研究者データベース
| 猪熊 泰英(イノクマ ヤスヒデ) |
| 工学研究院 応用化学部門 有機工業化学分野 |
| 教授 |
Last Updated :2023/12/05
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職歴
- 2023年04月 - 現在 北海道大学 大学院工学院 教授
- 2016年04月 - 2023年03月 北海道大学 工学研究院 准教授
- 2014年03月 - 2016年03月 東京大学 工学(系)研究科(研究院) 講師
- 2009年04月 - 2014年02月 東京大学 工学(系)研究科(研究院) 助教
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論文
- Akira Yokoi, Mayu Ukai, Takao Yasui, Yasuhide Inokuma, Kim Hyeon-Deuk, Juntaro Matsuzaki, Kosuke Yoshida, Masami Kitagawa, Kunanon Chattrairat, Mikiko Iida, Taisuke Shimada, Yumehiro Manabe, I-Ya Chang, Eri Asano-Inami, Yoshihiro Koya, Akihiro Nawa, Kae Nakamura, Tohru Kiyono, Tomoyasu Kato, Akihiko Hirakawa, Yusuke Yoshioka, Takahiro Ochiya, Takeshi Hasegawa, Yoshinobu Baba, Yusuke Yamamoto, Hiroaki KajiyamaScience Advances 9 27 2023年07月07日Cancer cell–derived extracellular vesicles (EVs) have unique protein profiles, making them promising targets as disease biomarkers. High-grade serous ovarian carcinoma (HGSOC) is the deadly subtype of epithelial ovarian cancer, and we aimed to identify HGSOC-specific membrane proteins. Small EVs (sEVs) and medium/large EVs (m/lEVs) from cell lines or patient serum and ascites were analyzed by LC-MS/MS, revealing that both EV subtypes had unique proteomic characteristics. Multivalidation steps identified FRα, Claudin-3, and TACSTD2 as HGSOC-specific sEV proteins, but m/lEV-associated candidates were not identified. In addition, for using a simple-to-use microfluidic device for EV isolation, polyketone-coated nanowires (pNWs) were developed, which efficiently purify sEVs from biofluids. Multiplexed array assays of sEVs isolated by pNW showed specific detectability in cancer patients and predicted clinical status. In summary, the HGSOC-specific marker detection by pNW are a promising platform as clinical biomarkers, and these insights provide detailed proteomic aspects of diverse EVs in HGSOC patients.
- Yuki Ide, Hayato Shirakura, Taichi Sano, Muthuchamy Murugavel, Yuya Inaba, Sheng Hu, Ichigaku Takigawa, Yasuhide Inokuma2023年05月26日Visual observations are frequently used as a preliminary evaluation of the chemical contents of mixtures, but their accuracy largely depends on the observer’s experience and intuition, which are difficult to share. Here, we report component ratio pre-diction using image-based machine learning (ML), which is applicable to analysis of various solid mixtures, such as mix-tures of organics and inorganics, polymorphous crystals, and enantiomers. The trained model with 300 images could predict the sugar/dietary salt weight ratio from an image within 4% error. The ML prediction pipeline was shown to be broadly ap-plicable to polymorphic glycine, D/L-tartaric acid, and four-component systems. As an application demonstration, we also used our ML system to analyze yield of a solid-state decarboxylation reaction. These results demonstrated that accumulation of researchers’ experience derived from visual information can be shared as trained ML models and used as a quantitative analysis method.
- Ranajit Saha, Jenny Pirillo, Yuki Ide, Yasuhide Inokuma, Yuh HijikataTheoretical Chemistry Accounts 142 5 2023年04月26日
- Kilingaru I. Shivakumar, Yumehiro Manabe, Tomoki Yoneda, Yuki Ide, Yasuhide InokumaPrecision Chemistry 1 1 34 - 39 2023年03月09日
- Yuya Inaba, Jian Yang, Yu Kakibayashi, Tomoki Yoneda, Yuki Ide, Yuh Hijikata, Jenny Pirillo, Ranajit Saha, Jonathan L Sessler, Yasuhide InokumaAngewandte Chemie International Edition 2023年02月13日 [査読有り][通常論文]
- Taichi Sano, Yuhua Sun, Taichi Mukai, Yuya Inaba, Tomoki Yoneda, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Yasuhide InokumaJournal of Porphyrins and Phthalocyanines 2023年01月21日 [査読有り][招待有り]
- Keita Watanabe, Ranajit Saha, Yuya Inaba, Yumehiro Manabe, Tomoki Yoneda, Yuki Ide, Yuh Hijikata, Yasuhide InokumaJournal of Porphyrins and Phthalocyanines 2022年11月11日
- Yuki Ide, Yumehiro Manabe, Yuya Inaba, Yusuke Kinoshita, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Kilingaru I. Shivakumar, Saki Tanaka, Hitoshi Asakawa, Yasuhide InokumaChemical Science 13 34 9848 - 9854 2022年09月 [査読有り][通常論文]
Critical chain length that divides small molecular crystallization from macromolecular crystallization is an important index in macro-organic chemistry to predict chain-length dependent properties of oligomers and polymers. However, extensive researches... - Narito Ozawa, Kilingaru I. Shivakumar, Muthuchamy Murugavel, Yuya Inaba, Tomoki Yoneda, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Yasuhide InokumaChemical Communications 58 18 2971 - 2974 2022年03月 [査読有り][招待有り]
Cyclic oligoketones composed of 3,3-dimethylpentane-2,4-diones showed crown ether-like alkali metal ion binding behavoir with association constants up to 1.7 x 104 M–1 in chloroform/acetonitrile (v/v, 9/1). The binding properties have... - Yuya Inaba, Yu Kakibayashi, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Yasuhide InokumaChemistry – A European Journal 28 17 2022年02月09日 [査読有り][通常論文]
- Teng Zhang, Yuichi Kitagawa, Ryoma Moriake, Pedro Paulo Ferreira da Rosa, Md. Jahidul Islam, Tomoki Yoneda, Yasuhide Inokuma, Koji Fushimi, Yasuchika HasegawaChemistry – A European Journal 27 58 14438 - 14443 2021年10月19日 [査読有り][通常論文]
In this study, we have demonstrated a two-legged, upright molecular design method for monochromatic and bright red luminescent LnIII -silica nanomaterials. A novel EuIII -silica hybrid nanoparticle was developed by using a doubly binding TPPO-Si(OEt)3 (TPPO: triphenyl phosphine oxide) linker. The TPPO-Si(OEt)3 was confirmed by 1 H, 31 P, 29 Si NMR spectroscopy and single-crystal X-ray analysis. Luminescent Eu(hfa)3 and Eu(tfc)3 moieties (hfa: hexafluoroacetylacetonate, tfc: 3-(trifluoromethylhydroxymethylene)camphorate) were fixed onto TPPO-Si(OEt)3 -modified silica nanoparticles, producing Eu(hfa)3 (TPPO-Si)2 -SiO2 and Eu(tfc)3 (TPPO-Si)2 -SiO2 , respectively. Eu(hfa)3 (TPPO-Si)2 -SiO2 exhibited the higher intrinsic luminescence quantum yield (93 %) and longer emission lifetime (0.98 ms), which is much larger than those of previously reported EuIII -based hybrid materials. Eu(tfc)3 (TPPO-Si)2 -SiO2 showed an extra-large intrinsic emission quantum yield (54 %), although the emission quantum yield for the precursor Eu(tfc)3 (TPPO-Si(OEt)3 )2 was found to be 39 %. These results confirmed that the TPPO-Si(OEt)3 linker is a promising candidate for development of EuIII -based luminescent materials. - Yasuhide Inokuma, Yuya InabaBulletin of the Chemical Society of Japan 94 9 2187 - 2194 2021年09月15日 [査読有り][招待有り]
