期刊
JOURNAL OF BIOLOGICAL INORGANIC CHEMISTRY
卷 22, 期 7, 页码 1029-1037出版社
SPRINGER
DOI: 10.1007/s00775-017-1480-1
关键词
Lytic polysaccharide monooxygenase; Density functional theory; Reaction mechanism; Computational chemistry
资金
- Swedish research council [2014-5540]
- COST [Action CM1305]
- Carlsberg Foundation [CF15-0208]
Lytic polysaccharide monooxygenases (LPMOs) are copper metalloenzymes that can enhance polysaccharide depolymerization through an oxidative mechanism, making them interesting for the production of biofuel from cellulose. However, the details of this activation are unknown; in particular, the nature of the intermediate that attacks the glycoside C-H bond in the polysaccharide is not known, and a number of different species have been suggested. The homolytic bond-dissociation energy (BDE) has often been used as a descriptor for the bond-activation power, especially for inorganic model complexes. We have employed quantum-chemical cluster calculations to estimate the BDE for a number of possible LPMO intermediates to bridge the gap between model complexes and the actual LPMO active site. The calculated BDEs suggest that the reactive intermediate is either a Cu(II)-oxyl, a Cu(III)-oxyl, or a Cu(III)-hydroxide, which indicate that O-O bond breaking occurs before the C-H activation step.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据