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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Anaerobic DNA cleavage activity in red light and photocytotoxicity of (pyridine-2-thiol)cobalt(III) complexes of phenanthroline bases
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Anaerobic DNA cleavage activity in red light and photocytotoxicity of (pyridine-2-thiol)cobalt(III) complexes of phenanthroline bases

机译：菲咯啉碱的（吡啶-2-硫醇）钴（III）配合物在红光中的厌氧DNA裂解活性和光细胞毒性

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摘要

Cobalt(III) complexes [Co(pnt)(B)2](NO3)2 (1–3) of pyridine-2-thiol (pnt) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d:2￠,3￠-f ]quinoxaline (dpq in 2) and dipyrido[3,2-a:2￠,3￠-c]phenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The crystal structure of 1a as mixed ClO4 - and PF6 - salt of 1 shows a CoIIIN5S coordination geometry in which the pnt and phen showed N,S- and N,N-donor binding modes, respectively. The complexes exhibit Co(III)/Co(II) redox couple near -0.3 V (vs. SCE) in 20% DMF–Tris-HCl buffer having 0.1 M TBAP. The complexes show binding propensity to calf thymus DNA giving Kb values within 2.2 ￥ 104–7.3 ￥ 105 M-1. Thermal melting and viscosity data suggest DNA surface and/or groove binding of the complexes. The complexes show significant anaerobic DNA cleavage activity in red light under argon atmosphere possibly involving sulfide anion radical or thiyl radical species. The DNA cleavage reaction under aerobic medium in red light is found to involve both singlet oxygen and hydroxyl radical pathways. The dppz complex 3 shows non-specific BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via both hydroxyl and singlet oxygen pathways. The dppz complex 3 exhibits photocytotoxicity in HeLa cervical cancer cells giving IC50 values of 767 nM and 19.38 mM in UV-A light of 365 nm and in the dark, respectively. A significant reduction of the dark toxicity of the dppz base (IC50 = 8.34 mM in dark) is observed on binding to the cobalt(III) center.
机译：吡啶-2-硫醇（pnt）和菲咯啉碱（B）的钴（III）配合物[Co（pnt）（B）2]（NO3）2（1-3），即。 1,10-菲咯啉（phen在1中），双嘧啶[3,2-d：2 ￠，3 ￠ -f]喹喔啉（dpq在2中）和二吡啶[3,2-a：2 ￠，3 ￠ -c]吩嗪（dppz in 3）已经制备，表征并研究了其光诱导的厌氧DNA裂解活性。作为1的混合ClO4-和PF6-盐的1a的晶体结构显示CoIIIN5S配位几何结构，其中pnt和phen分别显示N，S-和N，N供体结合模式。在具有0.1 M TBAP的20％DMF-Tris-HCl缓冲液中，络合物在-0.3 V（相对于SCE）附近具有Co（III）/ Co（II）氧化还原对。该复合物显示与小牛胸腺DNA的结合倾向，Kb值在2.2 ￥ 104–7.3 ￥ 105 M-1之间。热熔和粘度数据表明复合物的DNA表面和/或凹槽结合。在氩气气氛下，该复合物在红光下显示出明显的厌氧DNA裂解活性，可能涉及硫化物阴离子自由基或巯基自由基物种。发现在有氧介质中红光下的DNA裂解反应涉及单线态氧和羟基自由基途径。 dppz复合物3通过羟基和单线态氧途径在365 nm的UV-A光中显示非特异性BSA和溶菌酶蛋白的裂解活性。 dppz复合物3在HeLa宫颈癌细胞中表现出光细胞毒性，在365 nm的UV-A光和黑暗中的IC50值分别为767 nM和19.38 mM。与钴（III）中心结合后，可观察到dppz碱的暗毒性显着降低（暗处的IC50 = 8.34 mM）。

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