基于non-innocent配体钌配合物的DNA光断裂能力研究
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- 英文论文题名：DNA photocleavage by non-innocent ligand-based Ru(Ⅱ) complexes
- 论文作者：张阳阳 ; 周前雄 ; 郑月 ; 侯原军 ; 张宝文 ; 王雪松
- 英文论文作者：Yangyang Zhang ; Qianxiong Zhou ; Yue Zheng ; Yuanjun Hou ; Baowen Zhang ; Xuesong Wang ; Technical Institute of Physics and Chemistry ; Chinese Academy of Sciences
- 年：2016
- 作者机构：中国科学院理化技术研究所;
- 论文关键词：DNA光断裂试剂 ; 钌配合物 ; non-innocent配体
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第二十七分会：光化学
- 语种：中文
- 分类号：O641.4;Q523
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第二十七分会 ; 光化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：181k
- 原文格式：D
- 会议级别：全国
摘要
凭借对DNA结构和功能的高时空选择性调控,DNA光断裂试剂研究多年来一直广受关注[1]。我们首次发现基于non-innocent配体8-羟基喹啉的钌配合物[Ru(bpy)2(R-OQN)]+(bpy=2,2′-bipyridine,R-OQN=5-chloro-8-oxyquinolate or 5-bromo-8-oxyquinolate)能够实现DNA光断裂,且断裂效率高于[Ru(bpy)3]2+(Fig.1)。机理研究表明,这两种配合物可以光诱导产生羟基自由基,从而导致DNA断裂,这与已知钌配合物光断裂DNA的三种机制(经由单重态氧、MLCT态或Ru(III)物种)截然不同。有趣的是,8-羟基喹啉配体5位卤素取代起到至关重要的作用。当5-氯(溴)-8-羟基喹啉被8-羟基喹啉或者5-甲基-8-羟基喹啉替代后,相应配合物丧失DNA光断裂能力。
In this work, we demonstrate for the first time that [Ru(bpy)2(R-OQN)]+(bpy = 2,2'-bipyridine, R-OQN = 5-chloro-8-oxyquinolate or 5-bromo-8-oxyquinolate) are able to generate hydroxyl radical and cleave DNA effectively upon visible light irradiation. The potent electron-donating ability of the R-OQN-based non-innocent ligands renders the complexes high reducing capability, favoring the generation of superoxide anion radicals, from which hydroxyl radicals may be generated. More interestingly, the halogen substitution plays an important role. When 5-Cl(or Br)-8-oxyquinolate ligand is replaced by 8-oxyquinolae or 5-CH3-8-oxyquinolate, the corresponding complexes lose hydroxyl radical generation and DNA photocleavage abilities.
In this work, we demonstrate for the first time that [Ru(bpy)2(R-OQN)]+(bpy = 2,2'-bipyridine, R-OQN = 5-chloro-8-oxyquinolate or 5-bromo-8-oxyquinolate) are able to generate hydroxyl radical and cleave DNA effectively upon visible light irradiation. The potent electron-donating ability of the R-OQN-based non-innocent ligands renders the complexes high reducing capability, favoring the generation of superoxide anion radicals, from which hydroxyl radicals may be generated. More interestingly, the halogen substitution plays an important role. When 5-Cl(or Br)-8-oxyquinolate ligand is replaced by 8-oxyquinolae or 5-CH3-8-oxyquinolate, the corresponding complexes lose hydroxyl radical generation and DNA photocleavage abilities.
引文
[1]Armitage,B.Chem.Rev.1998,98:1171-1200.