- Hayato Shirakura, Yumehiro Manabe, Chika Kasai, Yuya Inaba, Makoto Tsurui, Yuichi Kitagawa, Yasuchika Hasegawa, Tomoki Yoneda, Yuki Ide, Yasuhide InokumaEuropean Journal of Organic Chemistry 2021 30 4345 - 4349 2021年08月13日 [査読有り][通常論文]
- Yuya Inaba, Yu Nomata, Yuki Ide, Jenny Pirillo, Yuh Hijikata, Tomoki Yoneda, Atsuhiro Osuka, Jonathan L. Sessler, Yasuhide InokumaJournal of the American Chemical Society 143 31 12355 - 12360 2021年08月11日 [査読有り][通常論文]
- Hayato Shirakura, Yuh Hijikata, Jenny Pirillo, Tomoki Yoneda, Yumehiro Manabe, Muthuchamy Murugavel, Yuki Ide, Yasuhide InokumaEuropean Journal of Inorganic Chemistry 2021 17 1705 - 1708 2021年05月07日 [査読有り]
Metal ion adsorbents are indispensable materials for the recovery of noble metal ions in a sustainable society. Herein, we report that poly(isopyrazole-3,5-diyl-trans-vinylene) (1) effectively adsorbed group 10 metal ions from solution in acetonitrile. Owing to its fully pi-conjugated and rigid structure, polyimine 1 was virtually insoluble in common organic solvents and water, making it advantageous for metal ion adsorption via a solid/liquid interface. Inductively coupled plasma (ICP) analysis showed that >= 90 % of Ni2+, Pd2+, and Pt2+ ions were adsorbed at a concentration of 10 mu M (order of <= 2 ppm) after stirring suspensions at room temperature. Metal ion desorption was achieved by treatment with ethylenediaminetetraacetic acid disodium salt (EDTA . 2Na), and the adsorbent was reused. Theoretical calculations supported that the desolvation energy was an important factor for effective adsorption in acetonitrile. - Yuya Inaba, Yasuhide InokumaChemistry Letters 49 882 - 884 2020年05月13日 [査読有り][通常論文]
- Modular synthesis of oligoacetylacetones via site-selective silylation of acetylacetone derivativesParantap Sarkar, Yuya Inaba, Hayato Shirakura, Tomoki Yoneda, Yasuhide InokumaOrganic & Biomolecular Chemistry 18 3297 - 3302 2020年04月 [査読有り][通常論文]
- Yumehiro Manabe, Keisuke Wada, Yudai Baba, Tomoki Yoneda, Tomoki Ogoshi, Yasuhide Inokuma, Yumehiro Manabe, Keisuke Wada, Yudai Baba, Tomoki Yoneda, Tomoki Ogoshi, Yasuhide InokumaOrganic Letters 2020 22 3224 - 3228 2020年04月 [査読有り][通常論文]
Conformational control of aliphatic oligoketones bearing two 1,3-diketone subunits is achieved by molecular recognition with pillar[5]arene. Pillar[S]arene binds to aliphatic ketones, with association constants K of similar to 10 M-1, to form pseudorotaxanes. The pseudorotaxanes are locked by BF, complexation at the 1,3-diketone sites through quasi-solid-state reactions. X-ray crystallography reveals linear conformations for the axis molecules. The effect of supramolecular conformational restriction is evaluated using an alkyl-linked dyad chromophore system that shows solvatochromism upon intramolecular aggregation. - Hitoshi Asakawa, Sayaka Matsui, Quang Thang Trinh, Hajime Hirao, Yasuhide Inokuma, Tomoki Ogoshi, Saki Tanaka, Kayo Komatsu, Akio Ohta, Tsuyoshi Asakawa, Takeshi FukumaJournal of Physical Chemistry C 124 14 7760 - 7767 2020年04月 [査読有り][通常論文]
Copyright © 2020 American Chemical Society. The self-assembly of organic molecules at the surface of highly oriented pyrolytic graphite (HOPG) is a promising process for constructing molecular-scale architectures. However, selectable organic molecules are generally restricted to two-dimensional molecules with planar Ï-conjugated structures and alkyl chains. We herein present the formation of self-assembled monolayers of tetrakis(4-ethynylphenyl)methane (TEPM) having a three-dimensional (3D) tetrapod geometry on HOPG, which was achieved by utilizing a simple spin-coating method. The arrangements of TEPM molecules in the monolayers were investigated using frequency-modulation atomic force microscopy (FM-AFM). The resulting subnanometer-resolution FM-AFM images revealed that the TEPM molecules formed linear rows with a periodicity of 0.85 nm oriented in a parallel configuration but with two alternating intervals of 0.7 and 1.0 nm. Moreover, the TEPM monolayers were classified into two chiral types with a relationship of mutual mirror-image symmetry, according to the observed molecular arrangements. Our results demonstrate the capability of TEPM molecules to act as 3D building blocks for the design of molecular-scale architectures at interfaces. - Therese Eriksson, Amber Mace, Yumehiro Manabe, Masahiro Yoshizawa-Fujita, Yasuhide Inokuma, Daniel Brandell, Jonas MindemarkJournal of The Electrochemical Society 167 7 070537 - 070537 2020年03月13日
- Yasushi Ogasawara, Yohei Shimizu, Yohei Sato, Tomoki Yoneda, Yasuhide Inokuma, Tohru DairiThe Journal of Antibiotics 73 2 125 - 127 2020年 [査読有り][通常論文]
Peptidoglycan is an indispensable component of bacterial cell walls. We recently discovered an alternative peptidoglycan biosynthetic pathway, which involves two enzymes, MurD2 and MurL, catalyzing the ligation of l-Glu to UDP-MurNAc-l-Ala and epimerization of the terminal l-Glu of the MurD2 product, respectively. Because the pathway operates in Xanthomonas oryze, a pathogen causing bacterial blight of rice, we searched for specific inhibitors from metabolites produced by actinomycetes to obtain a lead compound to function as an agrochemical. Actinomycin D was isolated from Streptomyces parvulus NBRC 13193 as a specific inhibitor of the pathway. In vitro analysis indicated that actinomycin D inhibited the MurD2 reaction. - Yasuhide Inokuma, Tomoki Yoneda, Yuki Ide, Shota YoshiokaChemical Communications 56 64 9079 - 9093 2020年 [査読有り][通常論文]
Synthesis, reactivity, and recent chemistry developments regarding aliphatic polyketones are highlighted with respect to chain sequences. These classic compounds are still showing new research potentials.
