraction between positively charged Lyz and FePtCu-SO(3)(-) NPs at pH 8, while detection of negatively charged albumin in human serum is not possible.

In-Situ TEM Observations of the Crystallization Process of Solution-Prepared MoS2 Amorphous Particles
Akinori Hanzawa, Toshihiro Shimada, Tetsuya Hasegawa, Takahiro Sato, Takeo Kamino, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 9, 11, 6736, 6740, AMER SCIENTIFIC PUBLISHERS, Nov. 2009, [Peer-reviewed]
English, Scientific journal, The crystallization of polymer-mixed amorphous molybdenum sulfide was observed in-situ by a TEM equipped with a heated specimen holder. High electron beam irradiation induced the formation of a crystal structure with a lattice spacing of 0.62 nm, which corresponds to the layer spacing of MoS2. With a lower electron dose, a possible new crystal structure of molybdenum sulfide with several fringe spacings was identified at room temperature. An ordered layered structure Of MoS2 appeared after annealing at 600 degrees C. The completely different crystal phase found here might be responsible for the high temperature required for the formation of the MoS2 layered structure.

各種マイクロ・ナノ粒子の生体内での分布状態の追跡とその可視化　　　　　　　　　　　　　　　
阿部 薫明, 岩寺 信喜, 武藤 麻未, 林 大輔, 大口 郁子, 赤坂 司, 宇尾 基弘, 亘理 文夫, 高田 知哉, 米澤 徹
日本バイオマテリアル学会大会予稿集, 31回, 414, 414, 日本バイオマテリアル学会, Nov. 2009
Japanese

Basic Studies and Recent Topics for Applications of Metal Nanoparticles
HYONO Atsushi, YONEZAWA Tetsu
Journal of the Japan Society of Colour Material, 82, 10, 468, 474, Japan Society of Colour Material, 20 Oct. 2009
Japanese, Recently, metal nanoparticles have been attracting much interest as a new industrial material with their unique properties such as localized surface plasmon resonance (LSPR) and catalytic properties depending on the particle sizes. Various preparation methods have been developed in order to obtain monodispersed and stable particles. Using a wet process, size and shape can be readily controlled. Au, Ag and Cu nanoparticles appear visible colors by LSPR and are developed as an inorganic pigment. Other properties such as spectral changes with their sizes and their surface enhanced Raman scattering are applied to quick and high sensitive bio-sensing. It is also expected their unique catalytic properties can be applied to green chemistry.

Observation of Biodistribution of Indium-Tin Oxide Nanoparticles in Mice
Shigeaki ABE, Tetsu YONEZAWA, Tsukasa AKASAKA, Motohiro UO, Fumio UCHIDA, Fumio WATARI
Nano Biomedicine, 1, 1, 70, 74, Jun. 2009, [Peer-reviewed]
English, Scientific journal

Detailed Investigation on the Possibility of Nanoparticles of Various Metal Elements for Surface-Assisted Laser Desorption/Ionization Mass Spectrometry
Tetsu Yonezawa, Hideya Kawasaki, Akira Tarui, Takehiro Watanabe, Ryuichi Arakawa, Toshihiro Shimada, Fumitaka Mafune
ANALYTICAL SCIENCES, 25, 3, 339, 346, JAPAN SOC ANALYTICAL CHEMISTRY, Mar. 2009, [Peer-reviewed]
English, Scientific journal, In this paper, we describe systematic detailed considerations of the feasibility of using various metal nanoparticles for organic-matrix-free surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS). In order to avoid the influence of organic molecules on the nanoparticles, stabilizer-free bare nanoparticles of Ag, Au, Cu and Pt were prepared by laser ablation. Although all metal nanoparticles absorbed N-2 laser light (337 nm) energy, the performance of desorption/ionization of a representative peptide, angiotensin 1, strongly depended on the metal element. Citrate buffer was used as a proton source; it reduced the amount of alkali cation adducts present. Then, protonated molecules of analytes predominated in the mass spectra when Au and Pt nanoparticles were used. Pt nanoparticles showed the highest performance in SALDI-MS, owing to their smaller heat conductivity and higher melting temperature. The selective desorption of a cationic surfactant with longer alkyl chains and a peptide with methionine was also observed.

Surface Immobilization of PSI Using Vitamin K(1)-Like Molecular Wires for Fabrication of a Bio-Photoelectrode
Mariko Miyachi, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara, Michinao Iwai, Masae Konno, Masako Iwai, Yasunori Inoue
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 9, 3, 1722, 1726, AMER SCIENTIFIC PUBLISHERS, Mar. 2009, [Peer-reviewed]
English, Scientific journal, We present a bio-photoelectrode made of photosystem I complex (PSI) of cyanobacteria, Thermosynechococcus elongatus, and molecular wires. The newly designed and synthesized molecular wire similar to vitamin K, (VK,) has a naphthoquinone moiety that can connect to PSI, and a terpyridine moiety for connection to a Co(II) ion. Surface immobilization of PSI and molecular wires was performed by a self-assembled monolayer (SAM) formation process at indium tin oxide (ITO) followed by stepwise coordination reactions. The PSI-immobilized ITO showed a photocurrent action spectrum, whose profile was consistent with that of PSI. We have demonstrated a new method for the immobilization of PSI on the electrode surface, useful in the construction of phovoltaic cells or photon-sensing devices.

Plugging a Molecular Wire into Photosystem I: Reconstitution of the Photoelectric Conversion System on a Gold Electrode
Nao Terasaki, Noritaka Yamamoto, Takashi Hiraga, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara, Tsutomu Ohmori, Makoto Sakai, Masaaki Fujii, Akihiko Tohri, Masako Iwai, Yasunori Inoue, Satoshi Yoneyama, Makoto Minakata, Isao Enami
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 48, 9, 1585, 1587, WILEY-V C H VERLAG GMBH, 2009, [Peer-reviewed]
English, Scientific journal

Gold-Nanoparticle-Supported Silicon Plate with Polymer Micelles for Surface-Assisted Laser Desorption/Ionization Mass Spectrometry of Peptides
Akira Tarui, Hideya Kawasaki, Takuma Taiko, Takehiro Watanabe, Tetsu Yonezawa, Ryuichi Arakawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 9, 1, 159, 164, AMER SCIENTIFIC PUBLISHERS, Jan. 2009, [Peer-reviewed]
English, Scientific journal, We developed surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) using nanocomposite films of cationic diblock copolymer micelles [poly(styrene-b-N-methyl-4-vinyl pyridinium iodide)] and ammonium citrated Au nanoparticles (AuNPs) on silicon. The nanocomposite film on silicon was suitable for use as a material for matrix-free LDI-MS of peptides due to its low matrix background from Au clusters and high ionization efficiency; this plate successfully ionized angiotensin I, and also insulin in the proton adduct forms, in contrast to methods using only AuNPs and those using nanocomposite films of cationic polymer in conjunction with Au NPs. The high ionization efficiency is discussed from the viewpoint of nanoparticle distribution controlled by polymers on the plate (aggregates vs. nonaggregates).

In-situ observation of silver nanoparticle ink at high temperature
Tetsu Yonezawa
BIO-MEDICAL MATERIALS AND ENGINEERING, 19, 1, 29, 34, IOS PRESS, 2009, [Peer-reviewed]
English, Scientific journal, In-situ TEM (transmission electron microscopy) of silver nanoparticle ink at high temperature was carried out. Into a carbon film tube coating the spiral tungsten filament which was attached to the TEM specimen holder, a silver nanoparticle ink was injected. After evaporation, silver nanoparticles with an aggregated structure could be observed. The temperature of the tungsten wire can be controlled by DC current supplied by dry batteries. Fusion of smaller nanoparticles was observed at a higher temperature and some particles were incorporated to larger particles. This technique can be generally used to consider the sintering temperature of such metal nanoparticles.

Production of Nanoparticles and Their Applications
YONEZAWA Tetsu
Jitsumu Hyomen Gijutsu, 59, 11, 712, 717, The Surface Finishing Society of Japan, 01 Nov. 2008
Japanese

Layer-by-layer self-assembled mutilayer films of gold nanoparticles for surface-assisted laser desorption/ionization mass spectrometry
Hideya Kawasaki, Tsuyoshi Sugitani, Takehiro Watanabe, Tetsu Yonezawa, Hiroshi Moriwaki, Ryuichi Arakawa
ANALYTICAL CHEMISTRY, 80, 19, 7524, 7533, AMER CHEMICAL SOC, Oct. 2008, [Peer-reviewed]
English, Scientific journal, Layer-by-layer (LBL) self-assembled multilayer films of gold nanoparticles (AuNPs) on a silicon wafer were demonstrated to be promising substrates for surface-assisted laser desorption/ionization (SALDI) mass spectrometry (MS) of peptides and environmental pollutants for the first time. LBL multilayer films, (AuNPs/PAHC)(n), consisting of alternating layers of ammonium citrate capped AuNPs and poly(allylamine hydrochloride) (PAHC) were prepared on a silicon surface. Silicon plates with aggregated AuNPs were more suitable than those with dispersed AuNPs for the SALDI-MS of peptides. The number of particle layers had a significant effect on the laser desorption/ionization of angiotensin I; the peak intensity of the peptide (molecular ion amount) increased with an increase in the number of layers of AuNPs. As a result, the (AuNPs/PAHC)(5) multilayer films increased the sensitivity of the angiotensin I to subfemtomoles and raised the useful analyte mass range, thus making it possible to detect small proteins (a 12 kDa cytochrome c). The signal enhancement when using (AuNPs/PAHC)(5) may be due to (i) the high absorption of the UV laser fight at 337 nm by the AuNP layers, (ii) the low thermal conductivity due to the AuNPs being covered with a thin monolayer of PAHC, and (iii) the increase in the surface roughness (similar to 100 nm) with the number of AuNP layers. Thus, laser-induced rapid high heating of AuNPs for effective desorption/ionization of peptides is possible. In addition, it was found that (AuNPs/PAHC)(5) could be used to extract environmental pollutants (pyrene and dimethyldistearylammonium chloride) from very dilute aqueous solutions with concentrations less than 10(-10) mg/mL, and the analytes trapped in the LBL film could be identified by introducing the film directly into the SALDI mass spectrometer without needing to elute the analytes out of the film.

Surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) of low molecular weight organic compounds and synthetic polymers using zinc oxide (ZnO) nanoparticles
Takehiro Watanabe, Hideya Kawasaki, Tetsu Yonezawa, Ryuichi Arakawa
JOURNAL OF MASS SPECTROMETRY, 43, 8, 1063, 1071, JOHN WILEY & SONS LTD, Aug. 2008, [Peer-reviewed]
English, Scientific journal, We have developed surface-assisted laser desorption/ionization mass spectrometry using zinc oxide (ZnO) nanoparticles with anisotropic shapes (ZnO-SALDI-MS). The mass spectra showed low background noises in the low m/z, i.e. less than 500 u region. Thus, we succeeded in SALDI ionization on low molecular weight organic compounds, such as verapamil hydrochloride, testosterone, and polypropylene glycol (PPG) (average molecular weight 400) without using a liquid matrix or buffers such as citric acids. In addition, we found that ZnO-SALDI has advantages in post-source decay (PSD) analysis and produced a simple mass spectrum for phospholipids. The ZnO-SALDI spectra for synthetic polymers of polyethylene glycol (PEG), polystyrene (PS) and polymethylmethacrylate (PMMA) showed the sensitivity and molecular weight distribution to be comparable to matrix-assisted laser desorption/ionization (MALDI) spectra with a 2,5-dihydroxybenzoic acid (DHB) matrix. ZnO-SALDI shows good performance for synthetic polymers as well as low molecular weight organic compounds. Copyright (C) 2008 John Wiley & Sons, Ltd.

Size-controlled oxidation-resistant copper fine particles covered by biopolymer nanoskin
Masanori Tomonari, Kiyonobu Ida, Hiromi Yamashita, Tetsu Yonezawa
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 8, 5, 2468, 2471, AMER SCIENTIFIC PUBLISHERS, May 2008, [Peer-reviewed]
English, Scientific journal, Size-controlled oxidation-resistant copper fine particles were prepared from insoluble CuO micronsized particles. The particle sizes were quite uniform and could be varied only by the concentration of the complex reagent from 45 to 175 nm. No template material was needed for size control. Gelatin was selected as the protective polymer. Addition of protease after formation of copper fine particles decomposed preferentially loop and tail parts of gelatin. The remaining nanoskin gelatin layer, covered on the particle surface, prevents oxidation of copper.

The preparation of copper fine particle paste and its application as the inner electrode material of a multilayered ceramic capacitor
Tetsu Yonezawa, Shinsuke Takeoka, Hiroshi Kishi, Kiyonobu Ida, Masanori Tomonari
NANOTECHNOLOGY, 19, 14, IOP PUBLISHING LTD, Apr. 2008, [Peer-reviewed]
English, Scientific journal, Well size-controlled copper fine particles (diameter: 100-300 nm) were used as the inner electrode material of multilayered ceramic capacitors (MLCCs). The particles were dispersed in terpineol to form a printing paste with 50 wt% copper particles. The MLCC precursor modules prepared by the layer-by-layer printing of copper and BaTiO3 particles were cosintered. Detailed observation of the particles, paste, and MLCCs before and after sintering was carried out by electron microscopy. The sintering temperature of Cu-MLCC was as low as 960 degrees C. The permittivity of these MLCCs was successfully measured with the copper inner layers.

Surface bottom-up fabrication of porphyrin-terminated metal complex molecular wires with photo-electron conversion properties on ITO
Mariko Miyachi, Makiko Ohta, Misaki Nakai, Yoshihiro Kubota, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara
CHEMISTRY LETTERS, 37, 4, 404, 405, CHEMICAL SOC JAPAN, Apr. 2008, [Peer-reviewed]
English, Scientific journal, We fabricated photoelectron conversion system with porphyrin-terminated "molecular wires" on an ITO surface synthesized using stepwise metal-terpyridine complexation reactions. The efficiency and the electrode potential singnificantly depended on the metal center of the bis(terpyridine) complex unit in the molecular wire.

Cross-sectional STEM observation of nanoparticle-attached silicon wafer: Specimen prepared by focused ion-beam
Tetsu Yonezawa, Yoshinori Yamanoi, Hiroshi Nishihara
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 8, 3, 1518, 1522, AMER SCIENTIFIC PUBLISHERS, Mar. 2008, [Peer-reviewed]
English, Scientific journal, A thermal hydrosilylation process could successfully immobilize 5-heptene-1-thiol-stabilized gold nanoparticles onto hydrogen-terminated silicon surfaces. In order to understand the immobilization structures, it is very important to observe the linkage between the nanoparticles and the substrate surface. For this purpose, a cross-sectional observation of gold nanoparticle-attached silicon substrate was carried out by using a high resolution scanning transmission electron microscopy (HR-STEM). The specimens were prepared by using a focused ion-beam (FIB) machine. According to the Ga ion-beam irradiation, many single-nano-sized nanoparticles were fused to grow up to larger particles and amorphous Si layers were generated.

Easy preparation of stable iron oxide nanoparticles using gelatin as stabilizing molecules
Tetsu Yonezawa, Keigo Kamoshita, Masayoshi Tanaka, Takatoshi Kinoshita
JAPANESE JOURNAL OF APPLIED PHYSICS, 47, 2, 1389, 1392, JAPAN SOC APPLIED PHYSICS, Feb. 2008, [Peer-reviewed]
English, Scientific journal, Iron oxide nanoparticles were prepared by adding NaBH(4) to aqueous solution of an Fe(3+) salt in the presence of gelatin as the stabilizing reagent. The obtained nanoparticles are relatively unique and can be separated by centrifugation. They can be collected in the dried powder form by centrifugation and freeze-drying. Their structural properties analyzed by transmission electron microscopy, atomic force microscopy and X-ray diffraction, as well as their magnetic properties measured by a superconducting quantum interface device are discussed in this paper.

Wet Preparation of Metal Nanoparticles and their Immobilization on Silicon Substrates
Tetsu Yonezawa, Yoshinori Yamanoi, Hiroshi Nishihara
Metal Nanoclusters in Catalysis and Materials Science: The Issue of Size Control, 453, 458, Elsevier, 2008, [Peer-reviewed]
English, In book

Room-temperature immobilization of gold nanoparticles on Si(111) surface and their electron behaviour
Tetsu Yonezawa, Kazuki Uchida, Yoshinori Yamanoi, Shintaro Horinouchi, Nao Terasaki, Hiroshi Nishihara
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 10, 46, 6925, 6927, ROYAL SOC CHEMISTRY, 2008, [Peer-reviewed]
English, Scientific journal, Successful covalent soft immobilization of gold nanoparticles on Si(111) surface by simple immersion of hydrogen-terminated silicon wafer into a toluene dispersion of gold nanoparticles was achieved by use of a phenylalkyne-type stabilizing ligand, and the electron behaviour was investigated using a conducting AFM.

Behavior of in vitro, in vivo and internal motion of micro/nano particles of titanium, titanium oxides and others
Fumio Watari, Shigeaki Abe, Chika Koyama, Atsuro Yokoyama, Tukasa Akasaka, Motohiro Uo, Makoto Matsuoka, Yasunori Totsuka, Mitsue Esaki, Manabu Morita, Tetsu Yonezawa
JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, 116, 1349, 1, 5, CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI, Jan. 2008, [Peer-reviewed]
English, Scientific journal, To clarify the effect of micro/nanosizing of materials onto biological organism, the particle size dependence of reaction of cells and tissue as investigated by both biochemical cell functional test and animal implantation test. Especially for nanoparticles the behavior of invasion and internal diffusion inside body was visualized using an XSAM (X-ray Scanning Analytical Microscope). The increase of specific surface area is usually counted as nanosizing effect which causes the enhancement of chemical reactivity and therefore toxicity of materials such as carcinogenicity found in 500 nm Ni particles for the long term implantation in the soft tissue of rat. Even biocompatible materials such as Ti and TiO2 shows stimulus with the decrease of particle size. They cause phagocytosis to cells and inflammation to tissue when the size of particles is below 3 mu m. For the size below 50 nm, they may invade into the internal body through the respiratory or digestive system and diffuse inside body. After compulsory exposure test of 30 nm TiO2 particles through the respiratory system, the Ti mapping by XSAM showed the internal diffusion inside the whole body. Nanoparticles injected from caudal vein diffused with time course to lung, liver and spleen. The uptake of 30 nm TiO2 particles through the digestive system and diffusion into these organs was also confirmed. These phenomena observed in biocompatible or bioinert materials are the nonspecific, physical particle and shape effects which occur independent of materials. Nanoparticles might be the objects whose existence has not been assumed by the living body defense system.

Effects of preparation conditions on the synthesis off nano-sized Ag metal particles by the wet-process using 3-mercapto-propionic acid
Masanori Tomonari, Kiyonobu Ida, Hironori Imanishi, Tetsu Yonezawa, Kohsuke Mori, Hiromi Yamashita
RESEARCH ON CHEMICAL INTERMEDIATES, 34, 5-7, 641, 647, VSP BV, 2008, [Peer-reviewed]
English, Scientific journal, By the addition of sodium borohydride as a reducing agent into an aqueous solution of AgNO3 mixed with 3-mercapto-propionic acid as a protective agent, nano-sized Ag metal particles could be synthesized. Using this advanced wet-process the synthesis of an aqueous Ag colloid system with a high density became possible, because the surfaces of the synthesized nano-sized Ag metal particles were covered and protected by the adsorbed 3-mercapto-propionic acid. By changing the mix ratio of AgNO3 to 3-mercapto-propionic acid, the particle size of synthesized nano-sized Ag metal particles could be controlled; a higher 3-mercapto-propionic acid/AgNO3 ratio was preferable in the synthesis of smaller Ag metal particles. From the relationship between the Ag metal particle size and the residual S content adsorbed on the metal particles, the mechanism of dispersion of Ag particles can be proposed as that the 3-mercapto-propionic acid having a thiol group adsorbs on Ag particles by forming Ag-S bonds as a protective agent.

Observation of electrochemical single-electron-transfer events of gold nanoparticles in aqueous solution in the presence of both ammonium and sulfonate surface-active agents
Misaki Nakai, Yoshinori Yamanoi, Yoshihiko Nishimori, Tetsu Yonezawa, Hiroshi Nishihara
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 35, 6699, 6702, WILEY-BLACKWELL, 2008, [Peer-reviewed]
English, Scientific journal

Fusion and growth behavior of gold nanoparticles stabilized by allylmercaptane
Naoto Shirahata, Tetsu Yonezawa, Yoshihiro Matsushita, Yoshitake Masuda, Kunihito Koumoto
MACROMOLECULAR SYMPOSIA, 270, 82, 87, WILEY-V C H VERLAG GMBH, 2008, [Peer-reviewed]
English, International conference proceedings, Fusion and growth behavior of gold nanoparticles in a relatively low temperature range were studied using a transmission electron microscopy (TEM). Using allylmercaptane (AM: 2-propene-1-thiol, HS-CH2-CH=CH2) as a particle stabilizer, a colloidal suspension of AM-terminated gold nanoparticles was prepared with a two-phase system. TEM observation revealed that the adjacent nanoparticles formed a particulate neck to give fused nanoproducts even at lower than 65 degrees C. Such fusion behavior allowed a non-spherical growth of the adjacent nanoparticles. Interestingly, the nanoparticle fused to form a nanowire-type structure when the thermal radical reaction occurred between the terminal double carbon bond of the stabilizer and the hydrogen terminated surface of silicon wafer.

Nanocage catalysts-rhodium nanoclusters encapsulated with dendrimers as accessible and stable catalysts for olefins and nitroarene hydrogenations
Ikuse Nakamula, Yoshinori Yamanoi, Tetsu Yonezawa, Takane Imaoka, Kimihisa Yamamoto, Hiroshi Nishihara
CHEMICAL COMMUNICATIONS, 44, 5716, 5718, ROYAL SOC CHEMISTRY, 2008, [Peer-reviewed]
English, Scientific journal, The phenylazomethine dendrimer generation 4 (TPP-DPA G4) and polyamidoamine dendrimer (PAMAM G4-OH) encapsulating rhodium nanocluster were found to be highly effective for olefin and nitroarene hydrogenations, affording high TOF (up to 17520 h(-1)); the important feature of the nanocage catalyst is that substrates can pass through the branches of the protecting groups of nanoclusters without releasing nanoclusters from the dendrimer.

