期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 23, 期 26, 页码 6406-6418出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201700363
关键词
cytochrome P450; density functional calculations; electronic structure; hydroxylation; oxidation
资金
- EU-COST Network Explicit Control Over Spin-States in Technology and Biochemistry (ECOSTBio) [CM1305]
- Ministerio de Economia y Competitividad of Spain [CTQ2014-54306-P, BES-2012-052801]
- Generalitat de Catalunya [2014SGR931]
- European Fund for Regional Development (FEDER grant) [UNGI10-4E-801]
- NRF of Korea through the CRI [NRF-2012R1A3A2048842]
- NRF of Korea through the GRL [NRF-2010-00353]
- Tertiary Education Trust Fund in Nigeria
- Xarxa de Referencia en Quimica Teorica i Computacional
- ICREA
The cytochromes P450 are versatile enzymes in human physiology that perform substrate hydroxylation reactions extremely efficiently. In this work, we present results of a computational study on the reactivity patterns of Compound I, Compound II, and protonated Compound II with model substrates, and we address the question of which of these compounds is the most effective oxidant? All calculations, regardless of the substrate, implicated that Compound I is the superior oxidant of the three. However, Compound II and protonated Compound II were found to react with free energies of activation that are only a few kcalmol(-1) higher in energy than those obtained with Compound I. Therefore, Compound II and protonated Compound II should be able to react with aliphatic groups with moderate C-H bond strengths. We have analysed all results in detail and have given electronic, thermochemical, valence bond, and molecular orbital rationalizations on the reactivity differences and explained experimental product distributions. Overall, the findings implied that alternative oxidants could operate alongside Compound I in complex reaction mechanisms of enzymatic and synthetic iron porphyrinoid complexes.
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