吉林大学学报（理学版）2017，Vol.55Issue(3)：717-724,8.DOI:10.13413/j.cnki.jdxblxb.2017.03.44
气相S-异亮氨酸向R-别异亮氨酸的旋光异构机理及水溶剂化效应
Optical Isomerism Mechanism and Water Solvation Effect from Gaseous Phase S-Isoleucine to R-Allo-isoleucine
摘要
Abstract
We studied optical isomerism mechanism and water solvation effect from gaseous phase S-isoleucine to R-allo-isoleucine by using the B3LYP method of density functional theory,the MP2 method of perturbation theory,and SMD model method of self-consistent reaction field (SCRF ) theory.The results show that there are three channels a,b and c in the reaction.The optical isomerism reaction requires three elementary reactions in the channel a and c, four elementary reactions in the channel b.Channel a is the main reaction channel and the step-determining Gibbs free energy barrier is 255.0 kJ/mol,which is generated by the transition state of proton transfer from the chiral carbon to the amino N.The step-determining reaction rate constant is 1.25×10-32 s-1 .The water solvation effect enables the step-determining energy barrier to reduce to 114.1 kJ/mol and the reaction rate constant to increase to 2.73 × 10-7 s-1 .It shows that water environment has better catalytic effect on S-isoleucine optical isomerization.关键词
手性/旋光异构/异亮氨酸/别异亮氨酸/密度泛函理论/过渡态/微扰理论/自洽反应场Key words
chirality/optical isomerism/isoleucine/allo-isoleucine/density functional theory/transition state/perturbation theory/self-consistent reaction field (SCRF)分类
化学化工引用本文复制引用
王丽萍,李晨洁,王佐成,闫红彦,杨晓翠,佟华..气相S-异亮氨酸向R-别异亮氨酸的旋光异构机理及水溶剂化效应[J].吉林大学学报（理学版）,2017,55(3):717-724,8.基金项目
吉林省自然科学基金(批准号:20130101131JC). （批准号:20130101131JC）