Platinum nanoflowers for surface-assisted laser desorption/ionization mass spectrometry of biomolecules
Hideya Kawasaki, Tetsu Yonezawa, Takehiro Watanabe, Ryuichi Arakawa
JOURNAL OF PHYSICAL CHEMISTRY C, 111, 44, 16278, 16283, AMER CHEMICAL SOC, Nov. 2007, [Peer-reviewed]
English, Scientific journal, No-template synthesis of surface clean platinum nanomaterials with thin projections (petals) on the Pt nanoparticle surface, termed Pt nanoflowers, has been developed, and Pt nanoflowers have achieved superior performance on surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) of biomolecules. With this new material, one can obtain high-resolution mass spectra with lower laser energy and smaller sample amounts, and no organic matrix is needed for laser desorption/ionization. The mass spectra also have fewer obstacle peaks at the lower m/z region. Furthermore, this novel substrate is quite stable against aging and showed no sweet-spot problems, that is, equal sensitivity on the whole substrate surface. Various biomolecules, including peptides and phospholipids, were examined, and Pt nanoflowers showed good performance for matrix-free laser desorption/ionization MS of these materials.

Positioning of cationic silver nanoparticle by using AFM lithography and electrostatic interaction
Tetsu Yonezawa, Tetsuya Itoh, Naoto Shirahata, Yoshitake Masuda, Kunihito Kournoto
APPLIED SURFACE SCIENCE, 254, 2, 621, 626, ELSEVIER SCIENCE BV, Sep. 2007, [Peer-reviewed]
English, Scientific journal, One-dimensional metal lines of silver nanoparticles with a nano-sized width were generated onto silicon surface by using a nano-level lithography technique, field induced oxidation (FIO) by AFM, on self-assembled monolayer-modified Si wafers. This FIO technique provided SiO2 lines a width of less than 100 nm. Short-time immersion of partially anodized silicon surface which is covered by a cationic silanol surfactant ((CH3O)(3)SiCH2CH2CH2N(CH3)(3)Cl-+(-))-monolayer into quaternary ammonium (HSCH2CH2N(CH3)(3)Br-+(-))-covered silver nanoparticles readily and reproducibly gave nano-metal lines of silver onto silicon wafers. Hydrophilicity of the whole wafer surface was indispensable for homogeneously wetting the anodized SiO2 area with a nanodimensional width. (c) 2007 Elsevier B.V. All rights reserved.

Fabrication of submillimeter-sized gold plates from thermal decomposition of HAuCl4 in two-component ionic liquids
Hideya Kawasaki, Tetsu Yonezawa, Kouhei Nishimura, Ryuichi Arakawa
CHEMISTRY LETTERS, 36, 8, 1038, 1039, CHEMICAL SOC JAPAN, Aug. 2007, [Peer-reviewed]
English, Scientific journal, We first report the fabrication of submillimeter-sized Au plates (up to about I mm in size) through the simple thermal decomposition of HAUCl(4) in two-component ionic liquids of 1-butyl-3-methylimidazolium hexafluorophosphate (C4ImPF6) and 1-octyl-3-methylimidazolium hexafluorophosphate (C8ImPF6), which were about ten times larger sizes than those from the single-component ionic liquid of the either.

Bio-photosensor: Cyanobacterial photosystem I coupled with transistor via molecular wire.
Nao Terasaki, Noritaka Yamamoto, Kaoru Tamada, Mineyuki Hattori, Takashi Hiraga, Akihiko Tohri, Ikutaro Sato, Masako Iwai, Michinao Iwai, Shunpei Taguchi, Isao Enami, Yasunori Inoue, Yoshinori Yamanoi, Tetsu Yonezawa, Katsuya Mizuno, Masaki Murata, Hiroshi Nishihara, Satoshi Yoneyama, Makoto Minakata, Tsutomu Ohmori, Makoto Sakai, Masaaki Fujii
Biochimica et biophysica acta, 1767, 6, 653, 9, Jun. 2007, [International Magazine]
English, Scientific journal, We report on the first successful output of electrons directly from photosystem I (PSI) of thermophilic cyanobacteria to the gate of a field-effect transistor (FET) by bypassing electron flow via a newly designed molecular wire, i.e., artificial vitamin K(1), and a gold nanoparticle; in short, this newly manufactured photosensor employs a bio-functional unit as the core of the device. Photo-electrons generated by the irradiation of molecular complexes composed of reconstituted PSI on the gate were found to control the FET. This PSI-bio-photosensor can be used to interpret gradation in images. This PSI-FET system is moreover sufficiently stable for use exceeding a period of 1 year.

Bio-photo sensor: Cyanobacterial photosystem I coupled with transistor via molecular wire
Nao Terasaki, Noritaka Yamamoto, Kaoru Tamada, Mineyuki Hattori, Takashi Hiraga, Akihiko Tohri, Ikutaro Sato, Masako Iwai, Michinao Iwai, Shunpel Taguchi, Isao Enami, Yasunori Inoue, Yoshinori Yamanoi, Tetsu Yonezawa, Katsuya Mizuno, Masaki Murata, Hiroshi Nishihara, Satoshi Yoneyama, Makoto Minakata, Tsutomu Ohmori, Makoto Sakai, Masaaki Fujii
BIOCHIMICA ET BIOPHYSICA ACTA-BIOENERGETICS, 1767, 6, 653, 659, ELSEVIER SCIENCE BV, Jun. 2007, [Peer-reviewed]
English, Scientific journal, We report on the first successful output of electrons directly from photosystem I (PSI) of thermophilic cyanobacteria to the gate of a field-effect transistor (FET) by bypassing electron flow via a newly designed molecular wire, i.e., artificial vitamin K-1, and a gold nanoparticle; in short, this newly manufactured photosensor employs a bio-functional unit as the core of the device. Photo-electrons generated by the irradiation of molecular complexes composed of reconstituted PSI on the gate were found to control the FET. This PSI-bio-photosensor can be used to interpret gradation in images. This PSI-FET system is moreover sufficiently stable for use exceeding a period of I year. (c) 2006 Elsevier B.V. All rights reserved.

Preparation of Metal Nanoparticles and Their Immobilization
YONEZAWA Tetsu
日本写真学会誌 = Journal of The Society of Photographic Science and Technology of Japan, 70, 1, 26, 29, 日本写真学会, 2007, [Invited]
Japanese, Scientific journal

Synthesis of nano-sized Ag metal particles protected by adsorbed 3-mercapto-propionic acid
Masanori Tomonari, Hilo Sadohara, Tetsu Yonezawa, Kohsuke Mori, Hiromi Yamashita
JOURNAL OF CERAMIC PROCESSING RESEARCH, 8, 3, 195, 198, KOREAN ASSOC CRYSTAL GROWTH, INC, 2007, [Peer-reviewed]
English, Scientific journal, Nano-sized Ag metal particles can be synthesized by the addition of sodium borohydride as a reducing agent into an aqueous solution of AgNO3 mixed with 3-mercapto-propionic acid as a protective agent. Using this method the synthesis of an aqueous Ag colloid system with a high density became possible, because the surfaces of synthesized nano-sized Ag metal particles were covered and protected by the adsorbed 3-mercapto-propionic acid. The strong electrostatic repulsion of the negative charge of the carboxylate anion of the adsorbed 3-mercapto-propionic acid disturbed the aggregation of metal particles in the solution with a high pH value (pH > 5), but the aggregation occurred in a solution of low pH value (pH < 2) because of the neutral surface of particles. Using simple coating and baking processes with this aqueous Ag colloid system, an Ag membrane can be formed on glass plate by the partial welding between the nano-size Ag particles. This Ag membrane exhibited a very low electrical resistivity even after baking at a low temperature such as 423 K.

Trial of functionalization of silicon tip surface by Si-C bonding
Tetsu Yonezawa, Naoto Shirahata, Yoshiko Miura
TRANSACTIONS OF THE MATERIALS RESEARCH SOCIETY OF JAPAN, VOL 32, NO 3, 32, 3, 767, 768, MATERIALS RESEARCH SOCIETY JAPAN-MRS-J, 2007, [Peer-reviewed]
English, International conference proceedings, Functionalization of silicon tip was carried out by photochemical/thermal hydrosilylation with an alkene-terminated sugar derivative. Si-C bond formation was suitable for preparation of monolayer on silicon surface. The tip was heated in a toluene solution of a sugar derivative with a special flask for hydrosilylation of small materials. With the functionalized tip, patterned surface of a silicon substrate was scanned.

Preparation and characterization of polypeptide-stabilized gold nanoparticles
Tetsu Yonezawa, Takashi Nomura, Takatoshi Kinoshita, Kunihito Koumoto
JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, 6, 6, 1649, 1654, AMER SCIENTIFIC PUBLISHERS, Jun. 2006, [Peer-reviewed]
English, Scientific journal, Helical polypeptides have a highly rigid conformation. In order to control self-assembling structure in nanoscale, the rigidity of the stabilizing molecules, which is working as scaffolds, is highly important. Furthermore, the molecular lengths of polypeptides can be readily controlled by using their unique polymerization methods. In this study, we have used helical polypeptides as the stabilizing reagent of metal nanoparticles. As for rigid helical polypeptides, poly(gamma-benzyl-L-glutamate) (PBLG) was selected, and was synthesized by N-carboxylic acid anhydride (NCA) polymerization. Preparation of helical polypeptide-stabilized gold nanoparticles using a two-phase reduction process from the corresponding metal salts with NaBH4 is therefore introduced. PBLG itself did not have good stabilizing ability for metal nanoparticles and a terminal attaching ligand was indispensable for nanoparticle stabilization and, for this purpose, lipoic acid was selected. It is estimated that lipoic acid functionalized polypeptide molecules were attached perpendicularly to the particle surface by lipoic acid group. The size and structure, as well as assembling will be discussed in this manuscript.

An efficient matrix that resists the nonspecific adsorption of protein to fabricate carbohydrate arrays on silicon
N Shirahata, A Hozumi, Y Miura, K Kobayashi, Y Sakka, T Yonezawa
THIN SOLID FILMS, 499, 1-2, 213, 218, ELSEVIER SCIENCE SA, Mar. 2006, [Peer-reviewed]
English, Scientific journal, Efficient matrix that resists the nonspecific adsorption of proteins from the contacting phosphate buffer silane (PBS) solution has been explored to fabricate carbohydrate arrays on silicon wafer. p-Vinylbenzyllactonoamide (VLA) was immobilized onto silicon through Si-C bond. The VLA-covered substrate was then photo lithographically micropatterned through a photomask by ultraviolet (UV) irradiation. The VLA-covered regions recognized specifically the lactose-binding lectin in PBS solution. On the other hand, the U-V-irradiated regions, i.e., SiOx surface, prevented the nonspecific adsorption of the lectin from the contacting PBS solution. Several control experiments have demonstrated that the resistant-ability of SiOx surface as the matrix was comparable to the best of known system for resisting the nonspecific adsorption. (c) 2005 Elsevier B.V All rights reserved.

Hydrogen storage properties of isocyanide-stabilized palladium nanoparticles
Shintaro Horinouchi, Yoshinori Yamanoi, Tetsu Yonezawa, Toshihiro Mouri, Hiroshi Nishihara
Langmuir, 22, 4, 1880, 1884, 14 Feb. 2006, [Peer-reviewed]
English, Scientific journal, Monodispersed palladium nanoparticles protected with n-octyl isocyanide were prepared, and their hydrogen absorption behavior was evaluated. The formation of the nanoparticles has been confirmed by means of 1H NMR and elemental analysis. Fourier transform infrared (FT-IR) showed that three distinct bands (2156, 1964, and 1611 cm-1) assigned to mono-, double-, and triple-bridged isocyanide ligands on the palladium surface. The average diameter of the particles was estimated to be 2.1±0.7 nm from observation by transmission electron microscopy (TEM). X-ray photoelectron spectroscopy (XPS) analysis revealed that the particles contained Pd(0) with little amounts of Pd(II) or Pd(IV), in sharp contrast to the thiol- or phosphine-stabilized palladium nanoparticles. The absorption and desorption of hydrogen were reversible, and the reactions were much faster for the nanoparticles than for the bulk palladium metal, whereas the storage capacity was almost the same, 0.6 wt %. © 2006 American Chemical Society.

Synthesis, single crystal X-ray analysis, and TEM for a single-sized Au-11 cluster stabilized by SR ligands: The interface between molecules and particles
K Nunokawa, S Onaka, M Ito, M Horibe, T Yonezawa, H Nishihara, T Ozeki, H Chiba, S Watase, M Nakamoto
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 691, 4, 638, 642, ELSEVIER SCIENCE SA, Feb. 2006, [Peer-reviewed]
English, Scientific journal, An SR-modified Au cluster with a sub-nanometer size, Au-11(S-4-NC5H4)(3)(PPh3)(7) (1), has been synthesized by NaBH4 reduction of Au(S-py)(PPh3)or by reacting [Au-9(PPh3)(8)](NO3)(3) with HS-4-py in good yield. Its molecular structure has been elucidated by single crystal X-ray diffraction, and TEM observation has been achieved for the first time for this size of SR-modified An clusters. The core structure is best described in terms of an incomplete icosahedron. CV measurements in CH2Cl2 have suggested that the cluster does not coagulate in solution with significant concentration. (c) 2005 Elsevier B.V. All rights reserved.

Photo-assisted immobilization of gold nanoparticles on silicon substrate
Tetsu Yonezawa, Naoto Shirahata, Nao Terasaki, Yoshinori Yamanoi, Hiroshi Nishihara
Polymer Preprints, Japan, 55, 1, 1309, 2006
International conference proceedings, Alkene thiol-stabilized gold nanoparticles were immobilized onto hydrogen-terminated silicon surface by using hydrosilylation. 1-Hexenethiol-stabilized gold nanoparticles were obtained by NaBH4 reduction of HAuCl4. About half of C=C bonds are saturated during the preparation of nanoparticles. The obtained gold nanoparticles were tried to be immobilized onto silicon surface by thermal- and photo-assisted (Lamp: Sanei UVF-203S) hydrosilylation. Comparing the SEM images of the obtained silicon surfaces, both systems work very well but photo-assisted process gave a more dispersed structure.

Structural analysis of silicon(111) surface immobilized by alkenylbenzenethiolato-protected gold nanoparticles
Kazuki Uchida, Shintaro Horinouchi, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara, Nao Terasaki
Polymer Preprints, Japan, 55, 2, 3490, 2006
International conference proceedings, 4-Ethynylbenzenethiolato-protected gold nanoparticles were prepared. Themal hydrosilylation was performed in order to immobilize nanoparticles onto a hydrogen-terminated silicon(111) surface through conjugated chains. The structure of the modified surface was mainly observed by SEM, AFM and IR.

Rh nanoparticles stabilized with phenylazomethine dendrimers as a catalyst for olefin hydrogenation
Ikuse Nakamula, Yoshinori Yamanoi, Tetsu Yonezawa, Hiroshi Nishihara, Kimihisa Yamamoto
Polymer Preprints, Japan, 55, 2, 4082, 2006
International conference proceedings, Rh nanoparticles stabilized in phenylazomethine dendrimers were prepared by the chemical reduction of Rh(III)-dendrimer complexes. TEM and MALDI-TOF-MS studies provided the information on the encapsulation of the Rh nanoparticles by the dendrimers. These Rh nanoparticles showed higher catalytic ability for the hydrogenation of alkenes than Wilkinson complex.

Detailed structural examinations of covalently immobilized gold nanoparticles onto hydrogen-terminated silicon surface
Y Yamanoi, N Shirahata, T Yonezawa, N Terasaki, N Yamamoto, Y Matsui, K Nishio, H Masuda, Y Ikuhara, H Nishihara
CHEMISTRY-A EUROPEAN JOURNAL, 12, 1, 314, 323, WILEY-V C H VERLAG GMBH, 2006, [Peer-reviewed]
English, Scientific journal, The modification of flat semi-conductor surfaces with nanoscale materials has been the subject of considerable interest. This paper provides detailed structural examinations of gold nanoparticals covalently immobilized onto hydrogen-terminated silicon surfaces by a convenient thermal hydrosilylation to form Si-C bonds. Gold nanoparticles stabilized by omega-alkene-1-thiols with different alkyl chain lengths (C-3,C- C-6, and C-11), with average diameters of 2-3 nm and a narrow size distribution were used. The thermal hydrosilylation reactions of these nanoparticles with hydrogen-terminated Si(111) surfaces were carried out in toluene at various conditions under N-2. The obtained modified surfaces were observed by high-resolution scanning electron microscopy (HR-SEM). The obtained images indicate considerable changes in morphology with reaction time, reaction temperature, as well as the length of the stabilizing omega-alkene-1-thiol molecules. These surfaces are stable and can be stored under ambient conditions for several weeks without measurable decompostion. It was also found that the aggregation of immobilized particles on a silicon surface occurred at high temperature (> 100 degrees C). Precise XPS measurements of modified surfaces were carried out by using a Au-S ligand-exchange technique. The spectrum clearly showed the existence of Si-C bonds. Cross-sectional HR-TEM images also directly indicate that the particles were covalently attached to the silicon surface through Si-C bonds.

Wet preparation of metal nanoparticles and their two-dimensional arrangement
Tetsu Yonezawa
TRANSACTIONS OF THE MATERIALS RESEARCH SOCIETY OF JAPAN, VOL 31, NO 2, 31, 2, 553, 555, ELSEVIER SCIENCE BV, 2006, [Peer-reviewed]
English, International conference proceedings, This review article describes about wet preparation of metal nanoparticles, especially, preparation is relatively easy and useful for high volume preparation. After the breakthrough of Brust's thiol stabilizing system, small and monodispersed nanoparticles have been demonstrated frequently. By using such thiol-stabilizing nanoparticles, their ordered two-dimensional arrangement has been prepared with tuned stabilizing molecules. In this manuscript, such techniques of 2-D arrangement preparation will be also discussed in detail.

A new 19-metal-atom cluster [ (Me2PhP)10Au 12Ag7(NO3)9] with a nearly staggered-staggered M5 ring configuration
Keiko Nunokawa, Mitsuhiro Ito, Tetsuya Sunahara, Satoru Onaka, Tomoji Ozeki, Hirokazu Chiba, Yasuhiro Funahashi, Hideki Masuda, Tetsu Yonezawa, Hiroshi Nishihara, Masami Nakamoto, Mari Yamamoto
Dalton Transactions, 16, 2726, 2730, 21 Aug. 2005, [Peer-reviewed]
English, Scientific journal, New mixed metal clusters with M19 metal frameworks have been synthesized by NaBH4 reduction of Au(NO3)(PMe 2Ph) together with AgNO3 in ethanol. Single crystal X-ray diffraction has revealed Au12Ag7 and Au 17Ag2 metal skeletons for these clusters, which are best described in terms of bicapped pentagonal antiprismatic cages with a staggered-staggered M5 ring configuration. These clusters connect the missing link between M13 icosahedral and M25 biicosahedral clusters providing a view of the cluster growth process. A TEM image of this cluster has been observed, which has clearly demonstrated single-sized nano-particles of less than 1.0 nm. © The Royal Society of Chemistry 2005.

Fabrication of periodic arrays of self-assembled monolayer by droplet-method　　　　　　　　　　　　　　　
Naoto Shirahata, Tetsu Yonezawa, Atsushi Hozumi, Yoshio Sakka
Polymer Preprints, Japan, 54, 1, 886, 2005
Japanese, International conference proceedings, We have successfully developed a novel fabrication method for periodic array structures of organosilane self-assembled monoalyers (SAMs) on one substrate under mild condition. In general, SAM array structures have been fabricated by a variety of well-developed lithography systems including deep-UV lithography. However, these general patterning methods cannot form different kinds of SAMs on one substrate. Thus, it has been impossible to fabricate the arrayed devices including molecular arrays and bioarrays. We have revolutionary realized to fabricate the array structures with different kinds of SAMs on one substrate under environmental friendly condition utilizing our developed droplet-method.

Self-assembled structure of peptide-Au nanoparticle mixed cast film　　　　　　　　　　　　　　　
Akihiro Miyata, Tetsu Yonezawa, Masayoshi Tanaka, Takatoshi Kinoshita
Polymer Preprints, Japan, 54, 1, 1151, 2005
Japanese, International conference proceedings, Self-organized structures in nano- and micro-meter scale are expected as electronic and optical devices owing to their periodicity. In order to construct the self-organized structure, cast method was adopted as a simple approach. At first, α-helical polypeptide, poly(y-benzyl L-glutamate) (PBLG), was synthesized by an NCA polymerization method, and dodecanethiol-stabilized Au nanoparticle was prepared. Then, a mixed solution of PBLG and Au nanoparticles was casted on a pure mica substrate to give a peptide-Au nanoparticle mixed film. The cast film formed was observed by AFM, TEM and SEM. From the AFM images, two-dimensional network structures composed of PBLG and Au nanoparticles were observed(Fig.1). The structures of cast films notably changed according to the conditions such as humidity, and mixed ratio. The result of TEM observation clearly showed that Au nanoparticle arranged along the PBLG network.

Wet Preparation of Metal Nanoparticles and Their Structure Characterization, and Technology of Their Painting and Immobilization
YONEZAWA Tetsu
Jitsumu Hyomen Gijutsu, 56, 12, 743, 747, The Surface Finishing Society of Japan, 2005, [Invited]
Japanese, Scientific journal

Immobilization of gold nanoparticles onto semiconductor surface
Yoshinori Yamanoi, Shintaro Horinouchi, Kazuki Uchida, Tetsu Yonezawa, Hirishi Nishihara, Naoto Shirahata, Nao Terasaki, Noritaka Yamamoto, Yoshitaka Matusi, Kazuyuki Nishio, Hideki Masuda, Yuichi Ikuhara
Polymer Preprints, Japan, 54, 2, 3541, 2005
International conference proceedings, Gold nanoparticles, which have unsaturated C-C bonds in stabilizers, were prepared and then covalently linked to a hydrogen-terminated silicon(111) surface with Si-C bonds via a thermal hydrosilylation reaction. The modified silicon surfaces were observed mainly by high-resolution scanning electron microscopy (HR-SEM) and the fixation of nanoparticles through Si-C bonds was finally investigated by XPS and cross sectional TEM.

Detailed structure observation of gold nanopracticles immobilized on silicon surface
Tetsu Yonezawa, Yoshinori Yamanoi, Hiroshi Nishihara, Nao Terasaki, Noritaka Yamamoto, Naoto Shirahata
Polymer Preprints, Japan, 54, 1, 965, 2005
International conference proceedings, Hydrogen-terminated silicon surface is now becoming one of promising substrates to provide good SAM layers with Si-C covalent bonds. Many kinds of SAM layers have been proposed, such as simple alkyl SAMs for preventing oxidation of the surface or SAMs of functional molecules, e. g., bio molecules for bio-sensing. We applied this technique to immobilize gold nanoparticles. By simple sintering of H-terminated Si wafers into toluene dispersions of ω-alkene-1-thiol-stabilized gold nanoparticles gives Au-nanoparticle immobilized Si surface. Detailed structural analyses of these wafers will be reported.

