L-缬氨酸旋光异构的两种光反应可能途径

引用本文: 马驰骋, 蒲敏, 卫敏, 李军男, 李志宏. L-缬氨酸旋光异构的两种光反应可能途径[J]. 物理化学学报, 2012, 28(08): 1830-1836. doi: 10.3866/PKU.WHXB201205162 shu

Citation: MA Chi-Cheng, PU Min, WEI Min, LI Jun-Nan, LI Zhi-Hong. Two Possible Photoreaction Pathways on the L-Valine Optical Isomerization[J]. Acta Physico-Chimica Sinica, 2012, 28(08): 1830-1836. doi: 10.3866/PKU.WHXB201205162 shu

L-缬氨酸旋光异构的两种光反应可能途径

马驰骋 ^1, ,
蒲敏 ^1, ,
卫敏 ^1, ,
李军男 ^1, ,
李志宏 ^2,

基金项目:
国家自然科学基金(21173019, 11079041)资助项目 (21173019, 11079041)

摘要:

利用密度泛函理论(DFT)和从头算分子轨道理论对L-缬氨酸的旋光异构光反应机理进行了研究. 分别用B3LYP和MP2方法在6-311++G(d, p)基组级别上全优化得到了S₀和T₁态反应路径上的反应物、产物、中间体以及过渡态结构的几何构型, 给出了反应能垒, 利用含时密度泛函理论(TD-DFT)中的B3LYP/6-311++G(d, p)方法优化得到了S₁态反应路径上的平衡态几何构型. 通过分析反应途径上各个驻点的几何构型特征, 确定了L-缬氨酸在激发态可能通过手性碳上的氢原子以羰基氧或氨基氮为中转媒介发生质子迁移来完成旋光异构反应. 进一步用自洽反应场理论中的极化连续模型(PCM)方法探讨了溶剂化效应对旋光异构反应机理的影响.

关键词:

English

Two Possible Photoreaction Pathways on the L-Valine Optical Isomerization

1.
1. State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, P. R. China;
2. Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, P. R. China
Received Date: 27 March 2012
Available Online: 10 July 2012
Fund Project:
国家自然科学基金(21173019, 11079041)资助项目

Abstract:

The photoreaction mechanism of L-valine optical isomerization was studied by the density functional theory (DFT) and ab initio molecular orbital theory. The geometric parameters of reactant, product, intermediates, and transition states on the reaction paths in S₀ and T₁ states were optimized at the level of B3LYP and MP2 methods and 6-311++G(d, p) basis sets and the reaction energy barriers were obtained by the same methods. The equilibrium geometries on the S₁ state of valine were also optimized by the method of time dependent density functional theory (TD-DFT) with B3LYP/6-311++G(d, p) level. Through the analysis of each stationary point geometric feature on the reaction path, the photoreaction mechanisms of L-valine optical isomerization were proposed in which the whole reaction was accomplished through hydrogen transfer with the help of carbonyl O or amino N atom in excited state. Furthermore the effect of solvent on the reaction mechanism of isomers was discussed by the method of polarizable continuum model (PCM) of self consistent reaction field theory.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

L-缬氨酸旋光异构的两种光反应可能途径

English

Two Possible Photoreaction Pathways on the L-Valine Optical Isomerization

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通讯作者: 陈斌, bchen63@163.com

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L-缬氨酸旋光异构的两种光反应可能途径

English

Two Possible Photoreaction Pathways on the L-Valine Optical Isomerization

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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