Rapid Communication Spin-Driven Activation of Dioxygen in Various Metalloenzymes and Their Inspired Models

被引：12

作者：

De La Lande, Aurelien ^{[1
,2
,3
]}

Salahub, Dennis R. ^{[1
,2
]}

Maddaluno, Jacques ^{[4
,5
]}

Scemama, Anthony ^{[6
]}

Pilme, Julien ^{[7
,8
]}

Parisel, Olivier ^{[8
]}

Gerard, Helene ^{[8
]}

Caffarel, Michel ^{[6
]}

Piquemal, Jean-Philip ^{[8
]}

机构：

[1] Univ Calgary, Dept Chem, Calgary, AB T2N 1N4, Canada

[2] Univ Calgary, Inst Biocomplex & Informat, Calgary, AB T2N 1N4, Canada

[3] Univ Paris 11, Chem Phys Lab, F-91405 Orsay, France

[4] Univ Rouen, CNRS, UMR 6014, F-76821 Mont St Aignan, France

[5] Univ Rouen, FR 3038, IRCOF, F-76821 Mont St Aignan, France

[6] Univ Toulouse, Lab Chim & Phys Quant, CNRS, IRSAMC,UMR 5626, F-31062 Toulouse, France

[7] Univ Lyon 1, Fac Pharm, F-69373 Lyon 08, France

[8] UPMC, Chim Theor Lab, UMR 7616, CNRS,CC 137, F-75252 Paris 05, France

来源：

JOURNAL OF COMPUTATIONAL CHEMISTRY | 2011年 / 32卷 / 06期

关键词：

enzyme; spin; electron localization; DFT; constrained DFT; ELECTRON LOCALIZATION; TOPOLOGICAL ANALYSIS; MONONUCLEAR COPPER; BETA-MONOOXYGENASE; INSIGHTS; REACTIVITY; TYROSINASE; GEOMETRIES; MECHANISM; OXIDATION;

D O I：

10.1002/jcc.21698

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Although potentially powerful, molecular oxygen is an inert oxidant due to the triplet nature of its ground state. Therefore, many enzymesse various metal cations (M) to produce singlet active species MnO2. In this communication we investigate the topology of the Electron Localization Function (ELF) within five biomimetic complexes which are representative of the strategies followed by metalloenzymes to activate O-2. Thanks to its coupling to the constrained DFT methods the ELF analysis reveals the tight connection between the spin state of the adduct and the spatial organization of the oxygen lone pairs. We suggest that enzymes could resort to spin state control to tune the regioselectivity of substrate oxidations. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 32: 1178-1182, 2011

引用

页码：1178 / 1182

页数：5

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