[Ru(bpy)_2(py-SO_3)]~+型配合物光诱导Ru-O键均裂的取代基效应和波长依赖性
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- 英文论文题名：Substituent effect and wavelength dependence of the photoinduced Ru-O homolysis in the [Ru(bpy)_2(py-SO_3)]~+–type complexes
- 论文作者：田娜娜 ; 郑月 ; 周前雄 ; 张阳阳 ; 李超 ; 侯原军 ; 王雪松
- 英文论文作者：Nana Tian ; Yue Zheng ; Qian-Xiong Zhou ; Yang-Yang Zhang ; Chao Li ; Yuan-Jun Hou ; Xue-Song 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：钌配合物 ; Ru-O键均裂 ; 取代基效应 ; 波长依赖性
- 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
- 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：272k
- 原文格式：D
- 会议级别：全国
摘要
[Ru(bpy)_2(py-SO_3)]~+(3,bpy=2,2’-bipyridine,py-SO_3=pyridine-2-sulfonate)光照后不仅能发生py-SO_3配体解离,还能发生Ru-O键均裂,从而产生py-SO_3●自由基,这使其能够在无氧环境下同时实现DNA光断裂和光交联,在光动力疗法和光活化化疗领域展现出应用前景1。为了深入理解Ru-O键均裂机制,我们设计合成了[Ru(4,4’-(R)_2-bpy)(py-SO_3)]~+(R=OCH_3(1),CH_3(2),COOCH_3(4)),研究表明,355 nm和470 nm光照下,只有前者能够产生py-SO_3●自由基,且效率遵循4>3>2>1。TD-DFT理论计算对取代基效应和波长依赖现象给出了合理解释2。
[Ru(bpy)_2(py-SO_3)]~+(3, bpy = 2,2'-bipyridine, py-SO_3 = pyridine-2-sulfonate) was recently found to undergo py-SO_3 ligand dissociation and py-SO_3· radical generation and therefore enable DNA cleavage and crosslinking under hypoxic conditions, showing application potentials in photodynamic therapy(PDT) and photoactivated chemotherapy(PACT).1To understand the underlying mechanism, [Ru(4,4'-(R)_2-bpy)(py-SO_3)]~+, where R =OCH_3(1), CH_3(2), COOCH_3(4), were synthesized and their photochemical and photobiological properties were compared in detail to that of 3.It was found that the irradiation at 355 nm but not at 470 nm led to the py-SO_3· radical generation, and the efficiencies followed the order of 4> 3>2>1.TD-DFT calculations provide reasonable explanations for the experimental results.2
[Ru(bpy)_2(py-SO_3)]~+(3, bpy = 2,2'-bipyridine, py-SO_3 = pyridine-2-sulfonate) was recently found to undergo py-SO_3 ligand dissociation and py-SO_3· radical generation and therefore enable DNA cleavage and crosslinking under hypoxic conditions, showing application potentials in photodynamic therapy(PDT) and photoactivated chemotherapy(PACT).1To understand the underlying mechanism, [Ru(4,4'-(R)_2-bpy)(py-SO_3)]~+, where R =OCH_3(1), CH_3(2), COOCH_3(4), were synthesized and their photochemical and photobiological properties were compared in detail to that of 3.It was found that the irradiation at 355 nm but not at 470 nm led to the py-SO_3· radical generation, and the efficiencies followed the order of 4> 3>2>1.TD-DFT calculations provide reasonable explanations for the experimental results.2
引文
[1]Zheng,Y.;Zhou,Q,X.;Lei,W.H.;Li,K.;Hou,Y.J.;Chen,Y.J.;Zhang,B.W.;Wang,X.S.Chem.Commun.,2015,51:428.
[2]Zheng,Y.;Zhou,Q.X.;Zhang,Y.;Wang,X.S.Dalton Trans.,2016,45:2897.
[2]Zheng,Y.;Zhou,Q.X.;Zhang,Y.;Wang,X.S.Dalton Trans.,2016,45:2897.