Shin Aoki, Yumiko Tomiyama, Yoshiyuki Kageyama, Yasuyuki Yamada, Motoo Shiro, Eiichi Kimura
Chem. Asian J. 4 (4) 561 - 573 1861-4728 2009/04/06
[Refereed][Not invited] Sulfonamide constitutes a ubiquitous functional group that is frequently used in organic chemistry, analytical chemistry, and medicinal chemistry. We report herein on the photolysis of a dansylamide moiety of 1-dansyl-1,4,7,10-tetraazzacyclododecane (N-dansylcyclen, L-2) in the presence of a zinc(II) ion in aqueous solution. By potentiometric pH titrations, the complexation constant for the 1:1 complex of L-2 and Zn2+, logK(s)(ZnL2), in aqueous solution at 25 degrees C with I=0.1 (NaNO3) was determined to be 6.5 +/- 0.1. The structure of the ZnL2 complex was confirmed by single-crystal X-ray diffraction analysis. During fluorescence titrations of L-2 With Zn2+ (irradiation at 308 or 350 nm) in aqueous solution at pH 7.4 (1.0 mM HEPES with I=0.1 (NaNO3)) and 25 degrees C, considerable enhancement in fluorescence emission of the Zn2+ complex of L-2 (ZnL2) was observed, while metal-free 12 exhibited only a negligible emission change upon UV irradiation. It was revealed that this emission enhancement arose from the photoinduced cleavage of a sulfonylamide moiety in ZnL2, yielding the Zn2+-cyclen complex and 5-dimethylaminonaphthalene-1-sulfinic acid, which has a greater quantum yield (0) for fluorescence emission than that of L-2 and ZnL2. For comparison, the photolysis of N-(1-naphthalenesulfonyl)cyclen (L-3) and its Zn2+ complex (ZnL3) under the same conditions (irradiation at 313 nm) gave the corresponding sulfonate (1-naphthylsulfonate). We also describe the results of a photoreversion reaction of cis,syn-cyclobutane thymine photodimer (T[c,s]T) utilizing the photolysis of ZnL2 and ZnL3.