Monolayer-derivative functionalization of non-oxidized silicon surfaces
N Shirahata, A Hozumi, T Yonezawa
CHEMICAL RECORD, 5, 3, 145, 159, JOHN WILEY & SONS INC, 2005, [Peer-reviewed]
English, Scientific journal, This article describes a variety of monolayers anchored directly onto silicon surfaces without an oxide interlayer, their formation mechanisms, their technological applications, and our personal views on the future prospects for this field. The chemical modification of non-oxidized silicon surfaces utilizing monolayers was first reported in 1993. The basic finding that a non-oxidized silicon surface could be neutralized with alkyl chains through direct covalent linkage, i.e., silicon-carbon, has offered chemical scientists ease of handling even in an ambient environment and, thus, research has been predictably focused on forming anti-stiction coating films for nano- and micro-electromechanical systems (NEMS/MEMS). Such surface reforming has also been achieved by using other monolayers, which form interfacial bonds, e.g., silicon-nitrogen and silicon-oxygen. The resultant monolayer surfaces are useful for silicon-based applications including molecular electron transfer films, monolayer templates, molecular insulators, capsulators, and bioderivatives. Such monolayers are applicable not only for surface modification, but also for manipulating individual nanomaterials. By modifying the terminal groups of monolayers with nanomaterials including nanocrystals and biomolecules, the nanomaterials can remarkably be immobilized directly onto non-oxidized silicon surfaces based on the formation mechanisms of the monolayer. Such immobilizations will revolutionize the analysis of the specific features and capabilities of individual nanomaterials. Furthermore, the path will be opened for the development of more advanced monolayer-derived chip technology. To achieve this goal, it is extremely important to thoroughly understand the functionalization processes on silicon, since the resultant internal structures and properties of monolayer-derivative silicon may strongly depend on their course of formation. (c) 2005 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Non-equilibrium structures of a-helix rod type hydrophobic polypeptide molecules on mica surfaces
Tetsu Yonezawa, Akihiro Miyata, Masayoshi Tanaka, Takatoshi Kinoshita
Transactions of the Materials Research Society of Japan, Vol 30, No 4, 30, 4, 1259, 1261, ELSEVIER SCIENCE BV, 2005, [Peer-reviewed]
English, International conference proceedings, A hydrophobic polypeptide, poly(gamma-benzyl-L-glutamate) (PBLG), has a solid and rod-like a-helix structure. According to this rigid molecular conformation, this type of peptide molecules forms good Langmuir-Brodgett (LB) thin films. In this study, non-equilibrium self-assembled structures, called dissipated structures, of PBLG were observed by putting and drying a 1,2-dichloroethane drop of PBLG on a hydrophilic mica surface. AFM images of the dried sample on mica clearly show the multi-layered structure of PBLG molecules with honeycomb structures under high humidity conditions. On the contrary, under low humidity conditions, densely packed cholesteric liquid crystal-like structures were observed without holes.

Synthesis of.surfactant-stabilized Co/Au bimetallic nanoparticles with a core-shell structure
Tetsu Yonezawa, Kazuhiko Shibuya, Hiroshi Nishihara
Transactions of the Materials Research Society of Japan, Vol 30, No 4, 30, 4, 1255, 1257, ELSEVIER SCIENCE BV, 2005, [Peer-reviewed]
English, International conference proceedings, Well-defined surfactant-stabilized "Co-shell Au-core" bimetallic nanoparticles were successfully prepared in the presence of the mixture of two surfactant molecules. The formation of these core-shell structures is driven by the thermal deposition of Co(CO)(g) by refluxing p-xylene solution in the presence of the pre-formed gold nanoparticles which were prepared by NaBH4-reduction of RAuCl4. Continuous layer of cobalt without vacancies wrapping the gold core was revealed by TEM observation and the obtained bimetallic nanoparticles could be dispersed stably.

Interfacial observation of an alkylsilane self-assembled monolayer on hydrogen-terminated Si
N Shirahata, WS Seo, T Kinoshita, T Yonezawa, A Hozumi, Y Yokogawa, T Kameyama, Y Masuda, K Koumoto
LANGMUIR, 20, 20, 8942, 8946, AMER CHEMICAL SOC, Sep. 2004, [Peer-reviewed]
English, Scientific journal, We have successfully observed that an octadecyltrichlorosilane self-assembled monolayer (OTS-SAM) can be anchored onto hydrated silicon surface utilizing several kinds of analytical methods as follows. HR-TEM observation found that no SiO2 interlayer formed between OTS-SAM and a hydrogen-terminated Si(001) surface. The static water-contact angle on the Si:H substrate increased with immersion time in anhydrous toluene containing 1.0 vol% of OTS molecules and reached 110°, resulting in formation of a pure methyl-terminated Si surface. The surface hydrophobicity was maintained even after the treatments of the scotch tape test and stringent sonication test in dilute alkaline aqueous base at pH 10. Octadecyltrimethoxysilane could not anchor onto the Si:H surface. It was thus clarified that only trichlorosilane molecule could anchor onto a Si surface without an intervening SiO2 interlayer.

Observation of selenium-77 nuclear magnetic resonance in octaneselenol-protected gold nanoparticles
Brian S. Zelakiewicz, Tetsu Yonezawa, YuYe Tong
Journal of the American Chemical Society, 126, 26, 8112, 8113, 07 Jul. 2004, [Peer-reviewed]
English, Scientific journal, We report the first observation of 77Se nuclear magnetic resonance (NMR) in octaneselenol-protected Au nanoparticles of an average particle size of 2.5 nm. The 77Se NMR characteristics observed, i.e., broad line shape, fast nuclear spin-lattice, and spin-spin relaxation rates, which are reminiscent of 13C NMR of CO on transition metal surfaces, strongly suggest that Se becomes metallic upon binding to the Au nanoparticle surfaces. Copyright © 2004 American Chemical Society.

Photoinduced cleavage of alkyl monolayers on Si
N Shirahata, T Yonezawa, WS Seo, K Koumoto
LANGMUIR, 20, 4, 1517, 1520, AMER CHEMICAL SOC, Feb. 2004, [Peer-reviewed]
English, Scientific journal, This is the first report for the photolithography of the Si-C linked monolayers directly bonded onto Si substrate surface. We experimentally found that the Si-C bonds formed between the terminated carbons of the monolayers and Si atoms at Si substrate surface are cleaved by ultra-violet (UV) irradiation in ambient air. In addition, HR-TEM observation clarified no SiO2 interlayer intervenes between alkyl monolayer and Si. This basic finding can extensively contribute to both the fields of (1) the academic photochemical study and (2) the monolayer technology including materials science, as follows.

Immobilization of gold nanoparticles onto silicon surfaces by Si-C covalent bonds
Y Yamanoi, T Yonezawa, N Shirahata, H Nishihara
LANGMUIR, 20, 4, 1054, 1056, AMER CHEMICAL SOC, Feb. 2004, [Peer-reviewed]
English, Scientific journal, A series of omega-alkene-1-thiol-stabilized gold nanoparticles were prepared by a wet process and then covalently linked to a hydrogen-terminated silicon(11 1) surface with Si-C bonds via a thermal hydrosilylation reaction. The modified silicon surfaces were observed mainly by high-resolution scanning electron microscopy (HR-SEM). The HR-SEM images revealed that the gold nanoparticles protected with 2-propene-1-thiol (0) were covalently bound to the hydrogen-terminated silicon surface, after which the nanoparticles self-fused; on the other hand, gold nanoparticles protected with 5-hexene-1-thiol (C6) or 10-undecene-1-thiol (C11) were linked to the hydrogen-terminated silicon surface independently. These surfaces were stable in air and can be stored for several months without detectable decomposition.

Atomic scale flattening of organosilane self-assembled monolayer and patterned tin hydroxide thin films
N Shirahata, Y Masuda, T Yonezawa, K Koumoto
JOURNAL OF THE EUROPEAN CERAMIC SOCIETY, 24, 2, 427, 434, ELSEVIER SCI LTD, 2004, [Peer-reviewed]
English, Scientific journal, We have succeeded in fabricating an atomic flattening surface of organosilane self-assembled monolayers (SAMs) on a Si substrate. In the present process, the octadecyltrichlorosilane (OTS) compound was selected as the starting material for the SAM. The OTS-SAM was formed by the reaction between the OTS molecules and the substrates, which were hydrogen terminated Si(001) (H:Si) and silica covered on Si(001) (SiO2/Si), at room temperature in a N-2 atmosphere. The formation rate of the OTS-SAM onto H:Si was smaller than that on SiO2/Si. Interestingly, the hydrophobicity of the OTS-SAM was observed to increase the amount formed on H:Si in comparison with that on SiO2/Si. The photo reactivity of the SAMs formed on each substrate was also investigated by using ultraviolet (UV) irradiation in ambient air. Tin hydroxide thin films were site-selectively deposited on the patterned OTS-SAM/Si substrate in order to clarify the cleavage of the OTS-SAM by the UV irradiation. (C) 2003 Elsevier Ltd. All rights reserved.

Patterned adsorption of protein onto a carbohydrate monolayer immobilized on Si
N Shirahata, T Yonezawa, Y Miura, K Kobayashi, K Koumoto
LANGMUIR, 19, 22, 9107, 9109, AMER CHEMICAL SOC, Oct. 2003, [Peer-reviewed]
English, Scientific journal, We propose a technique for fabricating a carbohydrate-terminated monolayer (CM) surface, which is extremely flat at the angstrom level. The CM was immobilized onto a Si surface by Si-C covalent bond. Specific adsorption of the protein molecule from a contacting solution was observed on the CM area of a patterned CM substrate surface, while its nonspecific adsorption was observed on the Si-O area.

Preparation of SrTiO3 thin films by the liquid phase deposition method
Yanfeng Gao, Yoshitake Masuda, Tetsu Yonezawa, Kunihito Koumoto
Materials Science and Engineering B: Solid-State Materials for Advanced Technology, 99, 1-3, 290, 293, 25 May 2003, [Peer-reviewed]
English, International conference proceedings, Successful preparation of strontium titanate (SrTiO3
STO) thin films has been realized by the liquid phase deposition method. The STO precursor solid thin films with close-packed grains smaller than 200 nm were fabricated from an aqueous solution of Sr(NO3)2/(NH4)2TiF6/H 3BO3 = 1/1/3 (molar ratio) at 50 °C on a Si substrate. X-ray photoelectron spectroscopy analysis showed that the as-deposited film contained fluorine as an impurity, which could be completely eliminated by annealing at 500 °C in air, accompanying the crystallization of the as-deposited amorphous thin film into perovskite-type STO. © 2002 Elsevier Science B.V. All rights reserved.

Room temperature deposition of a TiO2 thin film from aqueous peroxotitanate solution
Yanfeng Gao, Yoshitake Masuda, Zifei Peng, Tetsu Yonezawa, Kunihito Koumoto
Journal of Materials Chemistry, 13, 3, 608, 613, 01 Mar. 2003, [Peer-reviewed]
English, Scientific journal, A transparent, high purity, amorphous titanium dioxide thin film composed of densely packed nanometer-sized grains has been successfully deposited on a glass substrate at room temperature from an aqueous peroxotitanate solution using a simple, inexpensive, reproducible, and environmentally friendly method. The as-deposited thin film was 117 nm thick and composed of closely packed particles of 10-15 nm in diameter, but they aggregated into large grains of 50-100 nm in diameter. The aqueous peroxotitanate solution was obtained by dissolving metatitanic acid (H2TiO3) in a mixture of concentrated H2O2 and NH3·H2O. An anatase TiO2 thin film was obtained by heating the as-deposited thin film at 500°C for 1 h in air. A chemical composition of TiO1.4(O2)0.5(OH)0.2 ·1.34H2O is proposed for the as-deposited thin film, based on XPS, T-IR and TG-DTA data. Band gap energies of 3.20 eV for indirect transition and 3.63 eV for direct transition were obtained for the anatase TiO2 film.

Cationic silver nanoparticles dispersed in water prepared from insoluble salts
Tetsu Yonezawa, Hideo Genda, Kunihito Koumoto
Chemistry Letters, 32, 2, 194, 195, 05 Feb. 2003, [Peer-reviewed]
English, Scientific journal, Homogeneous and uniform-sized silver nanoparticles were obtained by reduction of insoluble silver halides. As the stabilizing reagent, a small cationic thiol, thiocholine bromide, was used. Even from large crystals of silver halides, nanosized particles were obtained. Under the optimum conditions, highly monodispersed nanoparticles with relative standard deviation of less than 7% were obtained.

Investigation of apatite deposition onto charged surfaces in aqueous solutions using a quartz-crystal microbalance
Peixin Zhu, Yoshitake Masuda, Tetsu Yonezawa, Kunihito Koumoto
Journal of the American Ceramic Society, 86, 5, 782, 790, American Ceramic Society, 2003, [Peer-reviewed]
English, Scientific journal, Hydroxyapatite (HAp) deposition onto positively charged surfaces (i.e., self-assembled monolayers (SAMs) terminated with NH2 head groups) and negatively charged surfaces (i.e., OH-SAMs (weak) and COOH-SAMs (strong)) soaked at 50°C in aqueous supersaturated solutions (1.5 SBF, pH 7.0-7.6
SBF = simulated body fluid) was investigated using a quartz-crystal microbalance. The results revealed that the solution conditions greatly influenced the formation of HAp on the charged surfaces. In a stable supersaturated solution of simulated body fluid (1.5 SBF, pH >
7.4), more strongly negative surfaces had a more powerful induction capability for the heterogeneous nucleation of HAp (COOH <
OH), whereas nucleation was obviously prohibited on a positive surface (NH2-SAM). On the other hand, after the calcium phosphate particles had nucleated homogeneously in an unstable soaking solution (1.5 SBF, pH ≧7.4), adhesion of the HAp microparticles to the NH2-SAM was observed. A two-step interaction is conceivable to describe the formation of HAp on the positive NH2-SAM: At the first stage, electrostatic interaction dominates the adhesion of HAp microparticles
at the second stage, hydrogen bonds possibly form between the HAp microparticles and the amino head groups of the NH2-SAM, for a firm bonding with the substrate, and the microparticles grow progressively into a thin film. The electrophoretic behaviors of the HAp microparticles confirmed this hypothesis.

Site-selective deposition and micropatterning of SrTiO3 thin film on self-assembled monolayers by the liquid phase deposition method
Yanfeng Gao, Yoshitake Masuda, Tetsu Yonezawa, Kunihito Koumoto
Chemistry of Materials, 14, 12, 5006, 5014, 01 Dec. 2002, [Peer-reviewed]
English, Scientific journal, We have succeeded in site-selective deposition of SrTiO3 (STO) thin films on patterned self-assembled monolayers (SAMs) by the liquid phase deposition (LPD) method. SAMs of heptadecafluoro-1,1,2,2,-tetrahydrodecyltrichlorosilanes [HFDTS, CF3(CF2)7(CH2)2SiCl3] were prepared on Si wafers and modified by UV irradiation through a photomask. This SAM template was composed of HFDTS surfaces (Si-CF3) and silanol surfaces. The patterned SAM-covered substrate was then immersed into a (NH4)TiF6/Sr(NO3)/H3 BO3 aqueous solution at 50°C to deposit a solid phase. (NH4)2TiF6, which could form [Ti(OH)nF6-n]2- slowly in an aqueous solution, was selected as a source of TiO32-. H3BO3 was a scavenger of fluorine and was used to control the reaction rate. The STO films were selectively deposited in the silanol regions. The as-deposited film was amorphous containing fluorine as a main impurity. With annealing at 500°C for 2 h in air, the as-deposited film was crystallized into SrTiO3 and the fluorine was eliminated. Film morphology was characterized by both SEM and AFM. Metal-oxide-semiconductor (MOS) devices were prepared by using an as-deposited film or a crystallized film as a gate oxide. The dielectric constant of SrTiO3 thin films and the leakage current of the MOS device were evaluated. These results indicate that the SrTiO3 film fabricated by a combination of the SAM technique with LPD method through a one-step process is promising for application to dielectric films.

Control over film thickness of SnO2 ultrathin film selectively deposited on a patterned self-assembled monolayer
N Shirahata, Y Masuda, T Yonezawa, K Koumoto
LANGMUIR, 18, 26, 10379, 10385, AMER CHEMICAL SOC, Dec. 2002, [Peer-reviewed]
English, Scientific journal, This paper presents a novel process for the fabrication of site-selectively deposited tin oxide ultrathin films (<10 nm) by using molecular recognition between the precursors and the surface of the Si substrate. Using this simple technique, the film thickness of micropatterned tin oxide films was easily controlled. Patterned self-assembled monolayers, in which both hydrophilic and hydrophobic areas formed, were used as templates for the site-selective deposition of the films. Two precursors of SnCl4 and C4H9SnCl3 were selected. The films were selectively deposited on the hydrophilic regions through the liquid phase. The growth rate of the film deposited in SnCl4 solution was approximately 6 times faster than that in C4H9SnCl3 solution. A quartz crystal microbalance measurement implied that film growth could be suppressed by the formation of hydrophobic surfaces on the growing films with increasing immersion time in C4H9SnCl3 solution.

Thermoelectric properties of textured ceramics of co-containing layer structured oxide
Nagahama, D., Masuda, Y., Yonezawa, T., Koumoto, K.
Key Engineering Materials, 228-229, Key Engineering Materials, 2002, [Peer-reviewed]
Scientific journal

Thermoelectric properties of Ca3Co4O9-based ceramics textured by templated grain growth method
Nagahama, D, Tani, T, Masuda, Y, Itahara, H, Yonezawa, T, Koumoto, K, IEEE
Xxi International Conference on Thermoelectrics, Proceedings Ict '02, 2002-, 211, 214, Institute of Electrical and Electronics Engineers Inc., 2002, [Peer-reviewed]
English, Scientific journal, We fabricated highly textured Ca3Co4O9-based ceramics by using plate-like particles as a template in order to extract highly anisotropic thermoelectric properties. Plate-like powder and fine powder of (Ca2.7Na0.15Bi0.15)Co4O9 were synthesized and wet-mixed at the ratio of 1:4. The slurry was tape-cast into a form with the platelets aligned parallel to the tape surface. The tapes were stacked, and sintered or hot-pressed at 1193 K. The resultant ceramics showed highly preferred orientation with the (001) plane parallel to the tape surface. The electrical conductivity in the direction of the ab-plane was improved to 1.8 x 104S/m at 1073 K by the texture given. The maximum power factor reached 5.9 x 10-4W/mK2 at the same temperature.

Site-selective deposition of TiO2 thin films using self-assembled monolayers and their dielectric properties
Masuda, Y., Wang, D., Yonezawa, T., Koumoto, K.
Key Engineering Materials, 228-229, Key Engineering Materials, 2002, [Peer-reviewed]
Scientific journal

Templated site-selective deposition of titanium dioxide on self-assembled monolayers
Masuda, Y., Jinbo, Y., Yonezawa, T., Koumoto, K.
Chemistry of Materials, 14, 3, 1236, 1241, 2002, [Peer-reviewed]
English, Scientific journal, TiO2 thin films were grown on several kinds of SAMs (self-assembled monolayers) using TC (titanium tetrachloride), TDD (titanium dichloride diethoxide), or TE (titanium tetraethoxide) as a starting material. We discussed the thin film formation mechanism and improvement of feature edge acuity through controlling the reactivity by changing functional groups of starting material and the surface functional groups of SAMs. The deposition of TiO2 from TC or TDD solution was promoted in the silanol group, and the deposition was suppressed on OTS (octadecyltrichloro-silane) SAM. On the other hand, TE was deposited regardless of the type of surface functional group in the whole area of patterned SAMs. The silanol group, which has high hydrophilicity, accelerated the growth of TiO2, and the OTS SAM, which has hydrophobicity, suppressed the growth of TiO2. It is also clarified that the chlorine atom in the starting material has high reactivity with silanol groups of SAMs.

Low-dimensional arrangement of SiO2 particles
Masuda, Y., Itoh, M., Yonezawa, T., Koumoto, K.
Langmuir, 18, 10, 4155, 4159, 2002, [Peer-reviewed]
English, Scientific journal, Novel processes to realize low-dimensional arrangement of SiOq2 particles were proposed. Particle wires and a pattern of the close-packed particle monolayer were fabricated in the solution at room temperature. SAMs (self-assembled monolayers) were formed on Si substrates and modified to be suitable for templates of precise arrangement. Particles were arranged precisely in the desired positions in the solution using well-controlled electrostatic interactions and chemical bond formation between particles and substrates.

Site-selective deposition and micropatterning of zirconia thin films on templates of self-assembled monolayers
Yanfeng Gao, Yoshitake Masuda, Tetsu Yonezawa, Kunihito Koumoto
Journal of the Ceramic Society of Japan, 110, 1281, 379, 385, Ceramic Society of Japan, 2002, [Peer-reviewed]
English, Scientific journal, Zirconia thin films were successfully micropatterned on octadecyltrichlorosilane (OTS)-self-assembled monolayers (SAM) in ZrOCl2 · 8H2O-ethanol solution at room temperature. OTS-SAM was modified by UV-irradiation through a photomask to change into a SAM template patterned with silanol and octadecyl groups. The films were selectively deposited in the silanol regions through hydration-alcoholysis and condensation reactions. The as-deposited film was amorphous with a complex composition, decomposed into tetragonal-zirconia at 500°C, and further transformed into monoclinic-zirconia at 600°C. The as-deposited film demonstrated a dielectric permittivity of 14 at 100 kHz, but a resistivity of 3.1 × 1011 Ω cm and a leakage current density of 9.0 × 10-7 Acm-2 obtained for a MOS device indicated that the film quality needed to be improved.

Chemical Modification of Metal Nanoparticles and Their Assembly Formation
YONEZAWA Tetsu
Kobunshi, 50, 4, 262, 262, The Society of Polymer Science, Japan, 01 Apr. 2001
Japanese

Three-dimensional assembly of cationic gold nanoparticles and anionic organic components: DNA and a bilayer membrane
Tetsu Yonezawa, Shin-ya Onoue, Toyoki Kunitake
Studies in Surface Science and Catalysis, 132, 623, 626, Elsevier Inc., 2001
English, International conference proceedings, Cationic gold nanoparticles and anionic components, DNA and anionic bilayer were assembled layer-by-layer to form controlled three-dimensional composite thin film. The QCM frequency changes revealed formation of ordered sandwich type layers. Densely charged positive particles formed close-packed layers on these anionic components. For formation of stable composites, rigid organic components were indispensable.

Preparation of ultrathin films filled with gold nanoparticles through layer-by-layer assembly with polyions
Tetsu Yonezawa, Hiroto Shimokawa, Mizuki Sutoh, Shin-ya Onoue, Toyoki Kunitake
Studies in Surface Science and Catalysis, 132, 619, 622, Elsevier Inc., 2001
English, International conference proceedings, Gold nanoparticles stabilized by a small mercapto-ligand were assembled by the layer-by-layer alternate adsorption. Due to high chemical stability of these nanoparticles, sodium chloride could be added to the dispersion to reduce the electrostatic repulsion between the particles. Obtained layers of gold nanoparticles showed golden metallic luster and electro-conductivity.

