中山大学学报（自然科学版）2017，Vol.56Issue(1)：14-23,10.DOI:10.13471/j.cnki.acta.snus.2017.01.003
MOR分子筛与水复合环境对赖氨酸手性转变反应的共催化机理
Theoretical study on the co-catalysis of MOR zeolite and water combined environment on the chiral transition of lysine molecules
摘要
Abstract
The chiral transition of lysine molecules confined in water and MOR zeolite combined environ-ment was studied in the paper by introducing the ONIOM methods using combination of quantum mechan-ics and molecular mechanics.The molecular structure researches show that hydrogen bond angle of the transition state molecules in the hydrogen transfer reactions with the help of two water molecules is signifi-cantly larger than that with the help of one water molecule.The study of reaction channels shows there are three channels a,b and c in the title reaction where lysine is confined in MOR zeolite,protons transfer with the help of water molecules from one side to the other of the chiral C with amino,carbonyl and hy-droxyl as a bridge,and at last the chiral transition is achieved.Calculations of potential energy surface show that channel a is the dominant reaction path and protons transfer the chiral C to amino is the step-determining where gibbs free energy barrier of two water-assisted proton transfers reaction is reduced to the minimum value 1 01.9 kJ · mol-1 ,that is significantly lower than the gibbs free energy barrier 252.6,229.7 and 1 23.9 kJ·mol-1 ,respectively corresponding to the bare reaction,confined in MOR zeolite and confined in water environment.The results show that water and MOR zeolite combined envi-ronment has a good co-catalysis on the chiral transition of lysine molecules,and S-Lys in vivo can be slowly optical isomerism.关键词
MOR分子筛/赖氨酸/手性转变/ONIOM方法/密度泛函/过渡态Key words
MOR zeolite/lysine/chiral transition/our own n-layered integrated molecule orbit and molecule mechanics methods/density functional/transition state分类
化学化工引用本文复制引用
刘逸轩,王佐成,董丽荣,赵晓波,杨晓翠,佟华..MOR分子筛与水复合环境对赖氨酸手性转变反应的共催化机理[J].中山大学学报（自然科学版）,2017,56(1):14-23,10.基金项目
吉林省科技发展计划资助项目自然科学基金 （）
