Fine control on the photochemical and photobiological properties of Ru(II) arene complexes
Fine control on the photochemical and photobiological properties of Ru(II) arene complexes
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Ru(II)芳烃配合物光化学和光生物学性质的精细控制
DOI：
10.1039/c5dt00939a
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发表时间：
2015-01-01
影响因子：
4
通讯作者：
Wang, Xuesong
中科院分区：
文献类型：
--
作者：
Chen, Yongjie;Lei, Wanhua;Wang, Xuesong
合成了一系列六种钌（芳烃）配合物[（eta（6）-p-cymene）Ru（dpb）（py-R）]（2+）（1-6，dpb = 2，3-双（2-吡啶基）苯并喹喔啉，py-R = 4-取代吡啶，R = N（CH 3）（2），NH 2，OCH 3，H，COOCH 3和NO2），并比较了它们的光化学和光生物学性质。R基团的电子推拉特性对配体的光解和O-1（2）的生成都有重要影响。在有氧和厌氧条件下，光诱导的DNA共价结合能力从1增加到6，并且在有氧环境中同时发生DNA光断裂。4对人肺癌A549细胞的光毒性最强。这种取代基效应可能是由于R基团对（MC）-M-3和（MLCT）-M-3能级以及（MC）-M-3、（MLCT）-M-3和dpb基（IL）-I-3能级之间的能隙的影响。在吡啶配体的二齿和芳烃配体或其他位点上的类似化学修饰可以产生具有PDT和/或PACT活性的更有效的试剂。
A series of six Ru(arene) complexes, [(eta(6)-p-cymene)Ru(dpb)(py-R)](2+) (1-6, dpb = 2,3-bis(2-pyridyl) benzoquinoxaline, py-R = 4-substituted pyridine, R = N(CH3)(2), NH2, OCH3, H, COOCH3 and NO2), were synthesized and their photochemical and photobiological properties were compared in detail. The electron push/pull character of the R groups has a significant impact on both ligand photodissociation and O-1(2) generation of the complexes. The photoinduced DNA covalent binding capabilities increase from 1 to 6 under both aerobic and anaerobic conditions, and DNA photocleavage occurs simultaneously in aerobic environments. 4 has the most potent phototoxicity against human lung carcinoma A549 cells among the examined complexes. The substituent effect may be ascribed to the influences of the R groups on the energy levels of (MC)-M-3 and (MLCT)-M-3 states as well as the energy gaps between (MC)-M-3, (MLCT)-M-3 and dpb-based (IL)-I-3 states. Similar chemical modification on bidentate and arene ligands or other sites of the pyridine ligand may lead to more efficient agents with PDT and/or PACT activities.