Theoretical assessment of the photosensitization mechanisms of porphyrin-ruthenium(II) complexes for the formation of reactive oxygen species

被引:10
作者
Coitino, E. Laura [1 ]
Mella, Andy [2 ]
Cardenas-Jiron, Gloria I. [2 ]
机构
[1] Univ Republica, Fac Ciencias, Inst Quim Biol, Lab Quim Teor & Computac, Montevideo 11400, Uruguay
[2] Univ Santiago Chile, USACH, Fac Quim & Biol, Lab Quim Teor, Santiago, Chile
关键词
Photosensitization; Electron transfer; Energy transfer; Porphyrin; Ruthenium; Reactive oxygen species; EFFECTIVE CORE POTENTIALS; MOLECULAR-ORBITAL METHODS; GAUSSIAN-TYPE BASIS; SINGLET-OXYGEN; PHOTODYNAMIC THERAPY; CATIONIC PORPHYRINS; DNA INTERACTIONS; BASIS-SETS; ENERGY; BINDING;
D O I
10.1016/j.jphotochem.2014.08.003
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Following a thermodynamics point of view, we analyzed a set of photosensitization mechanisms (energy transfer, electron transfer) given by seven reactions applied to porphyrin-ruthenium(II) complexes (1-6) and their fragments (ruthenium complexes: 7-12; porphyrin: 13) at the B3LYP/6-31G(d,p)/LANL2DZ level of theory in condensed phase (aqueous solution). We found that whereas for the fragments (7-13) an energy-transfer process between their first triplet excited state (T-1) and molecular oxygen (O-3(2)) to yield singlet oxygen (O-1(2)) is favored, the privileged channels for the photosensitizers (1-6) correspond to production of a superoxide anion radical (O-2(center dot-)) by electron transfer between O-3(2) and the photosensitizers (P) either in their P(T-1) excited state or as a radical anion P center dot- . The reaction channels involving P center dot- are more exergonic by 13-17 kcal/mol with respect to the process involving P(T-1). These results suggest that the anionic photosensitizer would likely acquire more importance for the photodamage in the cell. (C) 2014 Elsevier B.V. All rights reserved.
引用
收藏
页码:68 / 74
页数:7
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