- Tomoki Yoneda, Chika Kasai, Yumehiro Manabe, Makoto Tsurui, Yuichi Kitagawa, Yasuchika Hasegawa, Parantap Sarkar, Yasuhide InokumaChemistry–An Asian Journal 15 5 601 - 605 2020年 [査読有り][通常論文]
One- and two-dimensional coordination polymers composed of a structurally flexible, tetradentate diisopyrazole ligand and copper(I) halides were synthesized as crystalline solids. Complexation with copper(I) chloride or bromide resulted in the formation of infinite coordination chains through connecting each diisopyrazole ligand with two copper(I) ions in a trigonal planar coordination geometry. Contrarily, the combination of a diisopyrazole ligand and copper(I) iodide gave a two-dimensional coordination network comprising Cu4I4 units with stair-step type geometry and diisopyrazoles that acted as both tetradentate and bidentate bridging ligands. All the coordination polymers exhibited visible photo-emission upon UV irradiation, and the Cu4I4 complex showed thermochromic behavior. - Yuya Inaba, Tomoki Yoneda, Yuichi Kitagawa, Kiyoshi Miyata, Yasuchika Hasegawa, Yasuhide InokumaCHEMICAL COMMUNICATIONS 56 3 348 - 351 2020年 [査読有り][通常論文]
A dodecahexaene analogue cross-conjugated with four carbonyl groups was prepared from an aliphatic tetraketone. Exposure to LED light (>420 nm) led to the splitting of the dodecahexaene conjugation into two hexatriene subunits, connected through a stereogenic carbon atom. The two triene subunits exhibited excitonic coupling in the UV-Vis absorption and CD spectra. - Takayuki Hoshi, Eisuke Ota, Yasuhide Inokuma, Junichiro YamaguchiOrganic Letters 21 24 10081 - 10084 2019年12月20日 [査読有り][通常論文]
Copyright © 2019 American Chemical Society. A Rh-catalyzed asymmetric intramolecular Buchner ring expansion of α-alkyl-α-diazoesters has been developed. The present protocol generates a 5,7-fused ring system in an enantioselective manner while minimizing β-hydrogen migration, which has been a competing reaction when using α-alkyl-α-diazoesters. The ester functionality at the bridgehead position would be a useful synthetic handle for further derivatization to complex molecules including natural products. - Aliphatic Polyketones as Shapable Molecular Chains猪熊泰英有機合成化学協会誌 77 11 1078 - 1085 2019年11月 [査読有り][招待有り]
- Yumehiro Manabe, Mitsuharu Uesaka, Tomoki Yoneda, Yasuhide InokumaThe Journal of Organic Chemistry 84 16 9957 - 9964 2019年08月 [査読有り][通常論文]
The chemo- and stereo-selective two-step transformation of aliphatic polyketones composed of 3,3-dimethylpentane-2,4-dione units was achieved to generate pi-conjugated polyimines. Upon treatment with hydrazine, discrete oligoketones with 4-8 carbonyl groups afforded ethylene-bridged oligoisopyrazoles in 80-89% yields. These oligoisopyrazoles underwent stereoselective oxidation at the ethylene bridge to give fully pi-conjugated oligo(isopyrazole-3,5-diyl-trans-vinylene)s in 73-87% yields. Oxidation of the oligoimines drastically changed their absorption and metal-coordination behaviors. Finally, this two-step transformation was applied to polydisperse polymers. Imine formation proceeded almost quantitatively, even for longer polyketones, including docosamer. Subsequent oxidation of the polyimines furnished a virtually insoluble material that showed broad and red-shifted solid-state absorption over the whole visible region resulting from extended pi-conjugation. - Yoshiko Ashida, Yumehiro Manabe, Shota Yoshioka, Tomoki Yoneda, Yasuhide InokumaDalton Transactions 48 3 818 - 822 2019年01月 [査読有り][通常論文]
Structurally flexible oligoisopyrazole molecules were self-assembled into discrete complexes with structural diversity upon palladium coordination. Structural convergence was controlled by a stoichiometry change to induce stepwise metal coordination of isopyrazole subunits. Three different types of complexes were selectively generated from a diisopyrazole ligand. Furthermore, tetraisopyrazole ligands were quantitatively assembled into a discrete complex in a predictable manner. - Uesaka Mitsuharu, Saito Yuki, Yoshioka Shota, Domoto Yuya, Fujita Makoto, Inokuma YasuhideCOMMUNICATIONS CHEMISTRY 1 1 2018年04月19日 [査読有り][通常論文]
Abstract Flexible chain-like molecules can adopt various conformations, but fabrication of complex and higher-order architectures by chain networking or coiling is still a difficult task in organic chemistry. As the degree of freedom increases, the large entropy loss impedes conformation and orientation fixing. Here we report oligo (3,3-dimethylpentane-2,4-dione)s as flexible and shapable carbon chains with many carbonyl groups for chemical modification. Polycarbonylated chains of various lengths are synthesized by terminal-selective silylation and oxidative coupling reactions using silver(I) oxide. We use reactions of 1,3-diketones and 1,4-diketones to reduce the chain length and to induce favourable conformations. When the chains are treated with hydrazine, all the carbonyl groups are converted to imine groups, resulting in the formation of multidentate ligands. Finally, a two-dimensional sheet-like structure and a cylindrical assembly are generated by respectively networking and coiling the carbon chains, with the aid of metal coordination. - Yuki Saito, Masayuki Higuchi, Shota Yoshioka, Hisanori Senboku, Yasuhide InokumaChemical Communications 54 50 6788 - 6791 2018年 [査読有り][通常論文]
We report a bioinspired synthesis of 2,5-dihydropentalene-based chromophores from an aliphatic oligoketone bearing 1,3- and 1,4-diketone subunits. Unlike the natural polyketone sequence, fused five-membered rings were formed via an intramolecular aldol condensation. A subsequent Knoevenagel condensation reaction with malononitrile furnished a multiply cross-conjugated π-system with low-lying LUMO levels. Furthermore, pentalenes obtained from a non-conjugated aliphatic chain exhibited visible absorption and solid-state fluorescence. - KaKing Yan, Ritesh Dubey, Tatsuhiko Arai, Yasuhide Inokuma, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139 33 11341 - 11344 2017年08月 [査読有り][通常論文]
Chiral crystalline sponges with preinstalled chiral references were synthesized. On the basis of the known configurations of the chiral references, the absolute structures of guest compounds absorbed in the pores of the crystalline sponges can be reliably determined without crystallization or chemical modification. - Nicolas Zigon, Takashi Kikuchi, Junko Ariyoshi, Yasuhide Inokuma, Makoto FujitaCHEMISTRY-AN ASIAN JOURNAL 12 10 1057 - 1061 2017年05月 [査読有り][通常論文]
Volatile organic compounds are widely present as scents and odors in our daily lives and are readily found in a variety of natural extracts. Because these compounds are highly volatile and usually available only in minute quantities, little attention has been paid to X-ray diffraction as a technique for their structure determination. Here, we show that the structures of volatile organic compounds are easily elucidated using minute quantities of the compounds and the crystalline sponge method. The compound vapors can be directly absorbed into the sponge crystals, or alternatively, preparative gas chromatography can be used to separate the desired compound from a natural mixture. - Yasuhide Inokuma, Kazuki Matsumura, Shota Yoshioka, Makoto FujitaCHEMISTRY-AN ASIAN JOURNAL 12 2 208 - 211 2017年01月 [査読有り][通常論文]
Empirical searching conditions were adopted to identify suitable candidates from the Cambridge Structural Database (CSD) for crystalline sponge hosts for X-ray crystallographic analysis of incoming guest compounds. After optimization of the solvent and soaking conditions, one of the candidates was used as a crystalline sponge for the structure determination of an aromatic guest. - Shota Yoshioka, Yasuhide Inokuma, Vincent Duplan, Ritesh Dubey, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 138 32 10140 - 10142 2016年08月 [査読有り][通常論文]
The crystalline sponge method was used for the X-ray structure analysis of ozonide compounds. As this new technique requires only microgram quantities of the samples, structural analysis can be conducted without product isolation, isomer separation, or crystallization and most importantly without any risk of explosion. - Manabu Hoshino, Anupam Khutia, Hongzhu Xing, Yasuhide Inokuma, Makoto FujitaIUCRJ 3 139 - 151 2016年03月 [査読有り][通常論文]
