期刊
JOURNAL OF COMPUTATIONAL CHEMISTRY
卷 37, 期 18, 页码 1681-1696出版社
WILEY
DOI: 10.1002/jcc.24384
关键词
iron-sulfur clusters; inner and outer coordination spheres; bond covalency; ionic interactions; hydrogen bonding; protein environment
资金
- National Science Foundation, Molecular Cellular Biology program [0744820]
- Molecular Biosciences (MBS) [P20 RR16455-06]
- National Center for Research Resources (NCRR) National Institutes of Health (NIH) Kopriva Graduate Fellowship NASA Astrobiology Institute [NNA08C-N85A]
- Div Of Molecular and Cellular Bioscience
- Direct For Biological Sciences [0744820] Funding Source: National Science Foundation
The structural properties and reactivity of iron-sulfur proteins are greatly affected by interactions between the prosthetic groups and the surrounding amino acid residues. Thus, quantum chemical investigations of the structure and properties of protein-bound iron-sulfur clusters can be severely limited by truncation of computational models. The aim of this study was to identify, a priori, significant interactions that must be included in a quantum chemical model. Using the [2Fe-2S] accessory cluster of the FeFe-hydrogenase as a demonstrative example with rich electronic structural features, the electrostatic and covalent effects of the surrounding side chains, charged groups, and backbone moieties were systematically mapped through density functional theoretical calculations. Electron affinities, spin density differences, and delocalization indexes from the quantum theory of atoms in molecules were used to evaluate the importance of each interaction. Case studies for hydrogen bonding and charged side-chain interactions were used to develop selection rules regarding the significance of a given protein environmental effect. A set of general rules is proposed for constructing quantum chemical models for iron-sulfur active sites that capture all significant interactions from the protein environment. This methodology was applied to our previously used models in galactose oxidase and the 6Fe-cluster of FeFe-hydrogenase. (C) 2016 Wiley Periodicals, Inc.
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