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
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摘要
采用密度泛函理论的B3LYP方法,微扰理论的MP2方法及自洽反应场(SCRF)理论的SMD模型方法,研究气相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.结果表明:该反应有a,b,c 3个通道,在通道a和c实现旋光异构反应需经过3个基元反应,在通道b实现旋光异构反应需经过4个基元反应;a为主反应通道,决速步骤Gibbs自由能垒为255.0kJ/mol,由质子从α手性C向氨基N迁移的过渡态产生,决速步骤的反应速率常数为1.25×10-32 s~(-1);水溶剂效应使决速步骤能垒降至114.1kJ/mol,反应速率常数增至2.73×10-7 s~(-1),即水环境对S-异亮氨酸旋光异构具有较好的催化作用.
We studied optical isomerism mechanism and water solvation effect from gaseous phase S-isoleucine to R-allo-isoleucine by using the B3 LYP 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 is255.0kJ/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 114.1kJ/mol and the reaction rate constant to increase to 2.73×10-7 s~(-1).It shows that water environment has better catalytic effect onS-isoleucine optical isomerization.
We studied optical isomerism mechanism and water solvation effect from gaseous phase S-isoleucine to R-allo-isoleucine by using the B3 LYP 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 is255.0kJ/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 114.1kJ/mol and the reaction rate constant to increase to 2.73×10-7 s~(-1).It shows that water environment has better catalytic effect onS-isoleucine optical isomerization.
引文
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[2]Tohru Yoshimura,Nobuyoshi Esaki.Amino Acid Racemases:Functions and Mechanisms[J].J Bioscience and Bioengineering,2003,96(2):103-109.
[3]崔国红.DL-异亮氨酸合成新工艺研究[J].四川化工,2010,13(4):12-15.(CUI Guohong.Study on the New Synthesis of DL-Isoleucine[J].Sichuan Chemical Industry,2010,13(4):12-15.)
[4]罗明道,王辉宪,颜肖慈,等.亮氨酸、异亮氨酸的结构与热力学性质研究[J].武汉大学学报(自然科学版),1995,41(4):439-443.(LUO Mingdao,WANG Huixian,YAN Xiaoci,et al.Studies on Molecular Strucre and Thermodyanmics Properties of L-Leucine and L-Isoleucine[J].Journal of Wuhan University(Natural Science Edition),1995,41(4):439-443.)
[5]周光明,虞丹尼,黎司,等.亮氨酸与异亮氨酸的表面增强拉曼光谱[J].化学学报,2007,65(7):640-644.(ZHOU Guangming,YU Danni,LI Si,et al.Surface Enhanced Raman Spectroscopy of Leucine and Isoleucine[J].Acta Chimica Sinica,2007,65(7):640-644.)
[6]王玉婷,吴刘洋.酶法拆分制备D-异亮氨酸的工艺研究[J].氨基酸和生物资源,2011,33(4):36-37.(WANG Yuting,WU Liuyang.Study on Preparation of D-Isoleucine by Enzyme Resoluion[J].Amino Acids&Biotic Resources,2011,33(4):36-37.)
[7]王佐成,刘凤阁,吕洋,等.孤立条件下α-丙氨酸分子手性转变机制的密度泛函理论[J].吉林大学学报(理学版),2014,52(4):825-830.(WANG Zuocheng,LIU Fengge,LYang,et al.Chiral Transformation Mechanism ofα-Alanine under Isolated Condition by Density Functional Theory[J].Journal of Jilin University(Science Edition),2014,52(4):825-830.)
[8]李忠,佟华,杨晓翠,等.基于氨基作H转移桥梁单体α-Ala的手性转变机理[J].复旦学报(自然科学版),2015,54(5):642-647.(LI Zhong,TONG Hua,YANG Xiaocui,et al.The Chiral Transition Mechanism of Monomerα-Alanine Based on Amino as H Transfer Bridge[J].Journal of Fudan University(Natural Science),2015,54(5):642-647.)
[9]王佐成,范志琳,程彦明,等.半胱氨酸分子手性转变及水分子的催化机理[J].武汉大学学报(理学版),2016,62(4):368-374.(WANG Zuocheng,FAN Zhilin,CHENG Yanming,et al.Chiral Transformation of Cysteine Molecules and Catalytic Mechanism of Water Molecules[J].Journal of Wuhan University(Natural Science Edition),2016,62(4):368-374.)
[10]闫红彦,王佐成,邹晶,等.缬氨酸分子的手性转变及水分子的催化机理[J].中山大学学报(自然科学版),2016,55(2):68-75.(YAN Hongyan,WANG Zuocheng,ZOU Jing,et al.Chiral Enantiomers Transformation of Valine and Catalytic Mechanism of Water Molecules[J].Acta Scientiarum Naturalium Universitatis Suyatseni,2016,55(2):68-75.)
[11]Becke A D.Density-Functional Thermochemistry.Ⅲ.The Role of Exact Exchange[J].Chem Phys,1993,98(7):5648-5652.
[12]Marenich A V,Cramer C J,Truhlar D G.Universal Slovation Model Based on Solute Electron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant and Atomic Surface Tensions[J].J Phys Chem B,2009,113(18):6378-6396.
[13]Garrett B C,Truhlar D G.Criterion of Minimum State Density in the Transition State Theory of Bimolecular Reactions[J].The Journal of Chemical Physics,1979,70(4):1593-1598.
[14]Ishida K,Morokuma K,Komornicki A.The Intrinsic Reaction Coordinate.An ab initio Calculation for HNC→HCN and H-+CH4→CH4+H-*[J].The Journal of Chemical Physics,1977,66(5):2153-2156.
[15]徐光宪,黎乐民,王德民.量子化学:中册[M].北京:科学技术出版社,1985:962-986.(XU Guangxian,LI Lemin,WANG Demin.Quantum Chemistry:Middle[M].Beijing:Science Press,1985:962-986.)
[16]任宏江.黄嘌呤异构体质子转移异构化反应机理的理论研究[J].化学通报,2015,78(9):815-819.(REN Hongjiang.Theoretical Investigation on the Proton Transfer Isomerization of Xanthine[J].Chemistry Bulletin Chem Bul,2015,78(9):815-819.)
[17]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09.Revision D.01[CP/CD].Pittsburgh,PA:Gaussian Inc,2013.
[18]王佐成,佟华,王丽萍,等.水环境下α-丙氨酸分子手性的转变机制[J].吉林大学学报(理学版),2015,53(1):134-141.(WANG Zuocheng,TONG Hua,WANG Liping,et al.α-Alanine Molecule Chiral Shift Mechanism in Water[J].Journal of Jilin University(Science Edition),2015,53(1):134-141.)
[19]佟华,杨晓翠,闫红彦,等.α-Ala限域在螺手性SWBNNT(10,6)与水复合环境下的手性转变机理[J].复旦学报(自然科学版),2015,54(4):529-540.(TONG Hua,YANG Xiaocui,YAN Hongyan,et al.The Chiral Transition Mechanism ofα-Ala Confined in the Chiral Helicity SWBNNT(10,6)/Water Complex Environment[J].Journal of Fudan University(Natural Science),2015,54(4):529-540.)