Crystalline sponges are porous metal complexes that can absorb and orient common organic molecules in their pores and make them observable by conventional X-ray structure analysis (crystalline sponge method). In this study, all of the steps in the crystalline sponge method, including sponge crystal preparation, pore-solvent exchange, guest soaking, data collection and crystallographic analysis, are carefully examined and thoroughly optimized to provide reliable and meaningful chemical information as chemical crystallography. Major improvements in the method have been made in the guest-soaking and data-collection steps. In the soaking step, obtaining a high site occupancy of the guest is particularly important, and dominant parameters for guest soaking (e.g. temperature, time, concentration, solvents) therefore have to be optimized for every sample compound. When standard conditions do not work, a high-throughput method is useful for efficiently optimizing the soaking conditions. The X-ray experiments are also carefully re-examined. Significant improvement of the guest data quality is achieved by complete data collection at high angle regions. The appropriate disorder treatment of the most flexible ZnI2 portions of the host framework and refinement of the solvents filling the remaining void are also particularly important for obtaining better data quality. A benchmark test for the crystalline sponge method toward an achiral molecule is proposed with a guaiazulene guest, in which the guest structure (with similar to 100% site occupancy) is refined without applying any restraints or constraints. The obtained data quality with R-int = 0.0279 and R-1 = 0.0379 is comparable with that of current conventional crystallographic analysis for small molecules. Another benchmark test for this method toward a chiral molecule is also proposed with a santonin guest. The crystallographic data obtained [R-int = 0.0421, R-1 = 0.0312, Flack (Parsons) = -0.0071 (11)] represents the potential ability of this method for reliable absolute structure determination. - Guo-Hong Ning, Kazuki Matsumura, Yasuhide Inokuma, Makoto FujitaCHEMICAL COMMUNICATIONS 52 43 7013 - 7015 2016年 [査読有り][通常論文]
A coordination network composed of a mannose-based organic ligand and a sodium ion, 'sugar sponge', was synthesized for the crystalline sponge analysis of hydrophilic compounds. Owing to multiple hydrogen-bonding interactions, hydrophilic guests are firmly trapped in the 1-dimensional channel. The sugar sponge was utilized to analyze the structures of flexible alcohol and absolute configurations of chiral epoxides. - Yasuhide Inokuma, Tomoya Ukegawa, Manabu Hoshino, Makoto FujitaCHEMICAL SCIENCE 7 6 3910 - 3913 2016年 [査読有り][通常論文]
The structures of metabolites produced in microgram quantities by enzymatic reductions with baker's yeast were analyzed using the crystalline sponge method. The X-ray data provided reliable structures for trace metabolites including their relative and absolute stereochemistries that are not fully addressed by conventional NMR and LC-MS analyses. Technically, combining two or more chromatographic purification techniques is essential because, unlike abundant synthetic compounds, extracted metabolites contain many low level UV-silent impurities. The crystalline sponge method coupled with HPLC purification (LC-SCD) would thus be a useful method for metabolic analysis and drug discovery. - Nicolas Zigon, Manabu Hoshino, Shota Yoshioka, Yasuhide Inokuma, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54 31 9033 - 9037 2015年07月 [査読有り][通常論文]
Crystal structures of -humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio- and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold-related compounds were successfully determined for samples on a 5-50 mu g scale. - Shota Yoshioka, Yasuhide Inokuma, Manabu Hoshino, Takashi Sato, Makoto FujitaCHEMICAL SCIENCE 6 7 3765 - 3768 2015年 [査読有り][通常論文]
The absolute stereochemistry of compounds with axial and planar chirality is successfully determined by the crystalline sponge method without crystallization or derivatization of the compounds. This method is applied to absolute structure determination in the asymmetric synthesis of unique compounds with axial and planar chirality. - Shohei Matsuzaki, Tatsuhiko Arai, Koki Ikemoto, Yasuhide Inokuma, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136 52 17899 - 17901 2014年12月 [査読有り][通常論文]
We have developed a new synthetic protocol for the preparation of a microcrystalline powder (median size: X-50 = 25 mu m) of networked M6L4 cages 1a for the stationary phase of an affinity column on a greater than 50 g scale. Analogously to large single crystals 1b (X-50 approximate to 0.5 mm), microcrystals 1a accommodate guest molecules tetrathiafulvalene (TTF) and fullerene (C-60) at up to 32 and 35 wt %, respectively. Importantly, the hostguest interactions within networked cages could be evaluated in terms of the retention time from HPLC analysis by using microcrystals 1a as the stationary phase. In this way, favorable guests for networked cages 1 and even solution M6L4 cage 2 could easily be assessed by HPLC. - Yasuhide Inokuma, Makoto FujitaBULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 87 11 1161 - 1176 2014年11月 [査読有り][通常論文]
Porous coordination networks have two distinctive characteristics: robust coordination frameworks and fluid pores wherein molecules are mobile. These characteristics allow solution chemistry to be performed in the crystalline state, thus enabling single-crystal X-ray observation of various reactions and host-guest complexation usually observed in solution. From this viewpoint, porous coordination networks can be used as a tool for visualizing solution-based chemical reactions. Using this tool, we have visualized chemical reactions within porous coordination network crystals to elucidate the reaction mechanisms and to determine the molecular structures of the products and intermediates. When the nanospace of porous coordination networks is cleverly designed on the basis of the structures of hollow molecular hosts in solution, solution-like host guest chemistry is also reproduced in crystals, therefore enabling their visualization by X-ray crystallography. Furthermore, a new method based on crystalline-state host-guest chemistry was developed for the single-crystal X-ray analysis of trace amounts of noncrystalline compounds using porous coordination networks. In this account, we review and discuss the visualization of unique solution-like phenomena by single-crystal X-ray analysis using porous coordination networks as crystalline hosts. - Alexander G. O'Brien, Akinobu Maruyama, Yasuhide Inokuma, Makoto Fujita, Phil S. Baran, Donna G. BlackmondANGEWANDTE CHEMIE-INTERNATIONAL EDITION 53 44 11868 - 11871 2014年10月 [査読有り][通常論文]
Electrochemical reactions are shown to be effective for the C-H functionalization of a number of heterocyclic substrates that are recalcitrant to conventional peroxide radical initiation conditions. Monitoring reaction progress under electrochemical conditions provides mechanistic insight into the C-H functionalization of a series of heterocycles of interest in medicinal chemistry. - Koki Ikemoto, Yasuhide Inokuma, Kari Rissanen, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 136 19 6892 - 6895 2014年05月 [査読有り][通常論文]
Pd-mediated aromatic bromination is intriguing to synthetic and organometallic chemists due to both its synthetic utility and, more importantly, a proposed mechanism involving an uncommon Pd(IV)/Pd(II) catalytic cycle. Here, we report an X-ray snapshot observation of a Pd reaction center during a Pd-mediated aromatic bromination in a single crystal of a porous coordination network crystalline scaffold. Upon treatment of a single crystal with N-bromosuccinimide, sequential X-ray snapshots revealed that the aryl-Pd(II)-L species embedded in the network pores was converted to the brominated aryl product through a transient aryl-Pd(II)-Br species, which is normally unobservable because of its rapid dimerization into insoluble Pd-2(mu-Br)(2) species. Though the reaction pathway may be biased by the crystalline state, the new X-ray snapshot method relies on crystalline flasks to provide important mechanistic insight. - Preparation and guest-uptake protocol for a porous complex useful for 'crystal-free' crystallographyYasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Makoto FujitaNATURE PROTOCOLS 9 2 246 - 252 2014年02月 [査読有り][通常論文]
