Photodissociation of a ruthenium(II) arene complex and its subsequent interactions with biomolecules: a density functional theory study
Photodissociation of a ruthenium(II) arene complex and its subsequent interactions with biomolecules: a density functional theory study
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DOI：
10.1007/s00894-012-1467-3
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发表时间：
2012-06
影响因子：
2.2
通讯作者：
Hanlu Wang;Nathan J. DeYonker;Xiting Zhang;Cunyuan Zhao;L. Ji;Z. Mao
中科院分区：
文献类型：
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作者：
Hanlu Wang;Nathan J. DeYonker;Xiting Zhang;Cunyuan Zhao;L. Ji;Z. Mao
[（η6-benz）Ru（bpm）（py）]2+（benz =苯，bpm = 2，2 ′-联嘧啶，py =吡啶）是一种不稳定的芳烃配合物，在一定的时间尺度和生物反应条件下，可以被可见光激活，选择性地光解单齿配体（py）。本文采用密度泛函理论（DFT）和含时密度泛函理论（TDDFT）研究了光控钌（II）芳烃配合物[（η6-benz）Ru（bpm）（py）]2+与各种生物分子的水合和结合.计算了[（η6-benz）Ru（bpm）（py）]2+中Ru-N（py）键在单重态和三重态下的势能曲线（佩奇），为研究py的光解机理提供了有用的信息.计算各种生物分子的结合能，这使得所考虑的核酸或蛋白质结合位点之间的结合亲和力的顺序被辨别。研究了生物分子取代水络合物中水的动力学，结果表明鸟嘌呤在与RuIIaqua加合物配位方面比其他生物分子具有上级优势，这与实验结果基本一致。图络合物的光诱导水合和生物分子取代反应
The piano-stool RuIIarene complex [(η6-benz)Ru(bpm)(py)]2+(benz = benzene, bpm = 2,2′-bipyrimidine, and py = pyridine), which is conventionally nonlabile (on a timescale and under conditions relevant for biological reactivity), can be activated by visible light to selectively photodissociate the monodentate ligand (py). In the present study, the aquation and binding of the photocontrolled ruthenium(II) arene complex [(η6-benz)Ru(bpm)(py)]2+to various biomolecules are studied by density functional theory (DFT) and time-dependent DFT (TDDFT). Potential energy curves (PECs) calculated for the Ru–N (py) bonds in [(η6-benz)Ru(bpm)(py)]2+in the singlet and triplet state give useful insights into the photodissociation mechanism of py. The binding energies of the various biomolecules are calculated, which allows the order of binding affinities among the considered nuleic-acid- or protein-binding sites to be discerned. The kinetics for the replacement of water in the aqua complex with biomolecules is also considered, and the results demonstrate that guanine is superior to other biomolecules in terms of coordinating with the RuIIaqua adduct, which is in reasonable agreement with experimental observations.FigurePhotoinduced aquation and biomolecules replacement reaction for the complex