Photolysis of the sulfonamide bond of metal complexes of N-dansyl-1,4,7,10-tetraazacyclododecane in aqueous solution: a mechanistic study and application to the photorepair of cis,syn-cyclobutane thymine photodimer.
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 Zn(2+), log K(s)(ZnL(2)), in aqueous solution at 25 degrees C with I = 0.1 (NaNO(3)) was determined to be 6.5+/-0.1. The structure of the ZnL(2) complex was confirmed by single-crystal X-ray diffraction analysis. During fluorescence titrations of L(2) with Zn(2+) (irradiation at 308 or 350 nm) in aqueous solution at pH 7.4 (10 mM HEPES with I = 0.1 (NaNO(3))) and 25 degrees C, considerable enhancement in fluorescence emission of the Zn(2+) complex of L(2) (ZnL(2)) was observed, while metal-free L(2) 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 ZnL(2), yielding the Zn(2+)-cyclen complex and 5-dimethylaminonaphthalene-1-sulfinic acid, which has a greater quantum yield (Phi) for fluorescence emission than that of L(2) and ZnL(2). For comparison, the photolysis of N-(1-naphthalenesulfonyl)cyclen (L(3)) and its Zn(2+) complex (ZnL(3)) 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 ZnL(2) and ZnL(3).
Aoki
Shin
S
Faculty of Pharmaceutical Sciences, Tokyo University of Science, 2641 Yamazaki, Noda 278-8510, Japan. shinaoki@rs.noda.tus.ac.jp
Tomiyama
Yumiko
Y
Kageyama
Yoshiyuki
Y
Yamada
Yasuyuki
Y
Shiro
Motoo
M
Kimura
Eiichi
E
D018360:Crystallography, X-Ray; D000080027:Cyclams; D005456:Fluorescent Dyes / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D007700:Kinetics; D008968:Molecular Conformation; D010777:Photochemistry; D011740:Pyrimidine Dimers / Q000737:chemistry*; D013056:Spectrophotometry, Ultraviolet; D013237:Stereoisomerism; D013449:Sulfonamides / Q000737:chemistry*; D014867:Water / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*
D000080027:Cyclams; D005456:Fluorescent Dyes; D006571:Heterocyclic Compounds; D011740:Pyrimidine Dimers; D013449:Sulfonamides; D014867:Water; C038072:cyclen; D015032:Zinc