We recently reported a new method for single-crystal X-ray diffraction (SCD) analysis that does not require the crystallization of the target compound. In this 'crystal-free' crystallography, a tiny crystal of a porous complex is soaked in the solution of the target guest. The guest molecules are absorbed and oriented in the crystal pores and can be analyzed by X-ray diffraction. We describe here a detailed synthetic protocol for the preparation of uniform single crystals of the porous host complex and for the subsequent guest uptake. The protocol describes our most versatile porous complex, which is prepared from commercially available ZnI2 and 2,4,6-tri(4-pyridyl)-1,3,5-triazine. The host complex has large pores with a cross-section of 8 x 5 angstrom(2). Single crystals of the complex are grown from layered solutions of the two components. The pores of the as-synthesized complex are filled with nitrobenzene, which is replaced with the inert solvent cyclohexane. This solvent exchange is essential for the rapid and effective inclusion of target compounds. The most crucial and delicate step is the selection of high-quality single crystals from the mixture of crystals of various shapes and sizes. We suggest using the facial indices of the single crystals as a criterion for crystal selection. Single-crystal samples for X-ray analysis can be prepared by immersing the selected crystals in a cyclohexane/dichloromethane solution of target compound. After a very slow evaporation of the solvent, typically over 2 d, the final crystal can be picked and directly subjected to SCD analysis. The protocol can be completed within similar to 16 d. - Guo-Hong Ning, Yasuhide Inokuma, Makoto FujitaCHEMISTRY-AN ASIAN JOURNAL 9 2 466 - 468 2014年02月 [査読有り][通常論文]
Reactive acrylate esters were encapsulated in the cavity of networked molecular capsules in a single-crystal-to-single-crystal fashion. Owing to the encapsulation effect, acrylates inside the capsules do not undergo polymerization upon irradiation with UV light or heating, while the guest molecules can be quantitatively extracted by treatment with toluene. - Juwon Oh, Jooyoung Sung, Masaaki Kitano, Yasuhide Inokuma, Atsuhiro Osuka, Dongho KimCHEMICAL COMMUNICATIONS 50 72 10424 - 10426 2014年 [査読有り][通常論文]
A series of phenylene-bridged subporphyrin-Zn(II) porphyrin (SubP-ZnP) hybrid systems undergo extraordinarily fast excitation energy transfer (EET) processes from the SubP to the ZnP, aided by conjugative electronic elongation of the SubP to the phenylene-bridge. - Guo-Hong Ning, Yasuhide Inokuma, Makoto FujitaCHEMISTRY-AN ASIAN JOURNAL 8 11 2596 - 2599 2013年11月 [査読有り][通常論文]
- Yasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Yuki Hitora, Kentaro Takada, Shigeki Matsunaga, Kari Rissanen, Makoto FujitaNATURE 501 7466 262 - 262 2013年09月 [査読有り][通常論文]
- Yasuhide Inokuma, Shota Yoshioka, Junko Ariyoshi, Tatsuhiko Arai, Yuki Hitora, Kentaro Takada, Shigeki Matsunaga, Kari Rissanen, Makoto FujitaNATURE 495 7442 461 - + 2013年03月 [査読有り][通常論文]
X-ray single-crystal diffraction (SCD) analysis has the intrinsic limitation that the target molecules must be obtained as single crystals. Here we report a protocol for SCD analysis that does not require the crystallization of the sample. In our method, tiny crystals of porous complexes are soaked in a solution of the target, such that the complexes can absorb the target molecules. Crystallographic analysis clearly determines the absorbed guest structures along with the host frameworks. Because the SCD analysis is carried out on only one tiny crystal of the complex, the required sample mass is of the nanogram-microgram order. We demonstrate that as little as about 80 nanograms of a sample is enough for the SCD analysis. In combination with high-performance liquid chromatography, our protocol allows the direct characterization of multiple fractions, establishing a prototypical means of liquid chromatography SCD analysis. Furthermore, we unambiguously determined the structure of a scarce marine natural product using only 5 micrograms of the compound. - Yasuhide Inokuma, Guo-Hong Ning, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 51 10 2379 - 2381 2012年 [査読有り][通常論文]
- Yasuhide Inokuma, Nodoka Kojima, Tatsuhiko Arai, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 49 19691 - 19693 2011年12月 [査読有り][通常論文]
Two substrates, 4-hydroxydiphenylamine (3) and ethyl isocyanate (4), were successively introduced into the crystals of networked M6L4 cages 1. Because of the encapsulation effect, most of the initially introduced substrate 3 remained within the crystals during immersion in a solution of 4. X-ray analysis revealed that before the reaction, the nucleophilic NH group of 3 is effectively protected by tight packing within the cage units while the OH group is exposed to the incoming second substrate. Successive introduction of 4 into the crystal results in the chemoselective acylation of 3 at the less nucleophilic OH group. The observed chemoselectivity is consistent with that exhibited by discrete M6L4 cage 2 in solution. - Koki Ikemoto, Yasuhide Inokuma, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 42 16806 - 16808 2011年10月 [査読有り][通常論文]
In the pore of a porous coordination network, Diels-Alder reactants, a diene and a dienophile, are recognized by donor-acceptor and multiple H-bond interactions, respectively, and fixed at ideal positions for the reaction. Heating the crystals promoted the Diels-Alder reactions with enhanced reactivity and controlled regioselectivity as clearly monitored by in situ X-ray crystallography. - Yasuhide Inokuma, Masaki Kawano, Makoto FujitaNATURE CHEMISTRY 3 5 349 - 358 2011年05月 [査読有り][通常論文]
A variety of host compounds have been used as molecular-scale reaction vessels, protecting guests from their environment or restricting the space available around them, thus favouring particular reactions. Such molecular 'flasks' can endow guest molecules with reactivities that differ from those in bulk solvents. Here, we extend this concept to crystalline molecular flasks, solid-state crystalline networks with pores within which pseudo-solution-state reactions can take place. As the guest molecules can spontaneously align along the walls and channels of the hosts, structural changes in the substrates can be directly observed by in situ X-ray crystallography during reaction. Recently, this has enabled observation of the molecular structures of transient intermediates and other labile species, in the form of sequential structural snapshots of the chemical transformation. Here, we describe the principles, development and applications of crystalline molecular flasks. - Shin-ya Hayashi, Eiji Tsurumaki, Yasuhide Inokuma, Pyosang Kim, Young Mo Sung, Dongho Kim, Atsuhiro OsukaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 133 12 4254 - 4256 2011年03月 [査読有り][通常論文]
Subbacteriochlorins, which were prepared via hydrogenation of subporphyrins with Raney nickel, are modestly aromatic due to 14 pi-diazaannulenic circuit and exhibit characteristic blue-shifted Soret-like bands, intensified fluorescence spectra, and high oxidation potentials. - Shin-Ya Hayashi, Jooyoung Sung, Young Mo Sung, Yasuhide Inokuma, Dongho Kim, Atsuhiro OsukaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 50 14 3253 - 3256 2011年 [査読有り][通常論文]
- Yasuhide Inokuma, Satoshi Nishiguchi, Koki Ikemoto, Makoto FujitaCHEMICAL COMMUNICATIONS 47 44 12113 - 12115 2011年 [査読有り][通常論文]
A coordination network comprising 2-vinyltriphenylene was treated with AIBN at a high temperature, but the radical polymerization of the vinyl monomer was completely suppressed by spatial separation and otherwise hidden aerobic oxidation pathways are enhanced. - Yasuhide Inokuma, Tatsuhiko Arai, Makoto FujitaNATURE CHEMISTRY 2 9 780 - 783 2010年09月 [査読有り][通常論文]