Two-dimensional patterning of nanoparticles using dissipative structures
T. Sawadaishi, K. Ijiro, M. Shimomura, Y. Shiraishi, N. Toshima, T. Yonezawa, T. Kunitake
MOLECULAR CRYSTALS AND LIQUID CRYSTALS, 371, 123, 126, 2001, [Peer-reviewed]

Practical preparation of anionic mercapto ligand-stabilized gold nanoparticles and their immobilization
Tetsu Yonezawa, Toyoki Kunitake
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 149, 1-3, 193, 199, Elsevier Science Publishers B.V., 15 Apr. 1999, [Peer-reviewed]
English, International conference proceedings, Gold nanoparticles stabilized by a water-soluble mercapto ligand (sodium 3-mercaptopropionate) were produced by a modified citrate reduction of HAuCl4. No rigorous cleanliness is needed and the reductant is decomposed to CO2. Stable aqueous dispersions of gold nanoparticles without any precipitation for several months could be obtained. The particle size can be controlled by the stabilizer/gold ratios. These gold nanoparticles were incorporated successfully into the interlayers of cast films of cationic bilayers by immersion of the film in gold nanoparticle dispersions. Copyright (C) 1999 Elsevier Science B.V.

Visualized Polymers. Patterns Formed by Polymeric Systems. II. Formation of One-Dimensional Arrays of Gold Nanoparticles with DNA.
YONEZAWA Tetsu, ONOUE Shin-ya, KUNITAKE Toyoki
Kobunshi Kagaku, 56, 12, 855, 859, The Society of Polymer Science, Japan, 1999
Japanese, A close-packed one-dimensional array of gold nanoparticles was prepared with DNA as a rigid anionic polymer template. Gold nanoparticles with dense positive charges were prepared by modifying with dialkylammonium-disulfide. These cationic gold nanoparticles were adsorbed effectively on anionic DNA molecules. Electron microscopy indicated that the particle array had a close-packed structure with a small inter-particle distance. The formation mechanism of the close packing is discussed.

Preparation of cationic gold nanoparticles and their monolayer formation on an anionic amphiphile layer
Tetsu Yonezawa, Shin-Ya Onoue, Toyoki Kunitake
Chemistry Letters, 10, 1061, 1062, Chemical Society of Japan, 1999, [Peer-reviewed]
English, Scientific journal, Reduction of AuCl4 by sodium borohydride in the presence of quatemary ammonium disulfide gave an aqueous dispersion of cationic gold particles in nano-dimension. These cationic nanoparticles could be assembled effectively on an anionic amphiphile layer with a close-packed structure.

Growth of closely packed layers of gold nanoparticles on an aligned ammonium surface
Tetsu Yonezawa, Shin-Ya Onoue, Toyoki Kunitake
Advanced Materials, 10, 5, 414, 416, Wiley-VCH Verlag, 23 Mar. 1998
English, Scientific journal

Formation of ordered monolayer of anionic silica particles on a cationic molecular layer
Tetsu Yonezawa, Shin-Ya Onoue, Toyoki Kunitake
Chemistry Letters, 7, 689, 690, Chemical Society of Japan, 1998, [Peer-reviewed]
English, Scientific journal, Quartz crystal microbalance (QCM) measurements and scanning electron microscopy revealed the formation of defect-free monolayer of anionic silica nanoparticles on a solid substrate coated with a cationic organized molecular layer.

Practical preparation of size-controlled gold nanoparticles in water
Tetsu Yonezawa, Mizuki Sutoh, Toyoki Kunitake
Chemistry Letters, 7, 619, 620, Chemical Society of Japan, 1997, [Peer-reviewed]
English, Scientific journal, Facile, safe and efficient preparation of stable dispersions of gold nanoparticle from tetrachloroaureic(III) ion is achieved by simultaneous addition of citrate as reductant and sodium 3-mercaptopropionate as stabilizer. No rigorous cleanliness is needed and the reductant is decomposed to CO2. The particle size can be controlled in the range between 2.3 nm and 10 nm.

Photosensitized Reduction of Carbon Dioxide in Solution Using Noble-Metal Clusters for Electron Transfer
Naoki Toshima, Yumi Yamaji, Toshiharu Teranishi, Tetsu Yonezawa
Zeitschrift fur Naturforschung - Section A Journal of Physical Sciences, 50, 2-3, 283, 291, 01 Mar. 1995, [Peer-reviewed]
English, Scientific journal, Carbon dioxide was reduced to methane by visible-light irradiation of a solution composed of tris(bipyridine)ruthenium(III) as photosensitizer, ethylenediaminetetraacetic acid disodium salt as sacrificial reagent, methyl viologen as electron relay, and a colloidal dispersion of polymer-protected noble-metal clusters, prepared by alcohol-reduction, as catalyst. Among the noble-metal clusters examined, Pt clusters showed the highest activity for the formation of methane as well as hydrogen. In order to improve the activity, oxidized clusters and bimetallic clusters were also applied. For example, the CH4 yield in 3-h irradiation increased from 51 x 10−3 μmol with unoxidized Pt clusters to 72 x 10−3 μmol with partially oxidized ones. In the case of Pt/Ru bimetalic systems, the improvement of the catalytic activity by air treatment was much greater than in case of monometallic clusters. © - Verlag der Zeitschrift für Naturforschung

両親媒性分子の作る組織場中の金属超微粒子
米澤 徹, 戸嶋 直樹
高分子論文集, 52, 12, 809, 820, 高分子学会, 1995, [Peer-reviewed]
Japanese, Scientific journal

Metal clusters in organized media composed of amphiphilic molecules
T Yonezawa, N Toshima
KOBUNSHI RONBUNSHU, 52, 12, 809, 820, SOC POLYMER SCIENCE JAPAN, 1995, [Peer-reviewed]
Japanese, Scientific journal, Irradiation of visible light and introduction of hydrogen into aqueous solutions of noble metal salts in the presence of surfactants gave stable colloidal dispersions of nanoscopic noble metal clusters protected by surfactant micelles with relatively narrow size distributions. The concentration of the surfactant had to be higher than the corresponding critical micelle concentration (CMC). These clusters can be used as active catalysts for hydrogenation of olefins or visible-light-induced hydrogen-evolution from water. In the case of hydrogenation of unsaturated fatty acids and their salts, some regio-selectivity is observed, probably because the substrates are aligned in the organized media surrounding the metal clusters. The protective structures of noble metal cluster particles protected by surfactants are analyzed by the chemical shifts of surfactant molecules in C-13 and H-1 NMR. The Stokes' radii of the surfactant-protected particles measured by a Taylor dispersion method were also helpful.

Protecting structure model for nanoscopic platinum clusters protected by non-ionic surfactants: 13C nuclear magnetic resonance investigation
Tetsu Yonezawa, Yaeko Gotoh, Naoki Toshima
Reactive Polymers, 23, 2-3, 43, 51, 1994, [Peer-reviewed]
English, Scientific journal, Visible light irradiation of an aqueous solution of a platinum ion and a non-ionic surfactant, poly(ethylene glycol) monolaurate, gives a colloidal dispersion of nanoscopic platinum clusters protected by the surfactants. The structure of the surfactants protecting the platinum clusters is investigated by a nuclear magnetic resonance (NMR) technique. In the 13C NMR spectra, all carbon signals of the hydrophobic alkyl chain of the surfactant decrease in height with increasing concentration of the platinum cluster. This indicates that the platinum cluster particle is not incorporated into the central hydrophobic hole of the surfactant micelle, but is protected by the adsorption of surfactant molecules on the surface of the cluster particle at the hydrophobic part. © 1994.

THE POLYMER-PROTECTED PD-PT BIMETALLIC CLUSTERS HAVING CATALYTIC ACTIVITY FOR SELECTIVE HYDROGENATION OF DIENE - PREPARATION AND EXAFS INVESTIGATION ON THE STRUCTURE
N TOSHIMA, T YONEZAWA, M HARADA, K ASAKURA, Y IWASAWA
CHEMISTRY LETTERS, 5, 815, 818, CHEMICAL SOC JAPAN, May 1990, [Peer-reviewed]
English, Scientific journal

COLLOIDAL DISPERSIONS OF PALLADIUM-PLATINUM BIMETALLIC CLUSTERS PROTECTED BY POLYMERS - PREPARATION AND APPLICATION TO CATALYSIS
N TOSHIMA, K KUSHIHASHI, T YONEZAWA, H HIRAI
CHEMISTRY LETTERS, 10, 1769, 1772, CHEMICAL SOC JAPAN, Oct. 1989, [Peer-reviewed]
English, Scientific journal

金属ナノ粒子・微粒子の合成と回収の決め手　　　　　　　　　　　　　　　
米澤 徹, 日本ディスパージョンセンター技術研究会, May 2022, [Invited], [Lead author, Last author, Corresponding author]
Japanese, Lecture materials

Fabrication of Copper Fine Particles for Conductive Inks and Pastes Sintered at Low Temperatures
米澤徹, ナノ学会会報, 19, 2, Mar. 2022, [Invited]
Japanese, Introduction scientific journal

酸化グラフェン(GO)上におけるFe-Co-Ni合金ナノ粒子の化学合成
新開裕二, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2021 (CD-ROM), 2022, [Last author, Corresponding author]

画像誘導放射線治療に用いるフィデューシャルマーカーのためのRFプラズマを用いた金ナノ粒子の合成
古岡昂真, LIU Haoran, 宮本直樹, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2021 (CD-ROM), 2022, [Last author, Corresponding author]

バインダー利用によるα-MnO₂ベース亜鉛イオン電池の性能向上
村松樹, KHEAWHOM Soorathep, NGUYEN Mai Thanh, 米澤徹, 応用物理学会北海道支部/日本光学会北海道支部合同学術講演会講演予稿集, 56th-17th (CD-ROM), 2021

Manipulation of Two-Dimensional Supramolecular Assembly via Multiple Electrostatic Interaction and Its Direct Imaging by Electron Microscopy
石田洋平, 秋田郁美, 米澤徹, ナノ学会大会講演予稿集, 19th, 2021

Cationization of Neutral Ligands on Au₂₅ Cluster Surface Through Menshutkin Reaction
成田国広, 石田洋平, 米澤徹, ナノ学会大会講演予稿集, 19th, 2021

York-shell type micro-capsules for moderate-temperature heat transfer
米澤徹, 岩谷直治記念財団研究報告書, 44, 2021

さまざまな機能を生み出す粒ぞろいな粒子たち 導電性・熱伝導性ペーストに向けた金属微粒子・ナノ粒子
米澤徹, 粉体技術, 13, 12, 2021

多重静電相互作用による二次元分子配列制御と電子顕微鏡による可視化
石田洋平, 秋田郁美, 米澤徹, 日本顕微鏡学会北海道支部学術講演会講演要旨集, 2021 (CD-ROM), 2021

溶融塩還元による磁性体金属ナノ粒子の合成
高橋悠太, NGUYEN Thanh Mai, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2019, 2020

Atomic scale imaging of a free-standing monolayer clay mineral nanosheet by aberration corrected scanning transmission electron microscopy
石田洋平, 秋田郁美, 米澤徹, 日本化学会春季年会講演予稿集(CD-ROM), 100th, 2020

Atomic Scale Imaging of Free-standing Monolayer Clay Mineral Nanosheet and Remarkable Stability under Electron Beam Irradiation
秋田郁美, 石田洋平, 米澤徹, ナノ学会会報, 19, 1, 2020

低温焼成システム構築に向けたCuOx微酸化物系の構築
米澤徹, 塚本宏樹, マイクロエレクトロニクスシンポジウム論文集, 29th, 2019

低温でのCaH₂還元による磁性体FeNiナノ粒子の合成
高橋悠太, NGUYEN Thanh Mai, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2018, 2019

リガンド交換反応による超迅速なカチオン性金ナノ粒子分散液の合成
鈴木潤, 石田洋平, 米澤徹, 日本化学会春季年会講演予稿集(CD-ROM), 99th, 2019

Free-standing粘土鉱物ナノシートの収差補正ADF-STEM観察
秋田郁美, 石田洋平, 米澤徹, 日本顕微鏡学会北海道支部学術講演会講演要旨集, 2019, 2019

導電性部材などに向けた低温焼成新規銅微粒子システム
米澤徹, 塚本宏樹, 高分子学会予稿集(CD-ROM), 67, 2, 2018

リガンド交換法による超迅速なカチオン性金ナノ粒子合成手法の開拓
鈴木潤, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2017, 2018

マイクロ波液中プラズマ法を利用した黒色酸化チタンナノ粒子の合成と光触媒活性評価
松本大地, 石田洋平, 塚本宏樹, 徳永智春, 米澤徹, 化学系学協会北海道支部冬季研究発表会(Web), 2018, 2018

スパッタリング法による特異な発光特性を有するカチオン性金属/合金ナノ粒子の合成
秋田郁美, RYAN Corpuz D., 石田洋平, 米澤徹, 日本化学会春季年会講演予稿集(CD-ROM), 98th, 2018

スパッタリング法によるカチオン性金ナノ粒子の合成及びサイズ分画による金コアの構造と発光メカニズムの調査
森田晃広, 石田洋平, 米澤徹, 徳永智春, 日本化学会春季年会講演予稿集(CD-ROM), 98th, 2018

アニオン性粘土ナノシートをホストとする量子ドット集合構造内での励起エネルギー伝達反応系の実空間解析
秋田郁美, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2018, 2018

スパッタリング法で合成したカチオン性金ナノ粒子の発光特性および金コア構造の調査
森田晃広, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2018, 2018

半導体ナノ粒子-ナノシート集合系で進行する励起エネルギー移動反応の電子線トモグラフィ解析
石田洋平, 秋田郁美, 米澤徹, 日本化学会春季年会講演予稿集(CD-ROM), 98th, 2018

粘土鉱物ナノシートのHAADF-STEM観察
秋田郁美, 石田洋平, 米澤徹, 日本顕微鏡学会北海道支部学術講演会講演要旨集, 2018, 2018

PEのタネ 低温焼成銅微粒子システム~PEへの応用を目指して~
塚本宏樹, 米澤徹, コンバーテック, 45, 4, 48‐51, 51, 15 Apr. 2017
加工技術研究会, Japanese

未来を拓く分散・凝集技術 金属ナノ粒子・微粒子の電子部品部材への応用
米澤徹, 松原正樹, ケミカルエンジニヤリング, 62, 8, 2017

物理的手法で合成したチオラート保護金ナノ粒子のユニークな発光特性と二次凝集構造
秋田郁美, 石田洋平, 米澤徹, 日本化学会春季年会講演予稿集(CD-ROM), 97th, 2017

スパッタリング法により合成した金ナノ粒子の発光起源の解明
石田洋平, 秋田郁美, 米澤徹, 光化学討論会要旨集(CD-ROM), 2017, 2017

アニオン性粘土ナノシート-カチオン性量子ドット集合構造内での励起エネルギー伝達反応系の電子線トモグラフィ解析
秋田郁美, 石田洋平, 米澤徹, 粘土科学討論会講演要旨集, 61st, 2017

スパッタリング法によるカチオン性チオラート保護蛍光性金ナノ粒子の合成及びサイズ分画
森田晃広, 石田洋平, 米澤徹, 日本金属学会講演概要(CD-ROM), 161st, 2017

液中プラズマ法を用いた光触媒酸化チタンナノ粒子の合成
松本大地, 石田洋平, 徳永智春, 塚本宏樹, 米澤徹, 日本金属学会講演概要(CD-ROM), 161st, 2017

マイクロ波液中プラズマ法により合成された黒色酸化チタンナノ粒子の構造解析
松本大地, 石田洋平, 塚本宏樹, 米澤徹, 徳永智春, ナノ学会大会講演予稿集, 15th, 2017

量子ドット集合組織内励起エネルギー伝達反応の電子線トモグラフィによる実空間解析
秋田郁美, 石田洋平, 米澤徹, ナノ学会大会講演予稿集, 15th, 2017

スパッタリング法によるカチオン性チオラート保護金ナノ粒子の合成と発光特性
森田晃広, 石田洋平, 米澤徹, ナノ学会大会講演予稿集, 15th, 2017

Unique Fluorescent Nano-Fluids Prepared by a Matrix Sputtering Method
石田 洋平, 米澤 徹, 化学工学, 80, 3, 156, 159, Mar. 2016
化学工学会, Japanese

金属スズ微粒子の合成と低温焼結性能
米澤徹, 白井宏明, 石田洋平, NGUYEN Mai Thanh, Symposium on Microjoining and Assembly Technology in Electronics, 22nd, 2016

液中プラズマ法による酸化チタンナノ粒子の可視光応答性光触媒への改質
石田洋平, 元兼康智, 米澤徹, 徳永智春, 日本化学会春季年会講演予稿集(CD-ROM), 96th, 2016

マイクロ波液中プラズマ法による黒色酸化チタンナノ粒子の合成
松本大地, 石田洋平, 塚本宏樹, 徳永智春, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2016, 2016

マトリクススパッタリング法による特異な蛍光性金ナノ粒子生成メカニズムの解明
秋田郁美, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2016, 2016

硬磁性材料獲得へ向けたFe₅₀Ni₅₀合金ナノ粒子の液相合成
蓑島嵩人, NGUYEN Thanh Mai, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2016, 2016

酸化チタンナノ粒子へのプラズマ処理による簡便な可視光応答化技術の開発
石田洋平, 元兼康智, 米澤徹, 徳永智春, 日本化学会春季年会講演予稿集(CD-ROM), 96th, 2016

液中プラズマを用いた金属酸化物の合成
米澤徹, 塚本宏樹, 本野真梧, 道心渉, 石田洋平, 徳永智春, 日本化学会春季年会講演予稿集(CD-ROM), 96th, 2016

異なるチオール配位子で保護された銀ナノ粒子のマトリクススパッタリング合成
中林良太, 石田洋平, 米澤徹, 化学系学協会北海道支部冬季研究発表会講演要旨集(CD-ROM), 2016, 2016

PVP保護金属スズナノ粒子の化学合成と室温焼結
白井宏明, NGUYEN Thanh Mai, 石田洋平, 米澤徹, 化学系学協会北海道支部冬季研究発表会講演要旨集(CD-ROM), 2016, 2016

酸分解性ポリマー保護銅微粒子の低温焼結
蓑島嵩人, 松原正樹, 塚本宏樹, 田中洋己, 岡本和樹, 尾坂拓也, 米澤徹, 高分子学会予稿集(CD-ROM), 64, 1, ROMBUNNO.2F06, 12 May 2015
Japanese

低温焼結性高分子保護銅微粒子の焼結時の構造変化
米澤徹, 松原正樹, 塚本宏樹, 高分子学会予稿集(CD-ROM), 64, 1, ROMBUNNO.2F04, 12 May 2015
Japanese

非酸化性高分子保護銅微粒子の低温二段焼成
松原正樹, 塚本宏樹, 米澤徹, ナノ学会大会講演予稿集, 13th, 55, 11 May 2015
Japanese

アミン保護銅微粒子の二段焼成における酸化挙動
松原正樹, YONG Yingqiong, 塚本宏樹, 米澤徹, ナノ学会大会講演予稿集, 13th, 56, 11 May 2015
Japanese

低温焼結に向けた銅微粒子の合成と焼結手法
米澤徹, 塚本宏樹, 松原正樹, 化学工学会年会研究発表講演要旨集(CD-ROM), 80th, ROMBUNNO.V201, 19 Mar. 2015
Japanese

リポ酸を保護剤とするCuナノ粒子の合成と蛍光特性
千葉仁嗣, NGUYEN Thanh Mai, 石田洋平, 米澤徹, 応用物理学会北海道支部・日本光学会北海道地区合同学術講演会講演予稿集, 50th-11th, 2015

チオール配位子に保護された銀ナノ粒子のマトリクススパッタリング合成
中林良太, 石田洋平, 米澤徹, 応用物理学会北海道支部・日本光学会北海道地区合同学術講演会講演予稿集, 50th-11th, 2015

マトリクススパッタリング法によって合成した蛍光性銀ナノ粒子
中林良太, 石田洋平, 米澤徹, 日本化学会講演予稿集, 95th, 3, 2015

酸化チタンナノ粒子の液中プラズマによる酸素欠損形成
米澤徹, 元兼康智, 徳永智春, 石田洋平, 日本化学会講演予稿集, 95th, 3, 2015

ポリエチレングリコール中へのスパッタリングによる銀ナノ粒子の合成
中林良太, 石田洋平, 米澤徹, 高分子学会予稿集(CD-ROM), 64, 1, 2015

液中プラズマ法による酸化チタンナノ粒子の改質
元兼康智, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2015, 2015

水溶性チタン錯体への液中プラズマによる酸化チタンナノ粒子の新規合成法
道心渉, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同冬季講演大会概要集, 2014, 2015

マトリクススパッタリング法に有機配位子を共存させた発光性金ナノ粒子合成
石田洋平, 鷲見太希, 米澤徹, 日本化学会講演予稿集, 95th, 3, 2015

液体高分子内に取り込まれた発光性金ナノ粒子の物性
米澤徹, 石田洋平, 高分子学会予稿集(CD-ROM), 64, 2, 2015

メルカプト分子共存下におけるマトリクススパッタリングによる蛍光性金ナノ粒子の合成
米澤徹, 鷲見太希, 本野真梧, 石田洋平, 白幡直人, 高分子学会予稿集(CD-ROM), 64, 1, 2015

マイクロ波液中プラズマ法を用いた酸化チタンナノ粒子改質による可視光吸収
元兼康智, 石田洋平, 米澤徹, 日本顕微鏡学会北海道支部学術講演会講演要旨集, 2015, 2015

高分子に保護された金属微粒子の合成と焼結
米澤徹, 塚本宏樹, 松原正樹, 高分子学会予稿集(CD-ROM), 63, 2, ROMBUNNO.3S09, 03 Sep. 2014
Japanese

金属ナノ粒子の形状変化の高温その場TEM観察　　　　　　　　　　　　　　　
成島 隆, 米澤 徹, 顕微鏡, 49, 2, 88, 92, Sep. 2014, [Peer-reviewed]
Japanese, Introduction scientific journal

Stable Metal Nanoparticles-Preparation and Dispersion from the Point of View of Colloid Chemistry
米澤 徹, 塗装工学, 49, 2, 42, 50, 2014
日本塗装技術協会, Japanese

保護剤混合PEG中にスパッタリングで合成する蛍光性金ナノ粒子
鷲見太希, 石田洋平, 米澤徹, 応用物理学会秋季学術講演会講演予稿集(CD-ROM), 75th, 2014

