1206884-99-2Relevant academic research and scientific papers
Design and synthesis of a fluorescent probe for Zn2+, 5,7-Bis(N,N-dimethylaminosulfonyl)-8-hydroxyquinoline-Pendant 1,4,7,10-Tetraazacyclododecane and Zn2+-Dependent Hydrolytic and Zn2+-independent photochemical reactivation of its benzenesulfonyl-caged derivative
Ohshima, Ryosuke,Kltamura, Masanori,Morita, Akinori,Shiro, Motoo,Yamada, Yasuyuki,Lkekita, Masahiko,Kimura, Eiichi,Aoki, Shin
experimental part, p. 888 - 899 (2010/04/28)
We previously reported on a 8-quinolinol-pendant cyclen (L5) as a Zn2+ fluorophore (cyclen = 1,4,7,10-tetraazacyclododecane) and its caged derivative, 8-(benzenesulfonyloxy)-5-(N,N-dimethylaminosulfonyl)quinolin- 2ylmethyl-pendant cyclen (BS-caged-L5), which can be reactivated by hydrolysis of benzenesulfonyl group upon complexation with Zn2+ at neutral pH to give a 1:1 Zn2+-L5 complex (Zn(H -1L5)). We report herein on the synthesis of 5,7-bis(N,N-dimethylaminosulfonyl)-8-hydroxyquinolin-2-ylmethyl-pendant cyclen (L6) and its caged derivative (BS-caged-L6) for more sensitive and more efficient cell-membrane permeability than those of L 5 and BS-caged-L5. By Potentiometrie pH, 1H NMR, and UV-vis spectroscopic titrations, the deprotonation constants pK a1-pKaB of H5L6 were determined to be 3). The results of 1H NMR, Potentiometrie pH, UV-vis, and fluorescent titrations showed that L6 rapidly forms a 1:1 complex with Zn2+ (Zn(H-1L6)), the dissociation constant of which is 50 fM at pH 7.4. The fluorescent emission of Zn(H -1L6) at 478 nm is 32 times as large as that of L6 (excitation at 370 nm), and the fluorescent quantum yield of Zn(H -1L6) (F = 0.41) is much greater than that of Zn(H-1L5) (4>F = 0.044). The BScaged-L 6 was reactivated by hydrolysis of the benzenesulfonyl moiety more rapidly (completes in 30 min at pH 7.4 at 37 °C) than BS-caged-L 5, presumably enabling the practical detection of Zn2+ in sample solutions and living cells. The photochemical deprotection of BS-caged-L6 and the cell membrane permeability of L6 and BS-caged-L6 are also described.
Photochemical cleavage reactions of 8-quinolinyl sulfonates in aqueous solution
Kageyama, Yoshiyuki,Ohshima, Ryosuke,Sakurama, Kazusa,Fujiwara, Yoshihisa,Tanimoto, Yoshifumi,Yamada, Yasuyuki,Aoki, Shin
experimental part, p. 1257 - 1266 (2010/05/02)
Photochemical cleavage reactions of 8-quinolinyl benzenesulfonate derivatives and related sulfonates in aqueous solutions are reported. The 8-quinolinyl benzenesulfonates undergo photolysis upon photoirradiation at 300-330 nm to give the corresponding 8-quinolinols and benzenesulfonic acids with the production of only negligible amounts of byproducts. The effects of substituent groups of the 8-quinolinyl moiety and the benzene ring on the photolysis reactions were examined. Based on steady-state mechanistic studies using a triplet sensitizer, a triplet quencher, and electron donors, it was suggested that the photolysis proceeds mainly via the homolytic cleavage of S-O bonds in the excited triplet state.