Many molecular cages selectively bind guests in solution, but in the solid state close packing often prevents guest entry, which renders the cages inactive. We envisioned that coordination networks constructed from well-known molecular cages could transfer the richness of solution-state host-guest chemistry into the solid state. We report a crystalline coordination network generated from an infinite array of octahedral M(6)L(4) cage subunits (M = metal, L = ligand). This coordination network is a 'crystalline molecular sponge' engineered on the molecular level and retains similar guest recognition properties to those found in solution. The network crystallinity is robust and thus X-ray diffraction analysis can be used to unambiguously observe single-crystal to single-crystal guest inclusion. The void spaces define alternating M(12)L(8) and M(12)L(24) cuboctahedral molecular cages and these large cages absorb up to 35 weight per cent of C(60) or C(70) by simply soaking the crystals in a toluene solution of the fullerene. When the crystals are immersed in fullerene mixtures, C(70) is preferentially absorbed. - Shin-ya Hayashi, Yasuhide Inokuma, Atsuhiro OsukaORGANIC LETTERS 12 18 4148 - 4151 2010年09月 [査読有り][通常論文]
meso-Tris(oligo-2,5-thienylene)-substituted subporphyrins exhibit remarkably red-shifted and intensified absorption bands with increasing number of thienyl subunits. A dimeric subporphyrin obtained from homocoupling of a monobrominated tris(2-thienyl)-substituted subporphyrin exhibits a split Soret-like band due to the exciton coupling. - Ryu Sakamoto, Shohei Saito, Soji Shimizu, Yasuhide Inokuma, Naoki Aratani, Atsuhiro OsukaCHEMISTRY LETTERS 39 5 439 - 441 2010年05月 [査読有り][通常論文]
meso-Trifluoromethyl-substituted subporphyrin was obtained through an extrusion reaction from meso-trifluoromethyl-substituted heptaphyrin(1.1.1.1.1.1.1) upon combined metallation of Cu(II) and B(III) ions. The subporphyrin exhibited the most blue-shifted Soret-like absorption band among those ever prepared. - Shin-ya Hayashi, Yasuhide Inokuma, Shanmugam Easwaramoorthi, Kil Suk Kim, Dongho Kim, Atsuhiro OsukaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 2 321 - 324 2010年 [査読有り][通常論文]
- Kazuaki Ohara, Masaki Kawano, Yasuhide Inokuma, Makoto FujitaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 132 1 30 - + 2010年01月 [査読有り][通常論文]
All-trans retinal efficiently diffused into the pore of a porous coordination network consisting of Znl(2) and an electron-deficient triazine-cored ligand. Enclathrated retinal was isomerized into the 13-cis form and easily replaced with all-trans retinal in solution, thus revealing the catalysis of retinal isomerization by the porous network. - Takehide Kawamichi, Yasuhide Inokuma, Masaki Kawano, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 13 2375 - 2377 2010年 [査読有り][通常論文]
- Kazuaki Ohara, Yasuhide Inokuma, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 32 5507 - 5509 2010年 [査読有り][通常論文]
- Koki Ikemoto, Yasuhide Inokuma, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 33 5750 - 5752 2010年 [査読有り][通常論文]
- Yasuhide Inokuma, Shota Yoshioka, Makoto FujitaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 49 47 8912 - 8914 2010年 [査読有り][通常論文]
- Yasuhide Inokuma, Shin-ya Hayashi, Atsuhiro OsukaCHEMISTRY LETTERS 38 3 206 - 207 2009年03月 [査読有り][通常論文]
1,4-Phenylene-bridged subporphyrin-porphyrin hybrid molecules were prepared by the Suzuki-Miyaura cross coupling reaction of meso-(4-bromophenyl)-substituted subporphyrin 2 and 5-pinacolateboryl porphyrin 3. In all hybrid models examined, intramolecular energy transfer from the subporphyrin moiety to the porphyrin moieties proceeds efficiently. - Eiji Tsurumaki, Yasuhide Inokuma, Shanmugam Easwaramoorthi, Jong Min Lim, Dongho Kim, Atsuhiro OsukaCHEMISTRY-A EUROPEAN JOURNAL 15 1 237 - 247 2009年 [査読有り][通常論文]
Effective peripheral fabrication methods of meso-aryl-substituted subporphyrins were explored for the first time. Hexabrominated subporphyrins 2 were prepared quantitatively from the bromination of subporphyrins 1 with bromine. Hexaphenylated subporphyrins 3 and hexaethynylated subporphyrins 4 and 5 were synthesized by Suzuki-Miyaura coupling and Stille coupling, respectively, in good yields. X-ray crystal structures of 2b, 3b, 4b, and 5a revealed preservation of the bowl-shaped bent Structures with bowl depths similar to that of 1. Hexaethynylated subporphyrins exhibit large two-photon-absorption cross-sections clue to effective delocalization of the conjugated network to the ethynyl substituents. - Yasuhide Inokuma, Atsuhiro OsukaCHEMISTRY-A EUROPEAN JOURNAL 15 28 6863 - 6876 2009年 [査読有り][通常論文]
Capped subporphyrins 12-16 with C(3) molecular symmetry were synthesized from 5,10,15-tri(3-aminophenyl)-substituted subporphyrin 8 and tripodal trialdehydes 2-6 by Lindsey's entropically favored macrocyclization. X-ray diffraction analysis has revealed that the concave surface of the subporphyrin core is selectively capped with a 1,3,5-substituted benzene moiety. Capped subporphyrins 15 and 16, with a five-atom arm and thus large inner cavities, exhibit solvent incorporation behavior in their crystal structures. On the other hand, subporphyrins 12 and 13 exhibit tight structures, in which the cap and subporphyrin core are found much closer with average interplanar separations of 3.56 and 3.15 angstrom, respectively. Variable-temperature (1)H NMR measurements revealed that subporphyrins 12, 13, and 16 undergo spiral interconversions between P and M forms depending on the arm length and the electronic nature of the cap. Of these, subporphyrin 13, with a 1,3,5-tri(alkoxycarbonyl)benzene cap strapped by three-atom arms, exhibits a considerably slow spiral interconversion with a large enthalpy change of Delta H(not equal)= 76.4 kJ mol(-1) and a characteristic red-shift of the Soret-like band and enhancement of the Q(0,0) band. These properties are ascribed to considerable through-space charge-transfer interactions between the electron-deficient cap and the subporphyrin core and the multiple CH-pi interactions. - Shanmugam Easwaramoorthi, Jae-Yoon Shin, Sung Cho, Pyosang Kim, Yasuhide Inokuma, Eiji Tsurumaki, Atsuhiro Osuka, Dongho KimCHEMISTRY-A EUROPEAN JOURNAL 15 44 12005 - 12017 2009年 [査読有り][通常論文]
Donor-acceptor systems based on subporphyrins with nitro and amino substituents at meta and para positions of the meso-phenyl groups were synthesized and their photophysical properties have been systematically investigated. These molecules show two types of charge-transfer interactions, that is, from center to periphery and periphery to center depending on the peripheral substitution, in which the subporphyrin moiety plays a dual role as both donor and acceptor. Based on the solvent-polarity-dependent photophysical properties, we have shown that the fluorescence emission of para isomers originates from the solvatochromic, dipolar, symmetry-broken, and relaxed excited states, whereas the non-solvatochromic fluorescence of meta isomers is of the octupolar type with false symmetry breaking. The restricted meso-(4-aminophenyl) rotation at low temperature prevents the intramolecular charge-transfer (ICT)-forming process. The two-photon absorption (TPA) cross-section values were determined by photoexcitation at 800 nm in nonpolar toluene and polar acetonitrile solvents to see the effect of ICT on the TPA processes. The large enhancement in the TPA cross-section value of approximately 3200 GM (1 GM = 10(-50) cm(4)s photon(-1)) with donor-acceptor substitution has been attributed to the octupolar effect and ICT interactions. A correlation was found between the electron-donating/-withdrawing abilities of the peripheral groups and the TPA cross-section values, that is, p-aminophenyl > m-aminophenyl > nitrophenyl. The increased stability of octupolar ICT interactions in highly polar solvents enhances the TPA cross-section value by a factor of approximately 2 and 4, respectively, for p-amino- and m-nitrophenyl-substituted subporphyrins. On the other hand, the stabilization of the symmetry-broken, dipolar ICT state gives rise to a negligible impact on the TPA processes. - Yasuhide Inokuma, Atsuhiro OsukaORGANIC LETTERS 10 24 5561 - 5564 2008年12月 [査読有り][通常論文]