マトリクススパッタリング法を用いたシングルナノレベルの銀ナノ粒子の合成
中林良太, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2014, 2014

液中プラズマ法による酸化チタンナノ粒子の性質変化
元兼康智, 石田洋平, 米澤徹, 徳永智春, 大谷文章, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2014, 2014

保護剤混合PEGを用いたマトリクススパッタリングによる金ナノ粒子の粒子径制御
鷲見太希, 石田洋平, 米澤徹, 日本鉄鋼協会日本金属学会両支部合同サマーセッション概要集, 2014, 2014

マイクロ波液中プラズマ法を用いる酸化チタンナノ粒子の物性制御
元兼康智, 石田洋平, 米澤徹, 徳永智春, 大谷文章, 日本金属学会講演概要(CD-ROM), 155th, 2014

Effect of silver nanoparticles on cells : Comparison between 2 and 3 dimension culture systems
HASHIMOTO M, TOSHIMA H, YONEZAWA T, KAWAI K, KAGA M, ENDO K, The journal of the Japanese Society for Dental Materials and Devices, 32, 2, 86, 86, 25 Mar. 2013
This study evaluated biological responses of cultured murine macrophages (RAW264.7) to PVP-coated silver nanoparticles (nAg-PVP) using assay of WST-8, LDH release, RT-qPCR, and morphological analyses. Cell culture was conducted using traditional two-dimensional culture (2D) and three-dimensional spheroid culture system (3D). The NPs were taken up by receptor-mediated endocytosis, in which particles aggregated in the vesicles. Cell spheroid formation was obviously observed after 4 and s days culture. The cytotoxic effects of cells in 3D were lower than that in 2D., The Japanese Society for Dental Materials and Devices (JSDMD), Japanese

溶液合成した前駆体のMoS₂への変化過程
島田敏宏, 橋本遊, 柳瀬隆, 長浜太郎, 米澤徹, 応用物理学会春季学術講演会講演予稿集(CD-ROM), 60th, ROMBUNNO.27P-G12-5, 11 Mar. 2013
Japanese

SEM observation of biological samples using room temperature ionic liquids
ABE SHIGEAKI, HYONO ATSUSHI, AKASAKA TSUKASA, WATARI FUMIO, YONEZAWA TETSU, 日本歯科理工学会誌, 31, 5, 442, 442, 25 Sep. 2012
Ionic liquid is a kind of salt as a liquid even at room temperature. Because of their unique properties such as fluidity, high ionic conductivity and negligible vapor pressure, they have been attention for widely applications even under vacuum conditions. In this study, we investigated the ionic liquid for SEM pretreatment of several biomaterials. With regard to IL coating on the sample surface, we succeeded in high-quality observation of biomaterials. In addition, we also succeeded in applying the IL preparation to SEM-EDS measurement. These results suggested that this simple and rapid conductivity preparation for SEM observation., The Japanese Society for Dental Materials and Devices (JSDMD), Japanese

Effect of water-dispersible metal-based nanoparticles on macrophages
HASHIMOTO MASANORI, TOSHIMA HIROKAZU, YONEZAWA TETSU, KAWAI KOJI, KAWAI KOJI, KAGA MASAYUKI, ENDO KAZUHIKO, 日本歯科理工学会誌, 31, 5, 356, 356, 25 Sep. 2012
This study evaluated biological responses of water-dispersible gold (Au-NPs) and silver nanoparticles (Ag-NPs) stabilized by metal-C σ-bonds in cultured murine macrophages (RAW264.7) using assay of cell viability, LDH release, RT-qPCR, and morphological analyses. These results suggested that the Ag-NPs showed cytotoxicity that depended on the NP concentration. In contrast, no cytotoxic effects were observed in the Au-NPs. The expression level of IL-1α was increased after Au- and Ag-NP exposure. The NPs were taken up with minor cell morphological changes for Au-NPs compared to Ag-NPs, in which particles aggregated in the vesicles. The cell endocytosis may induce harmful effects due to expansion of cell vesicles after Ag-NP exposure., The Japanese Society for Dental Materials and Devices (JSDMD), Japanese

マイクロウェーブポリオール法による約2nmサイズの銅ナノ粒子の合成
川崎英也, 明神雄揮, 成島隆, 米澤徹, 荒川隆一, ナノ学会大会講演予稿集, 10th, 70, 14 Jun. 2012
Japanese

生体関連分子の効率よい脱離・イオン化に向けた新規SALDI‐MSシステム
米澤徹, 長谷川千裕, 七分勇勝, 小西克明, 高分子学会予稿集(CD−ROM), 61, 1, ROMBUNNO.3PA069, 15 May 2012
Japanese

サケ白子DNAをテンプレートとして用いたAgナノ粒子の調製法
武島智美, 武島智美, 山田義久, 多田祐也, 西原雅夫, 杉正人, 西則雄, 西則雄, 米澤徹, 古月文志, 高分子学会予稿集(CD−ROM), 61, 1, ROMBUNNO.2PA069, 15 May 2012
Japanese

高分子保護金属銅微粒子の生成メカニズムと表面状態
米澤徹, 内田佳希, 成島隆, 高分子学会予稿集(CD−ROM), 61, 1, ROMBUNNO.3PB024, 15 May 2012
Japanese

Effect of functionalized silver nanoparticles with water-soluble monomer of cells
HASHIMOTO MASANORI, TOSHIMA HIROKAZU, YONEZAWA TETSU, KAWAI KOJI, KAWAI KOJI, KAGA MASAYUKI, ENDO KAZUHIKO, 日本歯科理工学会誌, 31, 2, 90, 90, 25 Mar. 2012
Silver nanoparticles are the most frequent commercialized nanomaterials for various fields due to its strong antibacterial activity. Silver nanoparticles are also attractive for dental applications because of their antimicrobial activity and cell biocompatibility. Despite their widespread application, comprehensive biologic and toxicologic information is not well documented. Therefore, the purpose of this study was to evaluate the effect of water-soluble monomer functionalized silver nanoparticles on cells (RAW264.7 and MC3T3-E1) using morphological analysis of light-microscopy, SEM and TEM, measurement of cell viability, or cytokine assay of real-time qPCR., The Japanese Society for Dental Materials and Devices (JSDMD), Japanese

ナノ粒子の形状と配列制御
米澤徹, 日本化学会講演予稿集, 92nd, 1, 53, 09 Mar. 2012
Japanese

Preparation of Substrates for Surface Assisted Laser Desorptionionization (SALDI) Using Laser Ablation in Liquids
TSUJI Takeshi, YASUTOMO Masato, MIZUKI Takeshi, TSUJI Masaharu, KAWASAKI Hideya, YONEZAWA Tetsu, MAFUNE Fumitaka, レーザー研究, 40, 2, 111, 116, 15 Feb. 2012
レーザー学会, Japanese

金属系分野における人材の育成 北海道大学における金属材料系の教育
Toshiaki Otsuka, Ryosuke O. Suzuki, Tetsu Yonezawa, Kinzoku, 82, 1, 4, 8, Jan. 2012
アグネ技術センター, Japanese, Introduction scientific journal

P-46 Development of a novel SEM observation using an ionic liquid
Abe S, Hyono A, Akasaka T, Watari F, Yonezawa T, The journal of the Japanese Society for Dental Materials and Devices, 30, 5, 349, 349, 25 Sep. 2011
Ionic liquid is a kind of salt as a liquid even at room temperature. Because of their unique properties such as negligible vapor pressure at room temperature and high ionic conductivity, they have been attention for widely applications even under vacuum conditions. In this study, we investigated the ionic liquid for treatment of insulating SEM samples. Ionic liquid was found to put electrical conductivity to the samples similar to a metal or carbon coating., The Japanese Society for Dental Materials and Devices (JSDMD), Japanese

2-325 Activation of Faculty Education by Combination of Quarter System and Practice
SUZUKI Ryosuke, OHTSUKA Toshiaki, YONEZAWA Tetsu, HAYASHI Shigenari, OHNO Munekazu, UEDA Mikito, 工学教育研究講演会講演論文集, 23, 59, 526, 527, 22 Aug. 2011
Japanese Society of Engineering Education, Japanese

Si表面修飾の最適化によるDBTTF薄膜の成長制御
土田裕也, 大伴真名歩, 長浜太郎, 米沢徹, 島田敏宏, 応用物理学会学術講演会講演予稿集(CD-ROM), 72nd, ROMBUNNO.30A-V-9, 16 Aug. 2011
Japanese

電気化学的還元によるグラファイト上でのグラフェンエッジの作製
久保田翔生, 長浜太郎, 米澤徹, 島田敏宏, 応用物理学会学術講演会講演予稿集(CD-ROM), 72nd, ROMBUNNO.30P-ZT-1, 16 Aug. 2011
Japanese

ナノ物質の体内循環挙動の追跡とその生体親和性
阿部薫明, 岩寺信喜, 伊藤佐智子, 赤坂司, 宇尾基弘, 八若保孝, 高田知哉, 米澤徹, 亘理文夫, ナノ学会大会講演予稿集, 9th, 2011

Internal distribution of micro- / Nano-sized inorganic particles and their cytocompatibility
Shigeaki Abe, Nobuki Iwadera, Mitsue Esaki, Ikuhiro Kida, Mami Mutoh, Tsukasa Akasaka, Motohiro Uo, Yasutaka Yawaka, Manabu Morita, Koichi Haneda, Tetsu Yonezawa, Fumio Watari, IOP Conference Series: Materials Science and Engineering, 18, 13, 19201301, 2011
Nano-sized materials have received much attention lately, both in terms of their multiple applications and their biocompatibility. From both viewpoints, understanding the biodistribution of administered nano-materials is very important. In this study, we succeeded in visualizing the biodistribution of administered nano-materials using a scanning X-ray analytical microscope and magnetic resonance imaging method. Quantitative observation was carried out by inductively coupled plasma - atomic emission spectroscopy. We observed that the administered nano-particles accumulated in the liver, lung and spleen of mice. To estimate their cytocompatibility, the nano-particles were exposed to human liver cells. The results suggested that the micro-/ nano- particles have good cytocompatibility, except for copper oxide nano-particles. © 2011 Ceramic Society of Japan., English

Preface for Special Issue on Growth and Novel Functions of Nanocrystals(Preface)
Shimada Toshihiro, Yonezawa Tetsu, Journal of the Japanese Association of Crystal Growth, 37, 4, 265, 265, Jan. 2011
The Japanese Association for Crystal Growth (JACG), Japanese

A Novel Method for Microstructure Fabrication with Anodic Oxide Films
KIKUCHI Tatsuya, SAKAIRI Masatoshi, YONEZAWA Tetsu, JHA Himendra, TAKAHASHI Hideaki, Jitsumu Hyomen Gijutsu, 61, 2, 207, 207, 2010, [Invited]
The Surface Finishing Society of Japan, Japanese, Introduction scientific journal

シリコン表面へのヒドロシリル化によるナノ粒子固定
米澤 徹, コロイドアンドインターフェースコミュニケーション, 34, 3, 22, 24, Aug. 2009
日本化学会コロイドおよび界面化学部会, Japanese

MALDI-MS・SALDI-MS Systems to Analyze Polymer
YONEZAWA Tetsu, Journal of Materials Life Society, 20, 3, 125, 130, 31 Oct. 2008
マテリアルライフ学会, Japanese

生体系光受容体を用いた光電変換のための錯体分子連結系の構築
宮地麻里子, 山野井慶徳, 米澤徹, 西原寛, 岩井道直, 今野雅恵, 岩井雅子, 井上康則, 錯体化学討論会講演要旨集, 58th, 353, 05 Sep. 2008
Japanese

金属ナノ粒子を利用するLDI-MS
米澤徹, 川崎英也, 樽井章, 渡辺健宏, 荒川隆一, 島田敏宏, 真船文隆, 高分子学会予稿集(CD-ROM), 57, 1 Disk1, 2008

金属ナノ粒子の配列・固定化と機能
米澤 徹, 未来材料, 7, 3, 44, 49, Mar. 2007
エヌ・ティー・エス, Japanese

Adsorption-induced Self-fusion of Cationic Gold Nanoparticles on Tobacco Mosaic Virus (TMV)
YONEZAWA Tetsu, ONOUE Shin-ya, KIMIZUKA Nobuo, Chemistry Letters, 34, 11, 1498, 1499, 05 Nov. 2005
The surface of tobacco mosaic virus (TMV) is densely coated by quaternary ammonium-modified gold nanoparticles. By dropping gold nanoparticle dispersions onto TMV pre-cast substrates ("after-staining method"), nanoparticles are spontaneously adsorbed on TMVs. The adsorbed nanoparticles were fused to form semi-continuous structures. This observation indicates the possibility of preparing 1-D arrays from wide variety of nanosized materials, by using TMV tubules as templates. Copyright © 2005 The Chemical Society of Japan., English

光合成システムI-ナノ粒子バイオ共役ナノマテリアルの再構成
米沢徹, 山野井慶徳, 森山佳則, 西原寛, 藤利彰彦, 佐藤幾太郎, 井上康則, 寺崎正, 山本典孝, 玉田薫, 平賀隆, 米山賢史, 皆方誠, 大森努, 酒井誠, 藤井正明, ナノ学会大会講演予稿集, 3rd, 2005

光合成タンパク質複合体(PSI)をナノ部品とするバイオ共役ナノマテリアルの固定化と光電流応答
寺崎正, 山本典孝, 玉田薫, 平賀隆, 藤利彰彦, 佐藤幾太郎, 井上康則, 山野井慶徳, 米沢徹, 森山佳則, 西原寛, 米山賢史, 皆方誠, 大森努, 酒井誠, 藤井正明, ナノ学会大会講演予稿集, 3rd, 2005

光合成たんパく質複合体を利用した新規人工光電変換システムへのアプローチ
山野井慶徳, 森山佳則, 水野克哉, 米沢徹, 西原寛, 藤利彰彦, 佐藤幾太郎, 井上康則, 寺崎正, 山本典孝, 玉田薫, 平賀隆, 米山賢史, 皆方誠, 大森努, 酒井誠, 藤井正明, Review of Polarography, 51, 3, 2005

高分子を語る : 20-30代から
岩田 忠久, 岡村 直子, 上垣外 正己, 田中 賢, 林 真弓, 水谷 章子, 大和 雅之, 米澤 徹, 岡畑 恵雄, 高分子, 53, 1, 1, 12, 10 Oct. 2004
高分子学会, Japanese

Formation of an isolated spherical three-dimensional nanoparticle assembly as stable submicrometer-sized units by using an inorganic wrapping technique
T Yonezawa, H Matsune, N Kimizuka, ADVANCED MATERIALS, 15, 6, 499, 503, Mar. 2003
A general strategy for preparing a stable assembly of nanoparticles was demonstrated. It was emphasized that almost all the titanium dioxide-wrapped particles could be dispersed independently using this technique and their aggregation was not observed. As such, this nanoparticle assembly and wrapping technology can be widely applied to other metal and semiconductor particles as well as to nanosized materials., WILEY-V C H VERLAG GMBH, English

フレッシュマンのための「ナノテク・キーワード」－ナノテク活用技術の流れを読む－「自己組織化／自己集積」
米澤徹, 化学装置, 45, 3, 28, 30, 2003, [Invited]
工業調査会, Japanese, Introduction commerce magazine

Metal Goating of DNA Molecules by Cationic, Metastable Gold Nanoparticles
YONEZAWA Tetsu, ONOUE Shin-ya, KIMIZUKA Nobuo, Chem. Lett., 2002, 12, 1172, 1173, 05 Dec. 2002
Metastable cationic gold nanoparticles were newly developed by the use of thiocholine bromide (TCB) as stabilizer. The gold nanoparticles electrostatically bound to DNA molecules and then underwent self-fusion into the wire-like structures. The use of TCB as a labile ligand was essential to achieve non-electrochemical plating of the non-conductive molecules., English

Formation of Nanoparticle Arrays at the Interlayer of Aqueous Phosphate Bilayers
YONEZAWA Tetsu, ONOUE Shin-ya, KIMIZUKA Nobuo, Chemistry Letters, 2002, 5, 528, 529, 05 May 2002
Nanoparticle arrays were obtained by simply mixing anionic bilayer membranes and cationic, quaternary ammonium-stabilized gold nanoparticles under ultrasonication. The particles were immobilized densely into the hydrophilic interlayers of the dispersed lamellar structures and formed quasi one-dimensional structure., English

Direct preparation and size control of palladium nanoparticle hydrosols by water-soluble isocyanide ligands
T Yonezawa, K Imamura, N Kimizuka, LANGMUIR, 17, 16, 4701, 4703, Aug. 2001
One-pot direct synthesis of cationic palladium nanoparticles that are stabilized by newly synthesized quaternary ammonium alkylisocyanides is reported. Reduction of PdCl42- by hydrazine in the presence of cationic isocyanides gave a stable aqueous dispersion of cationic palladium nanoparticles. The particle size depended on the alkyl chain lengths of the stabilizer molecules., AMER CHEMICAL SOC, English, Report scientific journal

Preparation of Controlled Nanoparticles and Their Ordered Arrays
YONEZAWA Tetsu, 高分子学会予稿集, 50, 1, 46, 48, 07 May 2001
Japanese

Formation of uniform fluorinated gold nanoparticles and their highly ordered hexagonally packed monolayer
T Yonezawa, S Onoue, N Kimizuka, LANGMUIR, 17, 8, 2291, 2293, Apr. 2001
Fluorocarbon-stabilized gold nanoparticles were prepared for the first time by reduction of AuCl4- in the presence of fluorinated alkane thiols as stabilizers. Transmission electron microscopy revealed the formation of uniform gold nanoparticles. These fluoro-nanoparticles are soluble only in fluorocarbon media, and casting of these dispersions provided highly ordered, hexagonally packed monolayers on solid substrates., AMER CHEMICAL SOC, English, Report scientific journal

Self-Organized Superstructures of Fluorocarbon-Stabilized Silver Nanoparticles
YONEZAWA T, ONOUE S, KIMIZUKA N, Advanced Materials, 13, 2, 140, 142, 16 Jan. 2001
Mesoscopic honeycomb structures and regular, hexagonally packed monolayers were produced when fluorocarbon-stabilized silver particles were cast onto solid substrates from fluorocarbon solution. The resulting structures depend on the concentration of the solution and the humidity of the atmosphere.

Controlled growth of gold nanoparticles in organic gels
Tetsu Yonezawa, Masaya Fukumaru, Nobuo Kimizuka, Studies in Surface Science and Catalysis, 132, 525, 528, 01 Jan. 2001
Behavior of dodecanethiol-passivated gold nanoparticles immobilized into organic gels was investigated. Although these nanoparticles are quite stable and no significant changes are observed for months in solutions, growth of nanoparticle in the gel matrix was found by UV-Vis and TEM observation in a few days after the preparation.

Controlled formation of smaller gold nanoparticles by the use of four-chained disulfide stabilizer
T Yonezawa, K Yasui, N Kimizuka, LANGMUIR, 17, 2, 271, 273, Jan. 2001
Size control of gold nanoparticles by tuning molecular cross section of stabilizer molecules is reported. A newly synthesized four-chained disulfide ligand was used as the stabilizer of gold nanoparticles, and the nanoparticles were prepared by NaBH4 reduction of gold ions. By the use of this stabilizer, smaller and monodispersed gold nanoparticles were obtained, when compared to those prapred by using conventional monoalkanethiols. The present design of stabilizer molecules can be used to systematically control the size of nanoparticles with atomic precision., AMER CHEMICAL SOC, English, Report scientific journal

Preparation of Highly Positively Charged Silver Nanoballs and Their Stability
YONEZAWA T, ONOUE S, KIMIZUKA N, Langmuir, 16, 12, 5218, 5220, 13 Jun. 2000
Reduction of AgNO3by sodium borohydride in the presence of quaternary ammonium disulfide gave a stable aqueous dispersion of silver nanoballs. The obtained Ag nanoballs showed a strong plasmon absorption peak, indicating that they consisted of metal Ag, although the counteranion of the stabilizer was Br-. They are obtainable in a powder form by reprecipitation and can be kept without any change under air. Redispersibility of the obtained powder into water was high, and even in slightly acidic condition, they can be kept stably for more than a week. The stabilization mechanism is also discussed.

