文献类型：期刊文献

英文题名：Theoretical and crystallographic data investigations of noncovalent S???O interactions

作者：Lu Junming[1,2];Lu Yunxiang[1,2];Yang Subin[1,2];Zhu Weiliang[1,2,3]

机构：[1]E China Univ Sci & Technol, Sch Sci, Shanghai 200237, Peoples R China;[2]E China Univ Sci & Technol, Dept Chem, Shanghai 200237, Peoples R China;[3]Chinese Acad Sci, Shanghai Inst Mat Med, Drug Discovery & Design Ctr, Shanghai 201203, Peoples R China

年份：2011

卷号：22

期号：4

起止页码：757

外文期刊名：STRUCTURAL CHEMISTRY

收录：;EI(收录号：20242616543756);WOS:【SCI-EXPANDED(收录号:WOS:000292556800003)】；

基金：This study was financially supported by National Natural Science Foundation of China (20721003), the International Collaboration Program of MOST (2007DBF30370), and the Knowledge of Innovation Program of CAS (KSCX2-YW-R-18).

语种：英文

外文关键词：sigma-hole; AIM; NBO; ESP; Anti-bonding orbital

摘要：Weak S center dot center dot center dot O bonding, a specific noncovalent interaction, plays crucial roles in fields as diverse as molecular recognition, crystal engineering, and biological systems. This article presents an ab initio investigation of a series of dimeric complexes formed between formaldehyde and several sulfur-containing molecules as electron accepters. The bond-length change, interaction energy, topological property of the electron density, and charge transfer of these S center dot center dot center dot O bonds have been systematically investigated. Moreover, a comprehensive search for nonbonded S center dot center dot center dot O interactions in proteins was also performed. It was found that the O atom shows a strong intrinsic tendency to approach S from the backside of the R-S bond (in the sigma(s)* direction); the S atom tends to approach the O atom either from the orientation of the lone pair of O (in the n(o) direction) or from the vertical direction (in the pi(o) direction). Besides, the linearity of this interaction was further substantiated by the statistical study. As suggested by the results presented in this study, S center dot center dot center dot O contacts may control protein structures to some extent and the unique directional properties of S center dot center dot center dot O interactions could be applied in supermolecular assembly and biological design.