3,3'- and 4,4'-biphenylene-bridged subporphyrin dimers were synthesized by means of a Ni-catalyzed homocoupling reaction. Distinctly red-shifted absorption bands and enhanced fluorescence were observed only for the latter, indicating effective through-bond interactions through a 4,4'-biphenylene bridge, which is not possible for porphyrins. - Jeyaraman Sankar, Shigeki Mori, Shohei Saito, Harapriya Rath, Masaaki Suzuki, Yasuhide Inokuma, Hiroshi Shinokubo, Kil Suk Kim, Zin Seok Yoon, Jae-Yoon Shin, Jong Min Lim, Yoichi Matsuzaki, Osamu Matsushita, Atsuya Muranaka, Nagao Kobayashi, Dongho Kim, Atsuhiro OsukaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 41 13568 - 13579 2008年10月 [査読有り][通常論文]
meso-Aryl-substituted [28]hexaphyrins(1.1.1.1.1.1) have been examined by (1)H, (13)C, and (19)F NMR spectroscopies, UV-vis absorption spectroscopy, magnetic circular dichroism spectroscopy, and single-crystal X-ray diffraction analysis. All of these data consistently indicate that [28]hexaphyrins(1.1.1.1.1.1) in solution at 25 degrees C exist largely as an equilibrium among several rapidly interconverting twisted Mobius conformations with distinct aromaticities, with a small contribution from a planar rectangular conformation with antiaromatic character at slightly higher energy. In the solid state, [28]hexaphyrins(1.1.1.1.1.1) take either planar or Mobius-twisted conformations, depending upon the meso-aryl substituents and crystallization conditions, indicating a small energy difference between the two conformers. Importantly, when the temperature is decreased to -100 degrees C in THF, these rapid interconversions among Mobius conformations are frozen, allowing the detection of a single [28]hexaphyrin(1.1.1.1.1.1) species having a Mobius conformation. Detailed analyses of the solid-state Mobius structures of compounds 2b, 2c, and 2f showed that singly twisted structures are achieved without serious strain and that cyclic pi-conjugation is well-preserved, as needed for exhibiting strong diatropic ring currents. Actually, the harmonic-oscillator model for aromaticity (HOMA) values of these structures are significantly large (0.85, 0.69, and 0.71, respectively), confirming the first demonstration of stable Mobius aromatic systems consisting of free-base expanded porphyrins without the assistance of metal coordination. - Yasuhide Inokuma, Shanmugam Easwaramoorthi, Zin Seok Yoon, Dongho Kim, Atsuhiro OsukaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 37 12234 - + 2008年09月 [査読有り][通常論文]
A series of meso-(4-(N,N-dibenzylamino)phenyl)-substituted subporphyrins was synthesized by means of Buchwald-Hartwig amination protocol. Substitution of the amino group at the 4-position of the meso-phenyl substituent resulted in a remarkable red shift in the absorption spectra and drastic enhancement of fluorescence intensity probably as a consequence of intramolecular CT interaction. These characteristics have been utilized to construct a cation-sensing system by appending a 1-aza-15-crown-5 unit to subporphyrin that displays large spectral changes upon cation binding. - Eiji Tsurumaki, Shohei Saito, Kil Suk Kim, Jong Min Lim, Yasuhide Inokuma, Dongho Kim, Atsuhiro OsukaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 130 2 438 - + 2008年01月 [査読有り][通常論文]
meso-Aryl-substituted subchlorins were obtained as a side product in acid-catalyzed subporphyrin synthesis and were fully characterized. Subchlorins were more efficiently prepared by reduction of subporphyrins with p-losylhydrazide under basic conditions. Structural change from subporphyrin to subchlorin is accompanied by large optical and electrochemical changes that are quite similar to those observed upon change from porphyrin to chlorin. Optical and electrochemical properties of subchlorins are well understood with the framework of Gouterman's four-orbital theory. - Yasuhide Inokuma, Atsuhiro OsukaDALTON TRANSACTIONS 19 2517 - 2526 2008年 [査読有り][通常論文]
Subporphyrin is a ring-contracted porphyrin congener consisting of three pyrrolic subunits domed in a C(3) symmetric bowl arrangement. Subporphyrin had long been elusive until the first synthesis of tribenzosubporphine in 2006. Shortly after, synthetic protocols of subpyriporphyrin, meso-aryl-substituted subporphyrins, and meso-aryl substituted subchlorins were developed. Subporphyrins display interesting properties including distinct aromaticity arising from 14 pi-electronic conjugation, green fluorescence, and strong in fluences of meso-aryl substituents on the electronic network of the macrocycle. Besides the rational synthetic routes, an unexpected route to a specific subporphyrin from a [32] heptaphyrin(1.1.1.1.1.1.1) was discovered via a thermal extrusion reaction upon Cu(II)-B(III) cooperative metallation. In this Perspective, we review recent progress on subporphyrin chemistry and unprecedented ring-splitting reactions of medium size expanded porphyrins that are triggered upon metallation. - Yasuhide Inokuma, Shanmugam Easwaramoorthi, So Young Jang, Kil Suk Kim, Dongho Kim, Atsuhiro OsukaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 47 26 4840 - 4843 2008年 [査読有り][通常論文]
- Yasuhide Inokuma, Zin Seok Yoon, Dongho Kim, Atsuhiro OsukaJOURNAL OF THE AMERICAN CHEMICAL SOCIETY 129 15 4747 - 4761 2007年04月 [査読有り][通常論文]
Two synthetic methods of meso-aryl-substituted subporphyrins have been developed by means of the reaction of pyridine-tri-N-pyrrolylborane with a series of aryl aldehydes. One method relies on the condensation under Adler conditions with chloroacetic acid in refluxing 1,2-dichlorobenzene to afford subporphyrins in 1.1-3.2%, and the other is a two-step reaction consisting of the initial treatment of the two substrates with trifluoroacetic acid at 0 degrees C followed by air-oxidation in refluxing 1,2-dichlorobenzene to provide subporphyrins in up to 5.6% yield. H-1 NMR studies indicate that phenyl and sterically unhindered substituents at the meso position of subporphyrins rotate rather freely even at -90 degrees C, whereas the rotation of meso-2,4,6-trimethoxyphenyl substituents is strictly prohibited even at 130 degrees C. The structures of six subporphyins have been revealed by X-ray crystallographic analysis to be all cone-shaped tripyrrolic macrocycles. Dihedral angles of meso-phenyl and sterically unhindered aryl substituents to the subporphyrinic core are rather small (38.3-55.7 degrees) compared to those of porphyrin analogues, whereas those of meso-2,4,6-trimethoxy-substituted subporphyrins are large (68.7-75.7 degrees). These rotational features of the meso-aryl substituents lead to their large influences on the electronic properties of subporphyrins, as seen for 4-nitrophenyl-substituted subporphyrin 14e that exhibits perturbed absorption and fluorescence spectra, depending upon solvents. Large solvent-polarity dependence of the fluorescence of 14e suggests the charge-transfer character for its excited state. Electrochemical and theoretical studies are performed to understand the electronic properties. Overall, meso-aryl-substituted subporphyrins are promising chromophores in future functional devices. - Yasuhide Inokuma, Atsuhiro OsukaCHEMICAL COMMUNICATIONS 28 2938 - 2940 2007年 [査読有り][通常論文]
meso-Aryl-substituted subporphyrins bearing a 2-carboxyphenyl group were prepared and shown to form complementary face-to-face dimers upon azeotropic removal of methanol. - Y Inokuma, JH Kwon, TK Ahn, MC Yoo, D Kim, A OsukaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 45 6 961 - 964 2006年 [査読有り][通常論文]
- Y Inokuma, N Ono, H Uno, DY Kim, SB Noh, D Kim, A OsukaCHEMICAL COMMUNICATIONS 30 3782 - 3784 2005年 [査読有り][通常論文]
Enlargement of the pi-electronic network of meso-meso, beta-beta, beta-beta triply linked diporphyrin has been exploited by preparing a corresponding dibenzo-fused porphyrin dimer that exhibits a perturbed absorption spectrum and a large two-photon absorption cross section. - Y Inokuma, T Matsunari, N Ono, H Uno, A OsukaANGEWANDTE CHEMIE-INTERNATIONAL EDITION 44 12 1856 - 1860 2005年 [査読有り][通常論文]
- Y Inokuma, A OsukaORGANIC LETTERS 6 21 3663 - 3666 2004年10月 [査読有り][通常論文]
A series of meso-porphyrinyl-substituted expanded porphyrins were prepared from the 1:1 acid-catalyzed condensation reaction of 4-porphyrinyl-2,3,5,6-tetrafluorobenzaldehyde and pyrrole.