Structure of Monoalkyl-Monocationic Surfactants on the Microscopic Three-Dimensional Platinum Surface in Water(共著)
YONEZAWA T, TOSHIMA N, WAKAI C, NAKAHARA M, NISHINAKA M, TOMINAGA T, NOMURA H, Colloids and Surfaces A, 169, 1/3, 35, 45, 2000

N. Toshima and T. Yonezawa, Bimetallic Nanoparticles-Novel Materials for Chemical and Physical Applications
TOSHIMA N, YONEZAWA T, New J. Chem., 22, 11, 1179, 1201, 1998

Molecular Behavior on Micriscopic 3-Dimensional Metal Surface-Preparation and Structure of Highly Dispersed Metal Particles-
YONEZAWA Tetsu, 化学と工業 = Chemistry and chemical industry, 50, 2, 147, 150, 01 Feb. 1997
日本化学会, Japanese

金属コロイドの構造と触媒作用
米沢 徹, 戸嶋 直樹, 表面, 34, 7, 426, 438, Jul. 1996
広信社, Japanese

¹⁹⁵Pt NMR of Polymer-Protected Pt/Pd Bimetallic Catalysts(共著)
TONG Y Y, YONEZAWA T, TOSHIMA N, VAN DER KLINK J, J. Phys. Chem., 100, 2, 730, 733, 1996

T. Ypnezawa, T. Tominaga, and N. Toshima, Protecting Structure Analyses of Organic Molecule-Protected Nanoscopic Noble Metal ClusterT. Ypnezawa, T. Tominaga, and N. Toshima, Protecting Structure Analyses of Organic Molecule-Protected Nanoscopic Noble M・・・
YONEZAWA T, TOMINAGA T, TOSHIMA N, Polym. Adv. Tech., 7, 8, 645, 651, 1996
T. Ypnezawa, T. Tominaga, and N. Toshima, Protecting Structure Analyses of Organic Molecule-Protected Nanoscopic Noble Metal ClusterT. Ypnezawa, T. Tominaga, and N. Toshima, Protecting Structure Analyses of Organic Molecule-Protected Nanoscopic Noble Metal Clusters

Novel Characterization of the Structure of Surfactants on Naroscpic Metal Clusters by a Physico-Chemical Method, (共著)
YONEZAWA T, TOMINAGA T, TOSHIMA N, Langmuir, 11, 12, 4601, 4604, 1995

Mechanistic Consideration of Formatin of Polymer-Protected Nanoscopic Bimetallic Clusters, (共著)
YONEZAWA T, TOSHIMA N, J. Chem. Soc., Faraday Trans.,, 91, 22, 4111, 4119, 1995

GOLD-PLATINUM BIMETALLIC CLUSTER CATALYSTS FOR VISIBLE LIGHT-INDUCED HYDROGEN-PRODUCTION FROM WATER
N TOSHIMA, T YONEZAWA, PROCEEDINGS OF THE INDIAN ACADEMY OF SCIENCES-CHEMICAL SCIENCES, 105, 6, 343, 352, Dec. 1993
Simultaneous reduction of two kinds of noble metal ions by refluxing in alcohol in the presence of poly(N-vinyl-2-pyrrolidone) can generally give polymer-protected bimetallic dusters with a core structure. The structures of the clusters were determined by the EXAFS measurements. On the other hand, it is known that micelle-protected platinum clusters work as good catalysts for visible light-induced hydrogen production from water in a system of EDTA/Ru(bpy)3(2+)/methyl viologen. The stable dispersions of polymer- and micelle-protected gold/platinum bimetallic clusters were prepared by alcohol- and photoreduction, respectively. The dispersions prepared by photoreduction in the presence of micelle are mainly composed of the mixtures of monometallic gold and platinum clusters, which cannot work as more active catalysts than monometallic platinum clusters. In contrast, the dispersions prepared by alcohol-reduction in the presence of polymer are composed of Au/Pt bimetallic clusters with a ''Pt-surrounded Au-core'' structure, which are more active catalysts than the monometallic Pt clusters as catalysts for the hydrogen production., INDIAN ACADEMY SCIENCES, English

N. Toshima, T. Yonezawa, and K. Kushihashi, Polymer-Protected Palladium/Platinum Bimetallic Clusters. Preparation, Catalytic Properties and Structural Considerations.
TOSHIMA N, YONEZAWA T, KUSHIHASHI K, J. Chem. Soc., Faraday Trans., 89, 14, 2537, 2543, 1993

T. Yonezawa and N. Toshima, Polymer-and Micelle-Protected Gold/Platinum Bimetallic Systems. Preparation, Application to Catalysis for Visible Light-Induced Hydrogen Evolution, and Analysis of Formation Process with Optical Methods.
YONEZAWA T, TOSHIMA N, J. Mol. Catal., 83, 1/2, 167, 181, 1993

PREPARATION OF POLYMER-PROTECTED GOLD PLATINUM BIMETALLIC CLUSTERS AND THEIR APPLICATION TO VISIBLE LIGHT-INDUCED HYDROGEN EVOLUTION
N TOSHIMA, T YONEZAWA, MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA, 59, 281, 295, Jun. 1992
The dispersions of polymer-protected gold/platinum bimetallic clusters were easily and reproducibly prepared by refluxing the mixed solutions of tetrachloroaureic(III) acid and hexachloroplatinic(IV) acid in ethanol/water (1/1) at 90 approximately 95-degrees-C for 2 h in the presence of a protective polymer such as poly(N-vinyl-2-pyrrolidone) (PVP). The gold/platinum bimetallic clusters thus obtained were very small, well dispersed and very stable. The UV-Vis spectra and the transmission electron micrographs have indicated that each bimetallic particle has an alloy structure consisting of both gold and platinum atoms, and that the surface of the cluster particle is rich in platinum atoms and the inner core in gold atoms. The gold/platinum bimetallic clusters were used as the multi-electron redox catalysts for visible light-induced hydrogen evolution from water. The rate of hydrogen evolution depended on the mole ratio of the gold/platinum bimetallic clusters. The bimetallic clusters at the mole ratio of Au/Pt = 2/3 were the most active catalyst. The in-situ UV-Vis spectra during the reaction have indicated that the order of the aggregation in the two kinds of metal atoms is very important for structure determination of the Au/Pt bimetallic clusters. The protective polymer PVP plays a role not only in protecting hydrophobic colloidal particles in an aqueous solution, but also in determining the metal composition of the cluster surface., HUTHIG & WEPF VERLAG, English

N.Toshima, M.Harada, T.Yonezawa, K.Kushihashi, and K.Asakura, Structural Analysis of Polymer-Protected Pd-Pt Bimetallic Clusters as Dispersed Catalysts by Using Extended X-Ray Absorption Fine Structure Spectroscopy
TOSHIMA N, HARADA M, YONEZAWA T, KUSHIHASHI K, ASAKURA K, J.Phys.Chem., 95, 19, 7448, 7453, 1991

金属ナノ粒子の合成・設計・制御と応用技術　　　　　　　　　　　　　　　
米澤 徹
サイエンス＆テクノロジー, 16 Dec. 2022, 9784864282482, [Supervisor]

Reducing Agents in Colloidal Nanoparticle Synthesis　　　　　　　　　　　　　　　
Tetsu Yonezawa, Shilei Zhu, Mai Thanh Nguyen, Miscellancous Reductants” in “Reducing Agents in Colloidal Nanoparticle Synthesis
Royal Society of Chemistry, May 2021, 9781839161650, English, [Peer-reviewed]

ナノ材料解析の実際
米澤, 徹, 朝倉, 清高, 幾原, 雄一
講談社, Jun. 2016, 9784061543928, xii, 338p, Japanese, [Joint work]

産業応用を目指した無機・有機新材料創製のための構造解析技術
米澤, 徹, 陣内, 浩司
シーエムシー出版, Aug. 2015, 9784781310701, vi, 295p, Japanese, [Supervisor]

Encyclopedia of polymeric nanomaterials
小林, 四郎, Müllen, K. (Klaus), Metal Nanoparticles
Springer, 20 Jun. 2015, 9783642296475, 3v. (liv, 2617p. ), English, ［Internationally co-authored］, [Peer-reviewed], [Contributor]

粉体・ナノ粒子の創製と製造・処理技術 基礎物性からプロセス設計の実務・トラブル処理まで　　　　　　　　　　　　　　　
獅子内優, 米澤 徹, 金属ナノ粒子の創製
テクノシステム, 13 Nov. 2014

金属ナノ・マイクロ粒子の最新技術と応用
米澤, 徹
シーエムシー出版, Nov. 2013, 9784781308272, vi, 237p, Japanese, [Supervisor]

多重安定性を示す新しい金属錯体の創製と分子機能連動系の構築
西原, 寛, 米澤, 徹, 山野井, 慶徳, 久米, 晶子
西原寛, Jun. 2009, 357p

金属ナノ・マイクロ粒子の形状・構造制御技術
米澤, 徹
シーエムシー出版, Apr. 2009, 9784781301167, vii, 307p, Japanese

ナノ粒子の創製と応用展開
米澤, 徹
フロンティア出版, Jan. 2008, 9784902410136, ix, 322p, Japanese

Graphene Oxide Hybridized Transition Metal Oxide Catalysts for Zinc-Air Flow Cell　　　　　　　　　　　　　　　
Sim Wei Jian, Mai Thanh Nguyen, Soorathep Kheawhom, Tetsu Yonezawa
International Conference on Flow Battery 2023 (ICFlowBatt2023), 03 Feb. 2023, English, Invited oral presentation
03 Feb. 2023 - 10 Feb. 2023, [Invited]

High Current Density Zinc-Air Flow Cell with Graphene Oxide supported Fe/Co Oxide Electrocatalysts　　　　　　　　　　　　　　　
Wei Jian Sim, Mai Thanh Nguyen・Soorathep Kheawhom, Tetsu Yonezawa
化学系学協会北海道支部2023年冬季研究発表会, 25 Jan. 2023, Japanese, Oral presentation
24 Jan. 2023 - 25 Jan. 2023

カルボン酸保護銅ナノ粒子の合成と低温接合、粒子構造　　　　　　　　　　　　　　　
米澤 徹, 塚本宏樹, 戸倉凛太郎
第29回「エレクトロニクスにおけるマイクロ接合・実装技術」シンポジウム（Mate 2023）, 25 Jan. 2023, Japanese, Oral presentation
24 Jan. 2023 - 25 Jan. 2023

Synthesis of Pt single atoms catalyst by magnetron sputtering　　　　　　　　　　　　　　　
Feng Xiaoyi, NGUYEN Mai Thanh, Yonezawa Tetsu
化学系学協会北海道支部2023年冬季研究発表会, 24 Jan. 2023, Japanese, Oral presentation
24 Jan. 2023 - 25 Jan. 2023

Au25(SR)9(SR+)9クラスターのカチオン性リガンド交換反応における特異な反応性　　　　　　　　　　　　　　　
イドンフン, 石田洋平, 米澤 徹
化学系学協会北海道支部2023年冬季研究発表会, 24 Jan. 2023, Japanese, Oral presentation
24 Jan. 2023 - 25 Jan. 2023

フラッシュランプアニール法を用いた貴金属高エントロピー合金ナノ粒子の合成
新開裕二, 米澤 徹
2022年度日本鉄鋼協会・日本金属学会両北海道支部合同冬季講演大会, 19 Jan. 2023, Japanese, Oral presentation
19 Jan. 2023 - 20 Jan. 2023, 36960069

画像誘導放射線治療で用いる低侵襲マーカーのための高周波プラズマを用いた金ナノ粒子の自動合成　　　　　　　　　　　　　　　
古岡昂真, 米澤 徹
2022年度日本鉄鋼協会・日本金属学会両北海道支部合同冬季講演大会, 19 Jan. 2023, Japanese, Oral presentation
19 Jan. 2023 - 20 Jan. 2023, 室蘭工業大学, Japan, [Domestic Conference]

酸化銅ナノ粒子を表面に持つ銅マイクロ粒子を用いた低温焼結可能なダイボンディングペーストの合成　　　　　　　　　　　　　　　
阿曽崇志, 米澤 徹
2022年度日本鉄鋼協会・日本金属学会両北海道支部合同冬季講演大会, 19 Jan. 2023, Japanese
19 Jan. 2023 - 20 Jan. 2023

銅微粒子・低温分解性銅錯体を含む自己還元型混合インクを用いた高導電性銅膜の作製　　　　　　　　　　　　　　　
渡部 蓮, 米澤 徹
2022年度日本鉄鋼協会・日本金属学会両北海道支部合同冬季講演大会, 19 Jan. 2023, Japanese, Oral presentation
19 Jan. 2023 - 20 Jan. 2023

Transition Metal Oxide Catalyst on Reduced Graphene Oxide for High Current Operations of Zinc-Air Battery　　　　　　　　　　　　　　　
Tetsu Yonezawa
Department Seminar, Faculty of Engineering, Chulalongkorn University, 19 Dec. 2022, English, Invited oral presentation
19 Dec. 2022, [Invited]

Transition Multi Metal Oxide Catalyst Activation by Graphene Oxide Hybridization for High Current Zinc-Air Battery Operations　　　　　　　　　　　　　　　
Tetsu Yonezawa
The International Conference on Nanospace Materials 2022（ICNM2022）, 12 Dec. 2022, English, Keynote oral presentation
11 Dec. 2022 - 14 Dec. 2022, [Invited]

金属微粒子・ナノ粒子のインク・ペーストへの分散手法　　　　　　　　　　　　　　　
米澤 徹
第９回分散凝集化学技術講座「分散・凝集のすべて」, 02 Dec. 2022, Japanese, Nominated symposium
01 Dec. 2022 - 02 Dec. 2022, [Invited]

フラッシュランプアニールによる白金族ハイエントロピー合金ナノ粒子の合成　　　　　　　　　　　　　　　
新開裕二, 米澤 徹
令和4年度日本顕微鏡学会北海道支部学術講演会, 19 Nov. 2022, Japanese, Oral presentation
19 Nov. 2022 - 19 Nov. 2022

カルボン酸被覆銅ナノ粒子による接合　　　　　　　　　　　　　　　
田村 一樹, 高橋 悠太, 塚本 宏樹, 米澤 徹
第12回CSJ化学フェスタ, 20 Oct. 2022, Japanese, Poster presentation
18 Oct. 2022 - 20 Oct. 2022

金属ナノ粒子濃厚分散系の安定構築　　　　　　　　　　　　　　　
米澤 徹
第12回CSJ化学フェスタ 材料化学の最先端を歩み続ける濃厚分散系, 19 Oct. 2022, Japanese, Nominated symposium
18 Oct. 2022 - 20 Oct. 2022, [Invited]

Metal nanoparticles and synchrotron　　　　　　　　　　　　　　　
Synchrotron light research institute national lab., Thailand, 12 Oct. 2022, English, Nominated symposium
[Invited]

画像誘導放射線治療で用いる低侵襲マーカーに対する高周波プラズマで合成した金ナノ粒子の適用可能性　　　　　　　　　　　　　　　
古岡昂真, Liu Haoran, 米澤 徹
第73回コロイドおよび界面化学討論会, 22 Sep. 2022, Japanese, Poster presentation
20 Sep. 2022 - 22 Sep. 2022

低融点Bi-Sn-In合金を用いた潜熱蓄熱粒子の開発　　　　　　　　　　　　　　　
樋口翔大, 米澤 徹
第73回コロイドおよび界面化学討論会, 22 Sep. 2022, Japanese, Poster presentation
20 Sep. 2022 - 20 Sep. 2022

Formation Scheme of ZnTe Microspheres via Hot Injection Method　　　　　　　　　　　　　　　
チャウ ユエンティン, レイチェル・グエン タンマイ, 米澤 徹
第73回コロイドおよび界面化学討論会, 20 Sep. 2022, English
20 Sep. 2022 - 20 Sep. 2022

Structure of Bimetallic Nanoparticles Synthesized by Sputtered Deposition onto Liquid and Their Catalytic Properties　　　　　　　　　　　　　　　
Mai Thanh Nguyen, Tetsu Yonezawa
第73回コロイドおよび界面化学討論会, 20 Sep. 2022, English, Invited oral presentation
20 Sep. 2022 - 20 Sep. 2022, [Invited]

アルキルカルボン酸被覆銅微粒子の低温焼結とメカニズム解明　　　　　　　　　　　　　　　
米澤 徹, 戸倉凛太郎
第73回コロイドおよび界面化学討論会, 20 Sep. 2022, Japanese, Oral presentation
20 Sep. 2022 - 20 Sep. 2022

超音波照射下で誘起されるEGaIn液体金属ナノ粒子触媒によるエタノールからのグラファイトカーボン生成　　　　　　　　　　　　　　　
川﨑 英也, 大槻 朋子, 杉野 史弥, 山本 健, 徳永智春, 戸倉凜太郎, 米澤 徹
第73回コロイドおよび界面化学討論会, 20 Sep. 2022, Japanese, Oral presentation
20 Sep. 2022 - 20 Sep. 2022

アルギン酸ナトリウム保護金ナノ粒子の合成と低侵襲X線マーカーとしての利用　　　　　　　　　　　　　　　
米澤 徹, Haoran Liu
第73回コロイドおよび界面化学討論会, 20 Sep. 2022, Japanese, Invited oral presentation
20 Sep. 2022 - 20 Sep. 2022, [Invited]

Pt/Ag Solid Solution Alloy Nanoparticles Co-sputtered onto Liquid Polyethylene Glycol Substrate　　　　　　　　　　　　　　　
Mingbei Zhu, Mai Thanh Nguyen, Tetsu Yonezawa
IVC-22 (The 22nd International Vacuum Congress), 15 Sep. 2022, English, Oral presentation
11 Sep. 2022 - 16 Sep. 2022

Gold Nanoparticles Sputtered onto Oleic Acid and Oleylamine Liquids　　　　　　　　　　　　　　　
Mai Thanh Nguyen, Tetsu Yonezawa
IVC-22 (The 22nd International Vacuum Congress), 15 Sep. 2022, English, Oral presentation
11 Sep. 2022 - 16 Sep. 2022

エチレングリコールを用いて合成されたZnTe微粒子の生成機構　　　　　　　　　　　　　　　
Yuen-ting Rachel Chau, Tetsu Yonezawa
日本化学会北海道支部2022年夏季研究発表会, 23 Jul. 2022, 日本化学会コロイドおよび界面化学部会, Japanese, Oral presentation
23 Jul. 2022 - 23 Jul. 2022, 広島大学, Japan, [Domestic Conference]

銅ニッケル錯体混合インクの調製と低温焼結　　　　　　　　　　　　　　　
木村朋貴, 戸倉凜太郎, 米澤 徹
日本化学会北海道支部2022年夏季研究発表会, 23 Jul. 2022, Japanese, Oral presentation
23 Jul. 2022 - 23 Jul. 2022

金属ナノ粒子・微粒子ペースト作製の実際　　　　　　　　　　　　　　　
米澤 徹
日本ディスパージョンセンター技術研究会, 24 Jun. 2022, Japanese, Nominated symposium
24 Jun. 2022 - 24 Jun. 2022, [Invited]

金属ナノ粒子・微粒子の合成と回収の決め手　　　　　　　　　　　　　　　
米澤 徹
日本ディスパージョンセンター技術研究会, 27 May 2022, Japanese, Nominated symposium
27 May 2022 - 27 May 2022, [Invited]

Cobalt Nickel Oxides Embedded on reduced graphene oxide as Catalysts for Rechargeable Zinc-air Battery　　　　　　　　　　　　　　　
Zixuan Huang, Wei Jian, Sim・Tetsu Yonezawa・Thanh Mai Nguyen, Masayuki Takahashi
化学系学協会北海道支部2022年冬季研究発表会, 25 Jan. 2022, English
25 Jan. 2022 - 26 Jan. 2022

Graphene Oxide Induced Iron Cobalt Spinel Oxide Nanoparticles as Bifunctional Catalyst in Zinc-Air Battery　　　　　　　　　　　　　　　
Wei Jian Sim, Zixuan Huang, Masayuki Takahashi, Mai Thanh Nguyen・Tetsu Yonezawa
化学系学協会北海道支部2022年冬季研究発表会, 25 Jan. 2022, English
25 Jan. 2022 - 26 Jan. 2022

Cu2O形成を抑制することでネッキング促進されるカルボン酸被覆銅微粒子　　　　　　　　　　　　　　　
戸倉凜太郎, 米澤 徹
化学系学協会北海道支部2022年冬季研究発表会, 25 Jan. 2022, Japanese, Oral presentation
25 Jan. 2022 - 26 Jan. 2022

画像誘導放射線治療に用いるフィデューシャルマーカーのためのRFプラズマを用いた金ナノ粒子の合成　　　　　　　　　　　　　　　
古岡昂真, LIU Haoran, 宮本直樹, 米澤 徹
2021年度日本金属学会・日本鉄鋼協会両北海道支部合同冬季講演大会, 20 Jan. 2022, English
20 Jan. 2022 - 21 Jan. 2022

酸化グラフェン(GO)上におけるFe-Co-Ni合金ナノ粒子の化学合成　　　　　　　　　　　　　　　
新開裕二, 米澤 徹
2021年度日本金属学会・日本鉄鋼協会両北海道支部合同冬季講演大会, 20 Jan. 2022, English
20 Jan. 2022 - 21 Jan. 2022

プリンテッドエレクトロニクスにおけるカルボン酸被覆銅微粒子を利用した低温焼結の実現　　　　　　　　　　　　　　　
戸倉凜太郎, 米澤 徹
超異分野学会 北海道フォーラム, 04 Dec. 2021, Japanese, Public symposium
04 Dec. 2021 - 04 Dec. 2021

結晶構造を制御して実現する銅微粒子低温迅速焼成　　　　　　　　　　　　　　　
米澤 徹
長崎大学第3期中期目標・中期計画重点研究課題「次世代エネルギー関連技術に向けた革新的物質科学研究拠点」第20回講演会, 24 Nov. 2021, Japanese, Nominated symposium
24 Nov. 2021 - 24 Nov. 2021, [Invited]

Body temperature-activated in situ-formation gel for the delivery and fixation of alginate-stabilized gold nanoparticles for proton beam therapy　　　　　　　　　　　　　　　
Haoran Liu, Tetsu Yonezawa
The 5th A3 Foresight Symposium on Organic/Inorganic Nanohybrid Platforms for Precision Tumor Imaging and Therapy, 14 Oct. 2021, English, Invited oral presentation
13 Oct. 2021 - 14 Oct. 2021, [Invited]

Iron cobalt oxide nanoparticles supported on reduced graphene oxide bifunctional catalyst in high current density zinc-air battery　　　　　　　　　　　　　　　
Wei Jen Sim, Mai Thanh Nguyen, Tetsu Yonezawa
The 5th A3 Foresight Symposium on Organic/Inorganic Nanohybrid Platforms for Precision Tumor Imaging and Therapy, 13 Oct. 2021, English, Invited oral presentation
13 Oct. 2021 - 14 Oct. 2021, [Invited]

Bimetal solid-solution alloy nanoparticles synthesized by sputter deposition onto liquid　　　　　　　　　　　　　　　
Mai Thanh Nguyen, Tetsu Yonezawa
The 5th A3 Foresight Symposium on Organic/Inorganic Nanohybrid Platforms for Precision Tumor Imaging and Therapy, 13 Oct. 2021, English, Invited oral presentation
13 Oct. 2021 - 14 Oct. 2021, [Invited]

Copper Fine Particle and Nanoparticle Systems for Low Temperature Sintering　　　　　　　　　　　　　　　
Tetsu Yonezawa
The 11th International Conference on Flexible and Printed Electronics (ICFPE2021), 29 Sep. 2021, English, Invited oral presentation
27 Sep. 2021 - 01 Oct. 2021, [Invited]

Synthesis of Pt/Ag solid solution alloy nanoparticles on liquid polymer by co-sputtering　　　　　　　　　　　　　　　
Mingbei Zhu, Mai Thanh Nguyen, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会 国際シンポジウム, 21 Sep. 2021, English, Oral presentation
21 Sep. 2021 - 21 Sep. 2021

Alginate-stabilized gold nanoparticles preapred in microwave-induced plasma in liquid process with long-term strage stability for potential biomedical applications　　　　　　　　　　　　　　　
Haoran Liu, Kai Ikeda, Mai Thanh Nguyen, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会 国際シンポジウム, 21 Sep. 2021, English, Invited oral presentation
21 Sep. 2021 - 21 Sep. 2021

Effect of surface oxide on the sitnering of copper fine particels stablized surfacetant molecules in printed electronics　　　　　　　　　　　　　　　
Rinatro Tokura, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会 国際シンポジウム, 21 Sep. 2021, English
21 Sep. 2021 - 21 Sep. 2021

Femtosecond laser exiced THz wave from Cu/Cu2O interface　　　　　　　　　　　　　　　
Yuen-ting Rachel Chau, Hsin-hui Huang, Mai Thanh Nguyen, Koji Hatanaka, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会 国際シンポジウム, 21 Sep. 2021, English
21 Sep. 2021, ［Internationally co-authored］

High aspect ratio silver nanowires as top transparent conducting electrodes　　　　　　　　　　　　　　　
Min Jia Saw, Mai Thanh Nguyen, Naoto Shirahata, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会 国際シンポジウム, 21 Sep. 2021, English
21 Sep. 2021, On line

