基于氨基作为质子迁移桥梁的蛋氨酸分子旋光异构机理
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摘要
采用密度泛函理论的B3LYP方法和微扰理论的MP2方法,研究两种最稳定构型的蛋氨酸分子(Met)基于氨基作为质子迁移桥梁的旋光异构反应.结果表明:基于氨基作为质子迁移桥梁的蛋氨酸分子旋光异构反应有2条通道a和b;构型1的主反应通道为通道a,决速步骤为第1基元反应,自由能垒为264.2kJ/mol,由质子从手性C直接向氨基N迁移的过渡态产生;构型2的主反应通道也为通道a,决速步骤为第2基元反应,自由能垒为266.1kJ/mol,由羧基异构后质子从手性C向氨基N迁移的过渡态产生;两种构型的Met分子旋光异构速控步骤的反应速率常数分别为3.04×10~(-34),1.41×10~(-34) s~(-1).
We studied the optical isomerism reaction of two kinds of the most stable configurations of methionine molecules based on amino group as proton transfer bridge by using the B3LYP method of density functional theory and the MP2 method of perturbation theory.The results show that there are two channels a and b in the optical isomerism reaction of methionine molecules based on amino group as proton transfer bridge.The dominant reaction channel of the configuration one is channel a,the rate-determining step is the first elementary reaction,and the free energy barrier is 264.2kJ/mol that is generated by the transition state of proton transfer from the chiral C to the amino N.The dominant reaction channel of the configuration two is the channel a,the rate-determining step is the second elementary reaction,and the free energy barrier is 266.1kJ/mol that is generated by the transition state of proton transfer from the chiral C to the amino N after carboxyl group isomerism.The reactionrate constants of the optical isomerism rate-determining step of two configurations of methionine molecules are 3.04×10~(-34),1.41×10~(-34) s~(-1),respectively.
We studied the optical isomerism reaction of two kinds of the most stable configurations of methionine molecules based on amino group as proton transfer bridge by using the B3LYP method of density functional theory and the MP2 method of perturbation theory.The results show that there are two channels a and b in the optical isomerism reaction of methionine molecules based on amino group as proton transfer bridge.The dominant reaction channel of the configuration one is channel a,the rate-determining step is the first elementary reaction,and the free energy barrier is 264.2kJ/mol that is generated by the transition state of proton transfer from the chiral C to the amino N.The dominant reaction channel of the configuration two is the channel a,the rate-determining step is the second elementary reaction,and the free energy barrier is 266.1kJ/mol that is generated by the transition state of proton transfer from the chiral C to the amino N after carboxyl group isomerism.The reactionrate constants of the optical isomerism rate-determining step of two configurations of methionine molecules are 3.04×10~(-34),1.41×10~(-34) s~(-1),respectively.
引文
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[2]王冉,周岩民.动物蛋氨酸营养研究进展[J].粮食与饲料工业,1999(4):27-30.(WANG Ran,ZHOU Yanmin.Research Advance of Methionine Nutrition for Animals[J].Cereal and Feed Industry,1999(4):27-30.)
[3]Mary M B,Sasirekha V,Ramakrishnan V.Vibrational Spectral Analysis of DL-Valine DL-Valinium and DL-Methionine DL-Methioninium Picrates[J].Spectrochimica Acta Part A:Molecular and Biomolecular Spectroscopy,2006,65(3/4):955-963.
[4]Koleva B B.Solid-State Linear-Polarized IR-Spectroscopic Characterization of L-Methionine[J].Vibrational Spectroscopy,2007,44(1):30-35.
[5]王国营,胡琼,刘刚,等.蛋氨酸电离能与红外光谱的密度泛函理论计算研究[J].红外,2010,31(10):21-25.(WANG Guoying,HU Qiong,LIU Gang,et al.Calculation of Ionization Energy and Infrared Spectra of Methionine with Density Functional Theory[J].Infrared,2010,31(10):21-25.)
[6]刘阳,曹军卫,翟超.米曲霉菌体细胞固定化及DL-蛋氨酸的光学拆分[J].武汉大学学报(自然科学版),2000,46(6):769-772.(LIU Yang,CAO Junwei,ZHAI Chao.Immobilization of High Activity AminoacylaseProducing Aspergillus Oryzae Cells Applied for Resolution of DL-Methionine[J].J Wuhan Univ(Nat Sci Ed),2000,46(6):769-772.)
[7]王淑豪,李晓峰,吴艳玲,等.固定化米曲霉氨基酰化酶反应动力学及其连续拆分DL-蛋氨酸实验[J].过程工程学报,2001,1(3):293-296.(WANG Shuhao,LI Xiaofeng,WU Yanling,et al.Enzymatic Kinetics of Immobilized L-Aminoacylase and Its Continuous Resolution of DL-Methionine[J].The Chinese Journal of Process Engineering,2001,1(3):293-296.)
[8]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,LUYang,et al.Chiral Transformaition Mechanism ofα-Alanine under Isolated Condition by Density Functional Theory[J].Journal of Jilin University(Science Edition),2014,52(4):825-830.)
[9]王佐成,高峰,赵衍辉,等.α-丙氨酸分子手性转变反应通道及水分子作用的理论研究[J].浙江大学学报(理学版),2014,42(2):189-197.(WANG Zuocheng,GAO Feng,ZHAO Yanhui,et al.Theoretical Research on the Chiral Transformation Pathway ofα-Alanine and the Effect of Water Molecules[J].Journal of Zhejiang University(Science Edition),2014,42(2):189-197.)
[10]刘凤阁,辛春雨,闫红彦,等.气相赖氨酸分子手性转变机制的理论研究[J].武汉大学学报(理学版),2015,61(1):93-98.(LIU Fengge,XIN Chunyu,YAN Hongyan,et al.Theoretical Research on Chiral Change Mechanism of Gaseous Lysine Molecules[J].J Wuhan Univ(Nat Sci Ed),2015,61(1):93-98.)
[11]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.)
[12]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].J Wuhan Univ(Nat Sci Ed),2016,62(4):368-374.)
[13]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 Sunyatsent,2016,55(2):68-75.)
[14]Becke A D.Density-Functional Thermochemistry.Ⅲ.The Role of Exact Exchange[J].Chem Phys,1993,98(7):5648-5652.
[15]Parr R G,Yang W.Density-Functional Theory of Atoms and Molecules[M].Oxford:Oxford University Press,1994.
[16]Garrett B C,Truhlar D G.Generalized Transition State Theory.Classical Mechanical Theory and Applications to Collinear Reactions of Hydrogen Molecules[J].The Journal of Physical Chemistry,1979,83(8):1052-1079.
[17]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.
[18]Gonzalez C,Schlegel H.Reaction Path Following in Mass-Weighted Internal Coordinates[J].The Journal of Physical Chemistry,1990,94(14):5523-5527.
[19]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(7):2153-2156.
[20]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.)
[21]Binkley J S,Pople J A.Moeller-Plesset Theory for Atomic Ground State Energies[J].Int J Quantum Chem,1975,9(2):229-236.
[22]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,2015,78(9):815-819.)
[23]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09.Revision E.01[CP/CD].Pittsburgh,PA:Gaussian Inc,2013.