その他活動・業績
- 猪熊泰英 化学と工業 71 (10) 822‐823 2018年10月01日 [査読無し][通常論文]
- 猪熊泰英 Bulletin of Japan Society of Coordination Chemistry 63 (63) 29 -37 2014年05月31日 [査読無し][通常論文]
- 猪熊泰英, 小野昇, 宇野英満, 大須賀篤弘 複素環化学討論会講演要旨集 35th 275 -276 2005年10月10日 [査読無し][通常論文]
特許
- 藤田 誠, 猪熊 泰英, 堂本 悠也 国立大学法人 東京大学 202003019296205512
- 藤田 誠, 猪熊 泰英 国立大学法人 東京大学 201903013263324045
- WO2019-151419:ポリカルボニル化合物、その誘導体及びそれらの製造方法 2019年08月08日猪熊 泰英, 吉岡 翔太, 上坂 光晴, 齋藤 結大, 芦田 記子 国立大学法人北海道大学 202103020068718416
- 藤田 誠, 猪熊 泰英, 山口 健太郎 国立研究開発法人科学技術振興機構 201903011559534794
- 藤田 誠, 猪熊 泰英, 荒井 達彦 国立大学法人 東京大学 201703020981997173
- 藤田 誠, 猪熊 泰英 国立研究開発法人科学技術振興機構 201703015137264655
- 特開2017-036919:結晶構造解析用試料の作製方法、及び代謝物の分子構造決定方法 2017年02月16日藤田 誠, 猪熊 泰英 国立研究開発法人科学技術振興機構 201703009578350034
- 藤田 誠, 猪熊 泰英, 堂本 悠也 国立大学法人 東京大学 201603008117028765
- 藤田 誠, 猪熊 泰英 国立大学法人 東京大学 201603016965227460
- 藤田 誠, 猪熊 泰英, 吉岡 翔太, 有吉 絢子 国立研究開発法人科学技術振興機構 201603018979109862
- WO2016-017770:回折データの解析方法、コンピュータプログラム及び記録媒体 2016年02月04日藤田 誠, 猪熊 泰英, 山口 健太郎 国立研究開発法人科学技術振興機構 201703015667650068
- 藤田 誠, 猪熊 泰英, 荒井 達彦 国立大学法人 東京大学 201703018276972370
- 藤田 誠, 猪熊 泰英, 荒井 達彦 国立大学法人 東京大学 201503003951609139
- 特開2014-169265:細孔性ネットワーク錯体、その製造方法、及び、充填剤として使用する方法 2014年09月18日藤田 誠, 猪熊 泰英, 松崎 正平, 池本 晃喜 国立大学法人 東京大学 201403049017984831
- 藤田 誠, 猪熊 泰英, 吉岡 翔太, 有吉 絢子 国立研究開発法人科学技術振興機構 201603009919727452
- 藤田 誠, 猪熊 泰英, 荒井 達彦 国立大学法人 東京大学 201303020326161712
受賞
- 2022年04月 公益財団法人長瀬科学技術振興財団 長瀬研究振興賞
受賞者: 猪熊 泰英 - 2019年12月 Asian Chemical Congress Asian Rising Stars Lectureship
Aliphatic polyketones for clay-play like molecular synthesis受賞者: 猪熊 泰英 - 2019年04月 田中貴金属記念財団 「貴金属に関わる研究助成金」奨励賞
脂肪族ポリイミン化合物を基盤とする貴金属イオン吸着材料の開発受賞者: 猪熊泰英 - 2016年04月 東京大学大学院工学系研究科 東京大学工学系研究科長表彰
受賞者: 猪熊泰英 - 2015年09月 一般財団法人 フロンティアサロン財団 永瀬賞 特別賞
分子構造を捉える手法 「結晶スポンジ法」の開発受賞者: 猪熊泰英 - 2015年04月 文部科学省 文部科学大臣表彰 若手科学者賞
細孔性結晶を用いた微量化合物のＸ線結晶構造解析法の研究受賞者: 猪熊泰英 - 2014年12月 科学技術・学術政策研究所 (NISTEP) ナイスステップな研究者2014
ごく微量の化合物や非結晶物質の精緻なＸ線構造解析を可能にする「結晶スポンジ法」の開発受賞者: 猪熊泰英 - 2014年03月 日本化学会 進歩賞
細孔性錯体を用いた溶液化学のＸ線構造解析による可視化受賞者: 猪熊泰英 - 2013年11月 錯体化学会 研究奨励賞
細孔性錯体を用いた結晶化を必要としない結晶構造解析法の開発受賞者: 猪熊泰英 - 2013年03月 英国王立化学会 PCCP賞
Nano-to-microgram scale X-ray crystallography of non-crystalline compounds using crystalline sponges受賞者: 猪熊泰英
共同研究・競争的資金等の研究課題
- 水素イオンセラミックス日本学術振興会：科学研究費助成事業 特別推進研究研究期間 : 2022年04月 -2027年03月代表者 : 陰山 洋, 高津 浩, タッセル セドリック, 加藤 大地, 高村 仁, 猪熊 泰英, 内田 さやか, 藤井 進, 小林 俊介
- ポリケトンを基盤とする歪んだ環縮小ポルフィリノイドの化学日本学術振興会：科学研究費助成事業 基盤研究(B)研究期間 : 2022年04月 -2025年03月代表者 : 猪熊 泰英
- 化学反応で張力を発現する「分子ひも」の開発日本学術振興会：科学研究費助成事業 挑戦的研究(萌芽)研究期間 : 2020年07月 -2023年03月代表者 : 猪熊 泰英
- ｢中分子ひも｣を鍵とする巨大機能性分子の創成国立研究開発法人 科学技術振興機構：創発的研究支援事業研究期間 : 2022年04月
- 脂肪族カルボニル化合物を基盤とする巨大π共役系化合物の「一筆書き合成法」の開発公益財団法人 旭硝子財団：若手継続グラント研究期間 : 2019年04月 -2022年03月代表者 : 猪熊泰英
- 単結晶構造解析で切り拓くメゾスコピック領域の構造有機化学 研究課題日本学術振興会：若手研究(A)研究期間 : 2017年04月 -2021年03月代表者 : 猪熊泰英
- 脂肪族ポリイミン配位子によるアシンメトリック分子認識空間の構築 公募研究日本学術振興会：新学術領域研究(研究領域提案型)研究期間 : 2017年04月 -2019年03月代表者 : 猪熊泰英
- 重合反応のナノ空間精密制御による構造一義的なポリカルボニル化合物の合成手法開発公益財団法人 旭硝子財団：研究奨励研究期間 : 2016年04月 -2018年03月代表者 : 猪熊泰英
- 細孔性結晶を用いた微量薬物の分解・代謝過程の可視化国立研究開発法人 科学技術振興機構：さきがけ研究期間 : 2013年10月 -2017年03月代表者 : 猪熊泰英
- ネットワーク化分子カプセルを用いた新しい有機合成手法の開発日立財団：倉田奨励金研究期間 : 2012年04月 -2014年03月代表者 : 猪熊泰英
- 単結晶内ホストーゲスト化学を基盤とした機能性結晶マテリアルの開発 研究課題日本学術振興会：若手研究(B)研究期間 : 2011年04月 -2013年03月代表者 : 猪熊泰英
- 細孔性ネットワーク錯体をフラスコに用いた新規有機化学反応の開発と単結晶の機能化 研究課題日本学術振興会：研究活動スタート支援研究期間 : 2009年 -2011年03月代表者 : 猪熊泰英
教育活動情報
主要な担当授業
- 超分子化学開講年度 : 2021年課程区分 : 修士課程開講学部 : 総合化学院キーワード : ホストーゲスト化学、分子間相互作用、水素結合、大環状化合物、イオン認識、構造、立体化学、キラリティー
- 応用化学学生実験Ⅴ開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : 有機化学、高分子化学、安全教育、基礎実験、合成実験
- 化学Ⅱ開講年度 : 2021年課程区分 : 学士課程開講学部 : 全学教育キーワード : 有機化合物、官能基、分子構造、化学的性質、化学反応、機能性有機物、生体関連有機物質
- 有機化学Ⅰ開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : 有機化学 アルカン アルケン アルキン 立体化学
- 物質変換工学開講年度 : 2021年課程区分 : 学士課程開講学部 : 工学部キーワード : 有機合成，有機材料，化学プロセス，反応器設計，生体材料，高分子材料，分子機能，無機材料，複合材料，電子材料，光機能材料