Sputtering onto a liquid for synthesis of nanoparticles: particle size, aggregation state, composition, and alloy formation　　　　　　　　　　　　　　　
Mai Thanh Nguyen, Tetsu Yonezawa
第72回コロイドおよび界面化学討論会, 16 Sep. 2021, English
15 Sep. 2021 - 17 Sep. 2021, [Invited], [Domestic Conference]

Copper fine particles / nanoparticles for electroconductive materials　　　　　　　　　　　　　　　
Tetsu Yonezawa
Indo-Japan virtual workshop on “Cluster science by interdisciplinary approach: Emerging materials and phenomena”, 04 Sep. 2021, English
03 Sep. 2021 - 04 Sep. 2021, [Invited], [International presentation]

結晶構造を緻密に制御して実現する銅微粒子による低温迅速焼成　　　　　　　　　　　　　　　
米澤 徹
JST 新技術説明会, 02 Sep. 2021, JST, Japanese
02 Sep. 2021, [Invited]

Composition controllable Pt/Ag alloy nanoparticles synthesized by co sputtering onto liquid polymer　　　　　　　　　　　　　　　
Mingbei Zhu, Mai Thanh Nguyen, Tetsu Yonezawa
日本化学会北海道支部2021年夏季研究発表会, 17 Jul. 2021, English
17 Jul. 2021

低温分解性銅錯体を用いた銅微粒子インクによる導電被膜形成　　　　　　　　　　　　　　　
渡部 蓮, 米澤 徹
2021年度日本鉄鋼協会・日本金属学会両北海道支部合同サマーセッション, 15 Jul. 2021, Japanese
15 Jul. 2021

湿式法で合成された低温焼結銅微粒子の焼結メカニズムの解明　　　　　　　　　　　　　　　
戸倉凛太郎, 米澤 徹
第10回 JSCI/GSCシンポジウム, 29 Jun. 2021, Japanese
28 Jun. 2021 - 29 Jun. 2021

Au25クラスター表面での面種と金反応による中性配位子のカチオン化　　　　　　　　　　　　　　　
成田国広, 石田洋平, 米澤 徹
ナノ学会第19回大会, 20 May 2021, Japanese
20 May 2021 - 22 May 2021

多重静電相互作用による二次元分子配列構造制御と電子顕微鏡による可視化　　　　　　　　　　　　　　　
石田洋平, 秋田郁美, 米澤 徹
ナノ学会第19回大会, 20 May 2021, Japanese
20 May 2021 - 20 May 2021, [Invited]

Mixed oleic acid and oleylamine as the matrix for synthesizing metal nanoparticles by sputter deposition　　　　　　　　　　　　　　　
Mai Thanh Nguyen, Tetsu Yonezawa
日本化学会第101回春季年会, 21 Mar. 2021, English
19 Mar. 2021 - 21 Mar. 2021

ナノ粒子への興味とSDGs～合金触媒と低温接合　　　　　　　　　　　　　　　
米澤 徹
北海道大学アカデミックファンタジスタ講演会, 19 Mar. 2021, 北海道大学, Japanese, Public discourse
19 Mar. 2021, 北海高等学校, Japan, [Invited], [Domestic Conference]

金属ナノ粒子のペースト化と最新応用展開　　　　　　　　　　　　　　　
米澤 徹
日本ディスパージョンセンター 2020年度年次総会, 17 Mar. 2021, Japanese
16 Mar. 2021, [Invited]

“Pt/Ag solid solution alloy nanoparticles synthesized by co-sputtering onto liquid polymer　　　　　　　　　　　　　　　
Mingbei Zhu, Mai Thanh Nguyen, Tetsu Yonezawa
第56回応用物理学会北海道支部・第17回日本光学会北海道支部合同学術講演会, 10 Jan. 2021, English
09 Jan. 2021 - 10 Jan. 2021

バインダー利用によるα-MnO2ベース亜鉛イオン電池の性能向上　　　　　　　　　　　　　　　
村松 樹, Soorathep Kheawhom, Mai Thanh Nguyen, 米澤 徹
第56回応用物理学会北海道支部・第17回日本光学会北海道支部合同学術講演会, 09 Jan. 2021, Japanese
09 Jan. 2021 - 10 Jan. 2021

二次電池ナノ材料特論　　　　　　　　　　　　　　　
北海道大学 大学院共通科目
Aug. 2022 - Present

ナノ材料基礎特論　　　　　　　　　　　　　　　
北海道大学 大学院工学院
Jul. 2021 - Present

材料デザイン工学　　　　　　　　　　　　　　　
北海道大学
2012 - Present

材料工学演習I　　　　　　　　　　　　　　　
北海道大学 工学部
Present

無機化学　　　　　　　　　　　　　　　
千葉大学

無機化学　　　　　　　　　　　　　　　
東京大学

無機化学　　　　　　　　　　　　　　　
早稲田大学

金属材料学　　　　　　　　　　　　　　　
北海道大学

合成化学実験　　　　　　　　　　　　　　　
九州大学 工学部

無機化学実験　　　　　　　　　　　　　　　
東京大学 理学部

結晶解析学　　　　　　　　　　　　　　　
北海道大学

Present
日本金属学会　　　　　　　　　　　　　　　

Present
日本質量分析学会　　　　　　　　　　　　　　　

Present
高分子学会　　　　　　　　　　　　　　　

Present
American Chemical Society　　　　　　　　　　　　　　　

Present
Royal Society of Chemistry　　　　　　　　　　　　　　　

Present
日本顕微鏡学会　　　　　　　　　　　　　　　

Present
ナノ学会　　　　　　　　　　　　　　　

Preparation of High Entropy Alloy Nanoparticles with Flash Lamp Annealing
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
01 Apr. 2021 - 31 Mar. 2023
米澤 徹
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), Hokkaido University, 21H00138

Optimization of nanoparticles for development of ultra-broadband light sources
Grants-in-Aid for Scientific Research
09 Oct. 2018 - 31 Mar. 2022
Tetsu Yonezawa
Interaction of intense laser pulses with condensed matter, especially, nanoparticle stable aqueous dispersions, is expected to produce a variety of nonlinear optical effects. Among them, there have been independent experimental studies on high-energy pulsed X-ray (keV) generation through high-temperature plasmas for wavelength conversion and on low-energy terahertz wave (meV) generation based on higher-order nonlinear optical effects. In this study, femtosecond pulsed lasers have been irradiated to various nanoparticle aqueous dispersions and the energy generated from them have been detected. As a result, X-rays were efficiently extracted from Au nanoparticle aqueous dispersions, and THz-wave emission was also obtained from the Cu2O/Cu thin-layer interface. THz emission was also obtained from ZnTe nanoparticle aqueous dispersions, indicating that the interaction of intense laser pulses with condensed systems such as nanoparticles can produce an ultra-broadband light.
Japan Society for the Promotion of Science, Fund for the Promotion of Joint International Research (Fostering Joint International Research (B)), Hokkaido University, 18KK0159

Challenge to elucidate and optimize the radiation sensitizing effect of gold nanoparticles by quantum life science approach
Grants-in-Aid for Scientific Research
01 Apr. 2018 - 31 Mar. 2022
Hashimoto Takayuki
Radiation effects on metals, such as gold nanoparticles, was investigated to improve the results of radiotherapy for intractable cancers. Observation of gold particles in cellular microstructure was delayed due to damage to an ultra-high voltage electron microscope caused by the great earthquake, and proton irradiation experiments using gold nanoparticles that can be administered into the body were not conducted during the period due to the intermittent issuance of a state of emergency declaration and priority measures to prevent spread of the COVID-19. In relation to the interaction between metals in the body and radiation, we published papers on proton therapy for pediatric cancer, in which the radiosensitizing effect of gold particles is expected to be clinically applicable, and on a comparative study of the effects of proton beams and carbon ion beams on implantable medical devices such as pacemakers, respectively.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (C), Hokkaido University, 18K07660

Preparation of rapid conductive thin film layer by nano-copper blow-out by slightly oxidized copper particles and low temperature sintering
Grants-in-Aid for Scientific Research Grant-in-Aid for Challenging Research (Exploratory)
28 Jun. 2019 - 31 Mar. 2021
Yonezawa Tetsu
In this study, we synthesized copper nanoparticles with micro-oxide nanoparticles and slightly oxidized phase on the surface layer as copper particles for low temperature sintering. We succeeded in establishing an industrial synthesis method to obtain more than several tens of grams/batch. The obtained fine particles were dispersed in dipropylene glycol using a bead mill. By determining the bead mill conditions, we were able to synthesize a stable paste. At present, it was found that the copper particulate content could be as high as 80 wt% or more. When this paste was applied to a substrate and sintered at less than 200°C, we succeeded in forming a conductive film with a low resistivity within a few times that of the bulk. They also showed that the film formation mechanism is due to "nano-copper blowout," which is an enhanced diffusion of atoms.
Japan Society for the Promotion of Science, Grant-in-Aid for Challenging Research (Exploratory), Hokkaido University, 19K22094

High Entropy Alloy Nanoparticles Prepared by Plasma-in-Liquid Process
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
01 Apr. 2019 - 31 Mar. 2021
米澤 徹
液中でのプラズマ法を用いたハイエントロピー合金（HEA）ナノ粒子の直接合成に引き続き従事した。ハイエントロピー合金とは多元素を等モル程度含んだ合金のことである。液中プラズマ、さらには、レーザーアブレーション法の適用、酸化した多元素合金の還元、その際における合金ナノ粒子のカプセル化に挑戦し結果をえた。レーザーアブレーション法と同様液中プラズマ法においても、前周期遷移金属の場合には酸化したナノ粒子が生成した。溶媒を有機溶媒に代えても、還元体を得ることが難しかった。
本研究では前周期遷移金属に集中し、得られたナノ粒子は還元操作によってハイエントロピーナノ粒子化できると考え、水素環境場における還元によって微細な合金ナノ粒子の合成に挑戦した。
筆者らは酸化スズをベーマイトでコーティングし還元操作によってコアシェル構造を持つナノ粒子の合成に成功している。そこで、ハイエントロピー合金ナノ粒子においても、還元操作においては金属酸化物コーティングを行い、還元操作時の融合・凝集を防ぐ操作を行った。本研究においてもべーマイト処理法を用いて、それによって粒子1つをアルミナコートすることに成功した。つまり、べーマイトコーティング手法は汎用的で、比較的幅広い合金系に適応できる可能性を見出した。
得られたナノ粒子についてさらにXRD、TEM、SEMなどによって構造解析を行った。まだ十分なデータの蓄積が得られていないので引き続き検討する。
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area), Hokkaido University, 19H05162

Preparation of Stable and Efficient Fluorescent Alloy Nanoparticles by Matrix Sputtering
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B)
01 Apr. 2018 - 31 Mar. 2021
Yonezawa Tetsu
In this study, nanoparticle synthesis, especially alloy nanoparticles, was carried out by matrix sputtering method using a multidimensional magnetron sputtering system. The obtained particles were stable and well dispersed. Direct sputtering onto TEM grids was also performed. The obtained microstructures were investigated in detail using XRD and aberration-corrected (atom-resolved) STEM, and the optical properties were investigated.
Crystal structure analysis by XRD and atomic arrangement analysis by STEM revealed that each of the obtained nanoparticles is an alloy and has a solid solution structure. This was a characteristic of the matrix sputtering method. The optical properties were also investigated and showed luminescence.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), Hokkaido University, 18H01820

マトリクススパッタリング法による無機元素ブロック包埋機能性ハイブリッド樹脂の構築
科学研究費助成事業 新学術領域研究(研究領域提案型)
01 Apr. 2013 - 31 Mar. 2015
米澤 徹
設計したマグネトロンスパッタリング装置を用い、そのチャンバー内に直接液状高分子や樹脂モノマー液を導入し、また場合によっては、添加剤となる金属錯形成物質を導入して無機ヘテロ元素ブロックとしての金属ナノ粒子・金属酸化物ナノ粒子の直接合成を試みた。これをマトリックススパッタリング法と名付けた。
ナノ粒子の粒子径制御には、金属配位化合物の利用が効果的である。液体マトリックス中にチオールなどの金属配位化合物を導入することによりナノ粒子の粒子径制御が可能であることを見出している。一方で、液体マトリックスとは別に、やや揮発性の高いチオール分子をチャンバー内に入れ、チャンバーのガス雰囲気にチオール分子を導入することによっても、ナノ粒子の小粒径化に成功した。このとき、得られたナノ粒子の量子収率は極めて高かった。一般に金ナノ粒子の発光量子収率は1-2%程度であるが、この手法で得られた金ナノ粒子は、10%を越える量子収率を示すものも多く、最大で16%にも達した。これは、チャンバー雰囲気にチオール分子を導入することにより、クラスター状態でナノ粒子がチオールに覆われ、スパッタリング液表面でそれらが凝集したものをナノ粒子として回収しているからと考えられる。そのため、金錯体のような高い量子収率を示しながら、安定にその発光特性を維持できる金ナノ粒子を合成できたことになる。極めて興味深い実用的な材料である。
金属酸化物ナノ粒子の合成では、チタニアの樹脂内への導入について議論を行ってきたが、酸素欠損型のチタニアが多く得られる場合があった。
また、共同研究の大きな成果としては、銅－パラジウム合金ナノクラスターをDMFを還元剤として用いて可能とした。このとき、この合金クラスターは固溶体構造を取っていることがXPSより示唆された。また、発光量子収率も金属組成によって変化することが示され、興味ある合金素材となった。
日本学術振興会, 新学術領域研究(研究領域提案型), 北海道大学, 25102501

Development of biorelated-material-inspired ionic liquid for a visualizing agent for electron microscopic observations
Grants-in-Aid for Scientific Research Grant-in-Aid for Challenging Exploratory Research
2012 - 2012
YONEZAWA TETSU, ABE Shigeaki
In this study, we have used ionic liquids as the SEM visualizing reagent of non-conductive nanomaterials and bio-related samples including cells and construct an optimized pre-treatment method for SEM observation. Ionic liquids are organic salts which are in liquid at room temperature and do not evaporate even in a vacuum conditions. Therefore, they should be a suitable material for SEM visualization.
We have been able to establish the processes to visualize non-conductive nanomaterials during this research period. For bio-related samples, including cells, we applied choline-type structured ionic liquids as the visualizing agents. The samples were dispersed in the ionic liquids and put on a membrane filter. The dispersion was filtered gently under reduced pressure by using a syringe and excess ionic liquids were removed. Using this process, red blood cells could be observed by SEM without any deformation.
Japan Society for the Promotion of Science, Grant-in-Aid for Challenging Exploratory Research, Hokkaido University, Principal investigator, Competitive research funding, 24656026

Surface Assisted Laser Desorption Ionization Mass Analysis System for Drugs and Toxic Molecules
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (A)
2012 - 2012
Yonezawa Tetsu, FUJINO Tatsuya, ISHIDA Yohei
The aims of this study are to prepare suitable nanoparticles for surface-assisted desorption ionization mass spectroscopy and to understand the ionization mechanism by laser irradiation. Lager nanoparticles showed better soft-ionization ability. Therefore, milder increasing of the nanoparticle temperature is important for soft ionization. Also, sodium ion doped TiO2 nanoparticles showed a very high SALDI ability. This result strongly suggest that desorption of molecules by laser irradiation is quite effective and increasing of ionization ability of nanoparticles is an important key to obtain higher sensing ability of SALDI-MS systems.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (A), Hokkaido University, Principal investigator, Competitive research funding, 24241041

生体関連物質のソフトイオン化を目指すナノLDI-MS基板の開発とメカニズム解明
科学研究費補助金(特定領域研究)
2010 - 2011
米澤 徹, 菊地 竜也
本研究では、表面支援レーザー脱離イオン化質量分析法(SALDI-MS法)に用いられる金属ナノ粒子の合成とその挙動、さらには脱離・イオン化のメカニズム解明に挑戦した。まずは、サンプル用基板を作成するために、さまざまな金属・酸化物・半導体のナノ粒子および異方性粒子を作成した。結果として、その物質、構造、大きさ、形状がいずれも有機物の脱離に大きく影響することが分かった。そこで得られた粒子を用いて塗布した基板上に、波長を変えてパルスレーザーを照射したところ、可視光では、金ナノ粒子がそのプラズモン吸収で効率のいい脱離・イオン化性能を示したのに対し、紫外レーザーでは高い脱離・イオン化性能を示す酸化チタンナノ粒子は可視光では負の効果を示した、つまり脱離・イオン化する分子の量を平板基板よりも少なくしてしまった。この結果は、表面支援におけるレーザー脱離・イオン化においては、単純にパルスレーザー照射によって発生する局所的な熱による分子の基板表面からの脱離ではなく、光反応が脱離・イオン化に関与していることを明確に示している。さらに、紫外レーザーによる脱離では、金ではなく、白金は金属酸化物が効率のよい脱離とイオン化を見せていることから、単純に熱のみによるものではないことが分かる。メカニズムの明快な説明はまだできてはいないが、光による電子移動が関与している可能性がより高まったことで、SALDI-MSに...
文部科学省, 特定領域研究, 北海道大学, Principal investigator, Competitive research funding, 22018001

Surface-assisted laser desorption/ionization mass analysis system with nano-scale surface modified sample substrate
Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B)
2009 - 2011
YONEZAWA Tetsu, FUJII Masaaki, ISHIUCHI Shun-ichi, ARAKAWA Ryuichi, KAWASAKI Hideya
Development of surface assisted LDI (SALDI) system used for analyses of low molecular compounds has been carried out. Dealloy process with electrochemical etching could successfully provide nanoporous platinum plate. The structure of nanopores strongly varied with the alloy composition. These plates were applied as SALDI-MS sample plate, desorption/ionization of organic compounds could not be detected. On the other hand, aggregated sample plate of semiconductor nanoparticles effectively
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), Hokkaido University, Principal investigator, Competitive research funding, 21310072

光-分子強結合場を利用する合成高分子用LDI基板の構築
科学研究費補助金(特定領域研究)
2009 - 2010
米澤 徹
本研究では、光-分子強結合場を利用した、レーザー照射による有機分子の脱離とそのソフトイオン化について検討している。ソフトイオン化とは、有機物質を分解しないでイオン化することである。そこで、本年度は、光-分子強結合場を発現させる手段として金粒子の基板上への集積による表面支援レーザー脱離イオン化法について検証を行った。シリコン基板上にアミノシラン単分子膜を用いて作製した金粒子の集積した部分において、特に有機化合物の脱離・イオン化がレーザー照射によって起こりやすいことが見いだされた。一方で、単層の金粒子吸着層だと脱離・イオン化は生じにくい。このことは、レーザー脱離イオン化のメカニズムを考えるときに重要であり、金の場合においては、ナノ粒子の作る基板表面の凹凸ではなく、微粒子の凝集が有機物質の脱離およびイオン化に極めて有効に効いていることが明らかとなっている。つまり、ナノ粒子凝集エリアがつくる光-分子強結合場が脱離・イオン化を加速する方向に働いていることを示していると考えられる。一方で、レーザー照射による有機化合物の脱離量を相対的に比較したところ、金ナノ粒子の示すプラズモン吸収領域の波長のレーザーを用いた場合には脱離量が増大すると考えられた。この結果も、光-分子強結合場が光による基板表面からの有機物質の脱離・イオン化を促進していることを強く支持ずる。これは、本研究で目標とした、光-分子...
文部科学省, 特定領域研究, 東京大学->北海道大学, Principal investigator, Competitive research funding, 21020010

生体機能分子の非分解イオン化のための無機ナノ構造体LDI基板の設計と構築
科学研究費補助金(特定領域研究)
2008 - 2009
米澤 徹
本研究では、有機物のレーザーによる非分解イオン化(ソフトイオン化)のための無機ナノ構造体の設計を行っている。特に、これまでの研究から、先鋭化された部分をもつナノ構造を持たせた表面が電界集中に有効と考えられるため、そうしたナノ構造体の合成、基板構築を行ってきている。特に、白金などはそうした構造を作りやすい。また、レーザー照射による有機物の脱離量についても検証を行ってきた。これまでの検証から、白金を用いた場合のレーザーによる脱離量が非常に大きいことが見いだされた。また、半導体基板を用いたソフトイオン化についても検証した。その一方で、SALDI-MSではどうしても脱離・イオン化しない物質がいくつか見いだされた。低分子量の物質でもそのようなものがあるため、脱離とイオン化を分けて考えるシステムを構築する必要があることが明確となった。というのも、低分子量の物質が基板表面から脱離していないとは考えにくく、脱離したもののイオン化されていないと考察される。こうした物質をあつめ、構造を検証し、どのような構造が脱離・イオン化を抑制してしまうのか考える必要があると思われる。一方で、白金ナノ構造体を用いた基板上からは、長波長レーザーによっても有機物質をイオン化できることが明らかとなった。長波長のレーザーは、エネルギーが小さく、有機物質のソフトイオン化にはさらに好適であることは自明である。こうした可能性...
文部科学省, 特定領域研究, 東京大学->北海道大学, Principal investigator, Competitive research funding, 20050007

光-分子強結合場を利用する合成高分子用LDI基板の構築
科学研究費補助金(特定領域研究)
2008 - 2008
米澤 徹
従来、生体機能物質の非分解イオン化のためによく用いられてきたMALDI-MS法に代え、金属ナノ粒子を塗布した、ナノレベルの凹凸を有する基板を作製し、有機マトリクスフリーで、UVレーザーを用いて、合成高分子をソフト脱離・イオン化を起こすことを試みている。本研究では、特に、光-分子強結合場を利用したレーザーソフト脱離・イオン化を試みている。そこで、表面の清浄な金属ナノ粒子を合成するために、レーザーアビュレーション法を用いた。レーザーアビュレーション法は、インゴットから容易にナノ粒子を合成することができる手法である。その手法で、金、銀、白金、銅ナノ粒子を合成し、分子量10000程度までの分子のソフトイオン化を試みた。結果として、金および白金に顕著なソフト脱離・イオン化能があることが示された。白金は特に熱伝導率が小さいためにイオン化が促進されたと理解され、金の場合には、光-分子強結合場の可能性が見られた。しかし、銀および銅には脱離・イオン化能が見当たらず、現在、金ナノ粒子で試験を行っている。また、単層金ナノ粒子吸着では脱離イオン化能は見受けられないことから、高分子との交互積層を行った、ナノ粒子多積層体や、高濃度に基板上に塗布した金ナノ粒子凝集体が脱離・イオン化に重要なことも示されている。今後はさらに構造体制御を行って、効率のよいレーザー脱離・イオン化システムの構築を行う。
文部科学省, 特定領域研究, 東京大学, Principal investigator, Competitive research funding, 20043011

