中山大学学报（自然科学版）2017，Vol.56Issue(4)：75-83,9.DOI:10.13471/j.cnki.acta.snus.2017.04.013
几种稳定构型酪氨酸分子的手性转变反应机理及水溶剂化效应
Chiral conversion mechanism and water solvation effect of several tyrosine molecules of stable configurations
摘要
Abstract
The chiral conversion mechanism and water solvation effect of three kinds of the most stable configurations of tyrosine molecules were researched by using the B3LYP method of density functional theory,the MP2 method of perturbation theory,and smd model method of self consistent reaction field theory.The study of reaction channels shows that there are three channels a,b and c in the title reaction.For the configuration one and two,the proton of the chiral carbon is transferred with amino group after the carboxyl cis-trans isomerism,amino group and carboxyl/amino groups as the bridge,respectively.For the configuration three,the proton is transferred with amino group and carboxyl/amino groups as the bridge,and transferred proton of the carboxyl is transferred with amino group as the bridge,respectively.Calculations of potential energy surface show that channel a is the dominant reaction path in the configuration one and two,step-determining gibbs free energy barriers are 257.0 and 264.0 kJ·mol-1,respectively.In addition,channel b and c are the dominant reaction paths in the configuration three,step-determining gibbs free energy barriers are 257.4 and 257.0 kJ·mol-1,which are generated by the transition state of proton transfer from the chiral carbon to the amino N.The water solvation effect enables the step-determining energy barrier is reduced to 113.1 kJ·mol-1 for the dominant reaction path in the configuration one.The results show that: monomer tyrosine molecule is stable,tyrosine chiral conversion can be proceeded slowly in water environment.关键词
酪氨酸/手性/密度泛函理论/过渡态/微扰理论/自洽反应场Key words
tyrosine/chirality/density functional theory/transition state/perturbation theory/SCRF分类
化学化工引用本文复制引用
董丽荣,王佐成,闫红彦..几种稳定构型酪氨酸分子的手性转变反应机理及水溶剂化效应[J].中山大学学报（自然科学版）,2017,56(4):75-83,9.基金项目
吉林省科技发展计划资助项目自然科学基金(20130101308JC) （20130101308JC）
