Evidences for Cooperative Resonance-Assisted Hydrogen Bonds in Protein Secondary Structure Analogs.
Evidences for Cooperative Resonance-Assisted Hydrogen Bonds in Protein Secondary Structure Analogs.
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蛋白质二级结构类似物中协同共振辅助氢键的证据
DOI：
10.1038/srep36932
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发表时间：
2016-11-16
影响因子：
4.6
通讯作者：
Yu ZW
中科院分区：
文献类型：
--
作者：
Zhou Y;Deng G;Zheng YZ;Xu J;Ashraf H;Yu ZW
蛋白质中氢键网络的协同行为早已被发现。然而，这种合作性的结构根源仍在争论中。本文报道了一种将过量红外光谱与密度泛函理论计算相结合的新方法，对以BYN-甲基甲酰胺(NMF)和N-甲基乙酰胺(NMA)为代表的多肽类似物进行研究。有趣的是，在纯类似物中加入强氢键受体二甲基亚砜后，N-−-H伸缩红外吸收峰分别发生红移和蓝移。由于氢键的协同作用，NMA分子之间的自缔合能级显著降低，从而调和了这一矛盾。相反，NMF分子不能形成长链协同氢键，因为它们倾向于形成二聚体。更有趣的是，我们发现N−H/N−C/C = O的键级变化与形成氢键多聚体后获得的氢键能量之间存在良好的线性关系，有力地表明这种协同性来自共振辅助氢键。我们的发现为蛋白质的结构提供了洞察力，也可能为新型分子识别系统的合理设计提供启示。
Cooperative behaviors of the hydrogen bonding networks in proteins have been discovered for a long time. The structural origin of this cooperativity, however, is still under debate. Here we report a new investigation combining excess infrared spectroscopy and density functional theory calculation on peptide analogs, represented byN-methylformamide (NMF) andN-methylacetamide (NMA). Interestingly, addition of the strong hydrogen bond acceptor, dimethyl sulfoxide, to the pure analogs caused opposite effects, namely red- and blue-shift of the N−H stretching infrared absorption in NMF and NMA, respectively. The contradiction can be reconciled by the marked lowering of the energy levels of the self-associates between NMA molecules due to a cooperative effect of the hydrogen bonds. On the contrary, NMF molecules cannot form long-chain cooperative hydrogen bonds because they tend to form dimers. Even more interestingly, we found excellent linear relationships between changes on bond orders of N−H/N−C/C = O and the hydrogen bond energy gains upon the formation of hydrogen bonding multimers in NMA, suggesting strongly that the cooperativity originates from resonance-assisted hydrogen bonds. Our findings provide insights on the structures of proteins and may also shed lights on the rational design of novel molecular recognition systems.
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