Mapping the Oxygens in the Oxygen-Evolving Complex of Photosystem II by Their Nucleophilicity Using Quantum Descriptors

被引:1
作者
Amin, Muhamed [1 ,2 ]
Kaur, Divya [3 ]
Brudvig, Gary W. [4 ]
Brooks, Bernard R. [1 ]
机构
[1] NHLBI, Lab Computat Biol, NIH, Bethesda, MD 20892 USA
[2] Univ Groningen, Univ Coll Groningen, Dept Sci, NL-9718 BG Groningen, Netherlands
[3] Brock Univ, Dept Chem, St Catharines, ON L2S 3A1, Canada
[4] Yale Univ, Dept Chem, New Haven, CT 06520 USA
关键词
ELECTRON-PARAMAGNETIC-RES; O-2-EVOLVING COMPLEX; WATER OXIDATION; S-3; STATE; PROTON; QM/MM; TRANSITION; MODEL; EXAFS; ELECTROPHILICITY;
D O I
10.1021/acs.jctc.3c00926
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
The oxygen-evolving complex (OEC) of Photosystem II catalyzes the water-splitting reaction using solar energy. Thus, understanding the reaction mechanism will inspire the design of biomimetic artificial catalysts that convert solar energy to chemical energy. Conceptual Density Functional Theory (CDFT) focuses on understanding the reactivity of molecules and the atomic contribution to the overall nucleophilicity and electrophilicity of the molecule using quantum descriptors. However, this method has not been applied to the OEC before. Here, we use Fukui functions and the dual descriptor to provide quantitative measures of the nucleophilicity and electrophilicity of oxygens in the OEC for different models in different S states. Our results show that the mu-oxo bridges connected to terminal Mn4 are nucleophilic, and those in the cube formed by Mn1, Mn2, and Mn3 are mostly electrophilic. The dual descriptors of the bridging oxygens in the OEC showed a similar reactivity to that of bridging oxygens in Mn model compounds. However, the terminal water W1, which is bound to Mn4, showed very strong reactivity in some of the S3 models. Thus, our calculations support the model that proposes the formation of the O-2 molecule through nucleophilic attack by a terminal water.
引用
收藏
页码:1414 / 1422
页数:9
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