層状金属カルコゲナイドを母体とするナノクラスターの合成と物性探索
科学研究費補助金(萌芽研究)
2007 - 2008
島田 敏宏, 米澤 徹
有機物は柔らかいため曲げに強い印刷可能な電子素子を作成できる利点はあるが、分子間振動のエネルギーが数十meVと低いことから、室温では振動によるキャリヤ散乱の影響が大きく、無機物に比べて移動度が桁違いに小さくなってしまう。おそらくこの理由により有機半導体の室温移動度は低い。これに対し、無機物のクラスターは溶液中で安定化するためのキャッピング層が通常絶縁物であり問題である。層状物質はもともと層に垂直方向の化学結合が閉じているためこの方向にキャッピング層は必要なく、層が積み重なる形で凝集するために空間充填率も高くなることが期待される。本研究では、層状物質をナノクラスター化することにより新たなフレキシブル電子材料を開発することを目標に、合成法と物性評価を行った。溶液から合成した層状物質クラスターはX線回折が非常に弱く、大部分がアモルファスであることが判明した。層状構造への結晶化は600℃以上の高温が必要であった。その理由を探るため、その場加熱のできる電子顕微鏡を用いて結晶化の過程を観察した結果、400℃程度で未知の結晶構造を持つ別の準安定相ができ、それが層状物質への変化を妨げていることがわかった(論文発表済)。加熱後の物性は、今のところ半導体特性を測定できない絶縁物である。欠陥を少なくする方法が必要であり、気相を経由する方法に切り替えて研究を進めている。本研究に関連した報文は2件、図...
文部科学省, 萌芽研究, 東京大学, Coinvestigator not use grants, Competitive research funding, 19651048

Synthesis of novel metal complexes exhibiting multi-stabilities and creation of molecular systems exhibiting multi-functionalities
Grants-in-Aid for Scientific Research(基盤研究(A))
2005 - 2007
Hiroshi NISHIHARA, 山野井 慶徳, 久米 晶子, 米澤 徹
The purpose of this study is to create intelligent molecular systems where the chemical and physical structures and the optical, magnetic and electronic properties are changed reversibly and then to produce "molecular functional devices" by combining the molecular systems with electrode surface. As for □-conjugated redox complex oligomers and polymers, we have succeeded in bottom-up synthesis of one- and three-dimensional oligomer complex molecular wires by step-wise coordination reactions on the surface, and have found the phenomena of redox-conduction along the molecular wires for the fir...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(A), 東京大学, Coinvestigator not use grants, Competitive research funding, 17205007

Construction of Electro-functional Space Using Interfacial Bottom-up Synthesis of Coordination Bond Network
Grants-in-Aid for Scientific Research(特定領域研究)
2004 - 2007
Hiroshi NISHIHARA, 村田 昌樹, 山野井 慶徳, 久米 晶子, 米澤 徹
In this project, we aim at the construction of electro-functional interfacial space by assembling pi-conjugated and/or redox active metal complex molecular chains in one, two, or three dimensions. Bottom-up approach using successive coordination bond formation is utilized in order to create the space in which potential distribution can be controlled by external stimuli such as electrons and photons.Films of linear and branched oligomer wires of Fe (tpy)2 (tpy = 2,2' :6',2" -terpyridine) were constructed on a gold electrode surface by the interfacial stepwise coordination method employing a ...
Ministry of Education, Culture, Sports, Science and Technology, 特定領域研究, 東京大学, Coinvestigator not use grants, Competitive research funding, 16074204

単一粒径ナノ粒子の連続調製システムの構築
科学研究費補助金(萌芽研究)
2005 - 2006
米澤 徹, 齋藤 永宏
溶液中のプラズマを利用してナノ粒子を大量製造することを試みた。タングステン線を電極とし、高圧パルス電源を使用して、電極間に放電させ、プラズマを発生させた。電極間隔、印加電圧、電流、パルス間隔は、電極間にアーク放電が生じないようにするために適切に制御する必要があった。また、溶液の導電率をアルカリ金属塩の添加によって制御したが、それにはあまり大きく影響されなかった。このとき発生するラジカル、水素、電子によって金属イオンが還元されることが見出された。プラズマ計測を行ってみたところ、このような還元種が生成していることが見出された。また、金、白金、銀、パラジウム、ロジウムなどの貴金属イオンは還元されやすく、ナノ粒子を得ることができた。遷移金属塩からもナノ粒子が得られたように見受けられるが、十分な検証ができていない。多くの金属塩からナノ粒子を作ることに成功したが、ナノ粒子の安定性をさらに向上させるためには原料液の導電性制御のためのアルカリ金属塩の排除を行う必要があることが分かる。一方、原料塩のみでは還元によって導電性が変化していく問題があり、原料のさらなる検討が今後求められる。粒子径は、金属種にも依存するが、単一粒子径にほぼ近い形のものができ、全て球形のものが得られた。異方形状のものは残念ながら得られず、今後、更なる条件検討が必要である。さらに、連続調製装置を作製し、検討を行った。連続調...
文部科学省, 萌芽研究, 東京大学, Principal investigator, Competitive research funding, 17655059

Improvement in Energy Conversion Efficiency of Layered Oxide Thermoelectrics Through Self-assembled Texturing
Grants-in-Aid for Scientific Research(基盤研究(S))
2002 - 2006
Kunihito KOUMOTO, 米澤 徹, 増田 佳丈
Single crystals of homologous phase in the ZnO-In_2O_3 with layer structures were successfully grown by a flux method, and it was confirmed that the in-plane electrical conductivity is two orders of magnitude larger than cross-plane conductivity. Y-doped single crystal was found to show the in-plane conductivity similar to that of textured ceramic, and it was verified semi-quantitatively that ZT of this system would be ultimately achieved to be〜0.5.We have succeeded in preparing high-quality epitaxial thin films of Na_<0.8>CoO_2, which further enabled us to synthesize humidity-stable Sr_xCo...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(S), 名古屋大学, Coinvestigator not use grants, Competitive research funding, 14103008

Creation of Multifunctional Photochromic Metal Complexes
Grants-in-Aid for Scientific Research(基盤研究(A))
2002 - 2004
Hiroshi NISHIHARA, 栗原 正人, 村田 昌樹, 米澤 徹
This project aims at the creation of new photochromic metal complexes, the investigation of their unique multiple functionalities, and the fabrication of novel types of molecular switches and memories by organizing them at the electrode surfaces. Summary of the results obtained is as follows, 1)Azobenzene-bound tris(bipyridine)cobalt complexes and ferrocenylazobenzenes underwent novel reversible trans-cis isomerization of azobenzene moieties using the combination of photoirradiation with a single light source and redox reaction of a metal complex moiety. 2)Photoluminescence properties of az...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(A), 東京大学, Coinvestigator not use grants, Competitive research funding, 14204066

ポリジアセチレン酸を用いたナノ結晶の2次元配列形成
科学研究費助成事業 特別研究員奨励費
2003 - 2003
米澤 徹, MA Zhangfang
金属ならびに半導体のナノ粒子は「量子サイズ効果」を示す可能性が高く、バルクとも原子・分子とも異なる物性を示すことが期待される。現在はこうしたナノ粒子を湿式法で分散液として調製されることが多く、安価でナノサイズの粒子を単一粒径で得る技術が確立されつつある。こうした、ナノ粒子を材料として利用するとき、ある基板上に秩序を持たせて固定化することが望まれるが、本研究では、手法としてLB法を用いて、スタックさせる界面活性剤としてジアセチレン系カルボン酸に注目した。このカルボン酸は、紫外光によって均一に高分子化されたポリジアセチレン薄膜を形成する。
3種のジアセチレン系カルボン酸を用いて、等温線がpHによってどのような影響を受けるか検討した。その結果、比較的長鎖のカルボン酸が単分子膜を安定に作ることがわかった。さらに、半導体ナノ粒子であるCdSをジアセチレンカルボン酸単分子膜表面に形成させる試みを行った。調査カルボン酸では、1mM以上のカドミウムイオンを入れても安定に単分子膜ができた。しかし、現時点ではこれらを複写した膜はドメイン構造を作っていた。
日本学術振興会, 特別研究員奨励費, 東京大学, 02F00360

機能性無機微粒子の精密配列制御法の開発
科学研究費補助金(萌芽的研究)
2001 - 2001
河本 邦仁, 増田 佳丈, 米澤 徹
N_2雰囲気下でSi基板をPTCS(フェニルトリクロロシラン)溶液中に浸漬してPTCS自己組織膜を作製し、ここにフォトマスクを通してUV照射を行う事により、フェニル基とOH基のマイクロパターンを作製した。SiO_2粒子(500nmφ及び15nmφ)の表面にTCES(トリクロロシアノエチルシラン)を結合させて最表面をCN基とし、さらにt-BuOK(カリウムブトキシド)によりCOOH基へと変性した。このSiO_2粒子最表面のCOOH基と自己組織膜上のOH基をDCC(ジシクロヘキシルカルボジイミド)により縮合させてエステル結合を形成させることにより、自己組織膜上のOH基上に選択的にSiO_2粒子を配置させることを試みた。UV照射によりシラノール基へと変性した領域からは、SEM観察によりSiO_2粒子が確認され、フェニル基上からは粒子は観測されなかった。この手法により、マイクロメーターオーダーの2次元粒子配列パターンが形成された。また、ダイヤモンドチップで自己組織膜表面を走査する事により、機械的にフェニル基を取り去り、任意の箇所をシラノール基へと変性した自己組織膜上からも粒子の選択的配列が確認され、1次元の粒子細線が形成できた。また、AFMリソグラフにより変性した自己組織膜上からも選択的粒子配列が確認された。上記のエステル結合の形成に代えて、酸あるいは塩基により粒子表面のシラノール基...
文部科学省, 萌芽的研究, 名古屋大学, Coinvestigator not use grants, Competitive research funding, 13875122

新規な無機ナノボールの創出と特殊配列の付与
科学研究費補助金(奨励研究(A))
2000 - 2001
米澤 徹
ナノ粒子の調製において、本研究では、これまでにあまり研究例のない、水に良く分散するナノ粒子とフッ素系溶媒に分散するナノ粒子を調製した。これらのナノ粒子は安定で、酸化されたり、沈澱を生じたりしない。特に、フッ素系配位子を用いた場合には遷移金属の微細で単分散なナノ粒子を安定に調製することが可能であることを見出している(特許出願済)。水に分散するナノ粒子は、末端に4級アンモニウム基をもった保護剤で保護したもので、どのようなpHでも正のゼータ電位を有している。そのため、アニオン性の高分子や二分子膜、無機物質表面に容易に吸着し、パターニングによる特殊配列の付与が可能であることがわかった。このような吸着力をもつナノ粒子は、これから期待される塗布用ナノ粒子材料の基材として非常に重要であることが考えられる。また、フッ素系保護剤により保護されたナノ粒子の構造および物性を詳細に検討したところ、これらのナノ粒子が(1)空気下で安定に調製できる、(2)空気中に安定に保存できる、(3)沈殿させて粉末状に保存ができる。(4)フッ素系溶剤を用いて簡単に薄く塗布できる。という特徴を有することが分かった。この塗布技術により、ナノ粒子の2次元パターニングが容易にできることが見出され、特殊配列の付与ができたといえる。このように本研究により、研究者らは新しい性質をもつナノ粒子の創成に成功した。また、それらに特殊配列...
文部科学省, 奨励研究(A), 九州大学->名古屋大学, Principal investigator, Competitive research funding, 12740383

Fabrication of functhinal cermic devices using biomimetic processes
Grants-in-Aid for Scientific Research(基盤研究(B))
2000 - 2001
Kunihito KOUMOTO, 徐 元善, 増田 佳丈, 米澤 徹
We succeeded in fabricating micropatterns of titanium dioxide thin films on SAMs (self-assembled monolayers). SAMs of OTS (octadecyltrichloro-silane) were formed on Si wafers, and were modified by UV irradiation using a photomask to generate methyl / silanol-pattern. They were used as templates to deposit titanium dioxide thin films by the use of TDD (titanium dichloride diethoxide). Amorphous TiO2 films were selectively deposited on silanol regions. Line width variation of the-pattern of an as-deposited film was improved to be well below the electronics design rule, 5 %. Furthermore, Patte...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 名古屋大学, Coinvestigator not use grants, Competitive research funding, 12450350

分子膜と擬一次元金属錯体から成る超分子組織体の開発とその溶液化学
科学研究費補助金(特定領域研究(A))
2000 - 2000
君塚 信夫, 米澤 徹
ハロゲン架橋一次元白金混合原子価錯体[Pt(en)_2][PtCl_2(en)_2]と種々のアニオン性合成脂質とのポリイオンコンプレックス形成により、脂溶性の有機-無機超分子組織体を作成した。キラルなアニオン性脂質の合成について合成ルートを検討した結果、L-グルタミン酸ジドデシルエステルとスルホ酢酸を、ピリジン存在下BOP試薬で縮合させる方法が有効であることを明らかにした。この脂質と[Pt(en)_2]、[PtCl_2(en)_2]を含む水溶液を混合したところ、紫色の沈殿がえられた。この紫色はPt(II)→Pt(IV)の電荷移動吸収に基づくものであり、複合体中において一次元白金錯体が形成されていることが判った。この複合体はクロロホルムに分散すると淡黄色となり、これは分子錯体[PtCl_2(en)_2]の色であることから、クロロホルム中においてハロゲン架橋構造は解離していることがわかった。一方、ジクロルメタン中においては紫色の溶液として分散し、溶媒に依存して一次元白金錯体構造が保たれることが判った。この溶液について円偏光二色性スペクトルの測定を行ったところ、電荷移動吸収帯に励起子分裂型のコットン効果が観測された。これは、脂質の不斉によって一次元白金錯体にCDスペクトルが誘起された、はじめての例であり、脂質と一次元錯体の構造秩序性が極めて高いことが明らかとなった。さらに、AFM観...
文部科学省, 特定領域研究(A), 九州大学, Coinvestigator not use grants, Competitive research funding, 12023238

二分子膜ハイドロゲルの創成に基づく蛋白質機能の時空間制御
科学研究費補助金(特定領域研究(A))
1999 - 2000
君塚 信夫, 一ノ瀬 泉, 米澤 徹
我々は"分子組織性ハイドロゲル"を開発し、その基本特性を解明することを目的として、複数のアミド基を含み、かつグルタミン酸骨格を有するカチオン型脂質を合成した。その結果、従来の二分子膜形成化合物に比べて短いアルキル鎖(C_8:短鎖型脂質)ならびにイソプロピル基を疎水部側に導入した分岐型脂質に過塩素酸アニオン、ナフタレンスルホン酸などの疎水性アニオンを添加すると、ハイドロゲルが得られることが判った。これらの分散水溶液(1^〜2mM)について電子顕微鏡観察を行ったところ、幅8-10nm、長さ3μm以上のファイバー状会合体を基本とする網目状構造が観測された。これらの会合形態は二分子膜に特徴的なものであり、疎水性アニオンの添加によって、これらの短鎖型脂質や分岐型脂質が発達したファイバー状架橋構造を与えたことが判る。従来型の二分子膜形成化合物においては、このようなハイドロゲル形成が認められないことから、(i)結晶性を低めた疎水部構造、(ii)疎水性のイオンペアから成る親水部、かつ(iii)発達した水素結合ネットワークの形成が分子組織性ハイドロゲルを得るための条件であることが判った。ゲルを加熱すると、60-75℃の領域で溶解してゾルとなり、その後さらに加熱すると急激に白濁した。この変化は可逆的であり、冷却すると白濁が消失して元の均一なハイドロゲルが得られた。このように、分子組織性ハイドロゲ...
文部科学省, 特定領域研究(A), 九州大学, Coinvestigator not use grants, Competitive research funding, 11167264

Development of the Gel -Assisted Transfer Technique
Grants-in-Aid for Scientific Research(基盤研究(C))
1999 - 2000
Nobuo KIMIZUKA, 一ノ瀬 泉, 米澤 徹
We have studied two-dimensional organization of water-solubie nanoparticles by the use of hydrogel surface as substrate, and provide the first experimental report on gel-assisted transfer (GAT) of nanoparticles onto solid substrates.Colloidal dispersions of silica nano-particles (diameter, 100 nm) were spread on agarose gel surface. The spreading solution on the gel disappeared either by penetration or by evaporation after ca. 12 hrs. Solid substrates (HOPG, mica) were subsequently pressed against the gel surface. In scanning electron microscopy, densely packed silica nanoparticles are foun...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(C), 九州大学, Coinvestigator not use grants, Competitive research funding, 11640585

多核錯体の逐次吸着を利用する傾斜機能材料の作成
科学研究費補助金(特定領域研究(A))
1998 - 1998
一ノ瀬 泉, 米澤 徹
我々は、分子レベルで組成制御された傾斜機能材料を構築するために、新しい逐次吸着法によるナノ傾斜薄膜の作成を検討してきた。本研究では、互いに反対電荷を有する高分子電解質を用いた交互吸着法、金属アルコシキドの逐次吸着より酸化物ゲル薄膜を作成する表面ゾルゲル法、さらに重合溶媒から直に高分子超薄膜を作成する重合吸着法を確立し、様々な化学的機能の発現を謀った。表面ゾルゲル法では、分子的厚みの酸化物薄膜(チタン、インジウム、ニオブ等)や水酸基を有する有機分子を任意のシーケンスで積層化できる。我々は、酸化物ナノ薄膜とポルフィリン系色素分子との積層型薄膜を作成し、湿式系での光電変換特性を検討した。ITO基板に作成した約20ナノメートルの厚みのIn_2O_3/ポルフィリン多層薄膜にレーザーを照射すると、数μA/cm^2の光電流が観察された。光電流は、積層回数に比例して増大し、酸化物層の種類にも大きく依存した。一方我々は、末端に水酸基とチオール基を有する長鎖アルキル化合物を保護剤とし、粒径制御された金ナノ微粒子を合成する手法を確立させた。これらのナノ粒子は、表面に多くの水酸基を有し、チタンアルコキシドとの交互吸着により、ナノ粒子の構造を保持したまま、固体基板上への積層化が可能であった。表面ゾルゲル法を用いて水晶発振子上にアミノ酸誘導体を含んだ酸化チタンゲル薄膜を作成し、水酸化ナトリウム水溶液で処...
文部科学省, 特定領域研究(A), 九州大学, Coinvestigator not use grants, Competitive research funding, 10123219

金属ナノ粒子を用いた有機-無機複合材料の開発
科学研究費補助金(奨励研究(A))
1997 - 1998
米澤 徹
金属ナノ粒子として,本研究では金ナノ粒子を選択した.保護剤を添加せずにクエン酸還元法によって調製した金ナノ粒子はその濃縮が困難だが,限外ろ過膜を使用することで,常温で濃縮でき,さらに,分散液中に混在するクエン酸イオンなどを除去した.その分散液に,入れ子型構造単分子膜を形成している両親媒性分子基板を浸積すると,1度の浸積で,ほぼ最密充填の金ナノ粒子モノレイヤーが作成できた.このモノレイヤーも導電性を有し,透明である.静電相互作用でほぼ完璧なナノ粒子モノレイヤーの生成を報告したのはこれが世界で初めてである.こうした吸着挙動を高分子電解質を用いた場合や,様々な濃度の金ナノ粒子を用いる事によって比較検討した.また,粒径の揃った粒子ということで,同様にアニオン性のシリカナノ粒子の吸着挙動をモデルとして検討した.粒径によって,吸着挙動が異なる事が見出され,静電相互作用による粒子の有機層への吸着は,有機層自体の安定性や,相互作用の強さに大きく依存する事が示された.また,二分子膜の親水部層間に金イオンを取り込み,その後に還元する手法によっても金ナノ粒子を得ることができるが,この手法では,金ナノ粒子の形状が二分子膜の水中での膨潤状態によって異なり,分散液中による還元では得られにくい,プレート状や,珊瑚状の金ナノ粒子を得ることができた,さらには,金属と配位相互作用を持つ二分子膜物質を設計し,特異...
文部科学省, 奨励研究(A), 九州大学, Principal investigator, Competitive research funding, 09740527

銅酸化物粒子組成物、導電性ペースト及び導電性インク　　　　　　　　　　　　　　　
Patent right, 米澤 徹, 塚本 宏樹, 西本 大夢, 国立大学法人北海道大学、住友金属鉱山株式会社
特願2022-100508, 22 Jun. 2022
特開2022-136081, 15 Sep. 2022
Domestic

銅クラスター、混合粒子、導電性ペースト及び導電性インク　　　　　　　　　　　　　　　
Patent right, 米澤 徹, 西本 大夢, 国立大学法人北海道大学、住友金属鉱山株式会社
特願2019-61444, 27 Mar. 2019
特開2020-100893, 02 Jul. 2020
Domestic

Chair of International Symposium on Sustainable Energy 2023　　　　　　　　　　　　　　　
2023
Planner
北海道大学

アカデミックファンタジスタ　　　　　　　　　　　　　　　
2020 - 2021
Appearance
Visiting lecture
北海道大学
北海道新聞

日本顕微鏡学会 第73回学術講演会 実行委員会委員　　　　　　　　　　　　　　　
2016 - 2017
Planner
日本顕微鏡学会

科学研究費補助金 第一段審査 審査委員　　　　　　　　　　　　　　　
2015 - 2016
Investigator

科学研究費補助金 第一段審査 審査委員　　　　　　　　　　　　　　　
2010 - 2011
Investigator

平成22年度「希少金属代替・削減技術実用化開発助成事業」書面審査委員　　　　　　　　　　　　　　　
2010
Investigator
NEDO

Listed in September 2022 data-update for "Updated science-wide author databases of standardized citation indicators"
Oct. 2022
Elsevier
Internet
https://elsevier.digitalcommonsdata.com/datasets/btchxktzyw/4, [Internet]

ナノ学会 第21回大会 現地実行委員長　　　　　　　　　　　　　　　
2022 - 2023
Planning etc
ナノ学会

國立清華大学（台湾） 教授 外部書面審査委員　　　　　　　　　　　　　　　
2020
Review
國立清華大学

日本XAFS研究会 第21回XAFS討論会実行委員　　　　　　　　　　　　　　　
2018
Planning etc
日本XAFS研究会

國立清華大学（台湾） 准教授 外部書面審査委員　　　　　　　　　　　　　　　
2017 - 2017
Review
國立清華大学

ナノ学会 第15回大会 現地実行副委員長　　　　　　　　　　　　　　　
2016 - 2017
Planning etc
ナノ学会

日本顕微鏡学会 第73回学術講演会 実行委員会委員　　　　　　　　　　　　　　　
2016 - 2017
Planning etc
日本顕微鏡学会

ナノ学会 第９回大会 現地役員　　　　　　　　　　　　　　　
2011
Planning etc
ナノ学会

ナノ学会 第７回大会 現地役員　　　　　　　　　　　　　　　
2009
Planning etc
ナノ学会

Bachelor's degree program, School of Engineering

Master's degree program, Graduate School of Engineering

Doctoral (PhD) degree program, Graduate School of Engineering