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
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摘要
采用量子力学与分子力学组合的ONIOM方法,研究了赖氨酸限域在水与MOR分子筛复合环境下的手性转变.结构分析表明:2个水分子比1个水分子助氢迁移反应的过渡态分子氢键键角显著增大。反应通道研究发现:标题反应有a、b和c三个通道,是赖氨酸在MOR分子筛限域环境下,水助质子以氨基、羰基和羟基为桥从手性碳的一侧迁移到另一侧,实现手性转变。势能面计算表明,a是主反应通道,质子从手性碳向氨基的迁移是决速步骤,在2个水分子助决速步时,吉布斯自由能垒被降到最低值101.9 k J/mol,与裸反应、限域在MOR分子筛和限域在水环境的此通道决速步能垒252.6、229.7和123.9 k J/mol相比较,均有明显降低。结果表明:水与MOR分子筛复合环境对赖氨酸手性转变具有较好的共催化作用,左旋赖氨酸在生命体内可以缓慢地旋光异构。
The chiral transition of lysine molecules confined in water and MOR zeolite combined environment was studied in the paper by introducing the ONIOM methods using combination of quantum mechanics 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 significantly 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 hydroxyl 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 stepdetermining where gibbs free energy barrier of two water-assisted proton transfers reaction is reduced to the minimum value 101. 9 k J · mol~(-1),that is significantly lower than the gibbs free energy barrier252. 6,229. 7 and 123. 9 k J·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 environment has a good co-catalysis on the chiral transition of lysine molecules,and S-Lys in vivo can be slowly optical isomerism.
The chiral transition of lysine molecules confined in water and MOR zeolite combined environment was studied in the paper by introducing the ONIOM methods using combination of quantum mechanics 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 significantly 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 hydroxyl 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 stepdetermining where gibbs free energy barrier of two water-assisted proton transfers reaction is reduced to the minimum value 101. 9 k J · mol~(-1),that is significantly lower than the gibbs free energy barrier252. 6,229. 7 and 123. 9 k J·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 environment has a good co-catalysis on the chiral transition of lysine molecules,and S-Lys in vivo can be slowly optical isomerism.
引文
[1]王建军,王晓春,欧阳一山,等.用镧系位移试剂研究L-赖氨酸在水溶液中的结构[J].物理化学学报,1992,8(5):647-653.WANG Jianjun,WANG Xiaochun,OUYANG Yishan,et al.Research on the structure of L-lysine in aqueous solution with lanthanide shift reagent[J].Journal of Physical Chemistry,1992,8(5):647-653.
[2]李菁,刘骞,孔保华,等.L-赖氨酸与三种还原糖美拉德反应产物的理化特性及抗氧化活性的研究[J].食品科学,2013,34(3):80-85.LI Jing,LIU Qian,KONG Baohua,et al.Research on the physicochemical properties and antioxidant activity of L-lysine and three reaction products of sugar Maillard[J].Food Science,2013,34(3):80-85.
[3]MNNISTM,VANDERKERKEN S,TONCHEVA V,et al.Structure-activity relationships of poly(L-lysines):effects of pegylation and molecular shape on physicochemical and biological properties in gene delivery[J].Journal of Controlled Release,2002,83(1):169-182.
[4]KIM S C,SPRUNG R,ZHAO Y M.Substrate and functional diversity of lysine acetylation revealed by a proteomics survey[J].Molecular Cell,2006,23(4):607-618.
[5]PAINTER P C,KOENIG J L.The solution conformation of poly(L-lysine):a Raman and infrared spectroscopic study[J].Biopolymers,1976,15(2):229-240.
[6]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.
[7]刘凤阁,王佐成,梅泽民,等.水环境下赖氨酸分子的手性转变机理[J].武汉大学学报(理学版),2015,61(5):491-496.LIU Fengge,WANG Zuocheng,MEI Zemin,et al.Chiral shift mechanism of lysine molecules under water enviroment[J].J Wuhan Univ(Nat Sci Ed),2015,61(5):491-496.
[8]王晓玲,高峰,佟华,等.基于氨基作为质子转移桥梁的赖氨酸分子手性转变机理[J].吉林大学学报(理学版),2016,54(5):1161-1167.WANG Xiaoling,GAO Feng,TONG Hua,et al.Chiral transition mechanism of lysine molecules based on amino as proton transfer bridge[J].Journal of Jilin University(Science Edition),2016,54(5):1161-1167.
[9]闫红彦,梅泽民,王佐成,等.MOR分子筛对赖氨酸手性转变反应的限域催化[J].吉林大学学报(理学版),2016,54(6):1437-1444.YAN Hongyan,MEI Zemin,WANG Zuocheng,et al.The confined catalysis of the MOR zeolite on the lysine chiral transition reaction[J].Journal of Jilin University(Science Edition),2016,54(6):1437-1444.
[10]王佐成,梅泽民,佟华,等.α-Ala限域在扶手椅型SWCNT(9,9)与水复合环境下的手性转变机制[J].复旦学报(自然科学版),2015,54(1):107-118.WANG Zuocheng,MEI Zemin,TONG Hua,et al.The chiral shift mechanism ofα-Ala confined in the complex environment of armchair SWCNT(9,9)and water[J].Journal of Fudan University(Science Edition),2015,54(1):107-118.
[11]王佐成,高峰,佟华,等.α-丙氨酸限域在螺旋手性SWCNT(12,6)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(3):261-276.WANG Zuocheng,GAO Feng,TONG Hua,et al.The chiral transition mechanism ofα-alanine confined in the chiral helicity SWCNT(12,6)/water complex environment[J].Journal of Fudan University(Science Edition),2015,54(3):261-276..
[12]梅泽民,佟华,夏立利,等.α-丙氨酸限域在扶椅型SWBNNT(9,9)与水复合环境下的手性转变机制[J].中山大学学报(自然科学版),2015,54(3):85-92.MEI Zemin,TONG Hua,XIA Lili,et al.Chiral transition mechanism ofα-alanine confined in the armchair SWBNNT(9,9)/water complex environment[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,2015,54(3):85-92.
[13]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.Chiral transition mechanism ofα-alanine confined in the armchair SWBNNT(10,6)/water complex environment[J].Journal of Fudan University(Science Edition),2015,54(4):529-540.
[14]赵衍辉,程彦明,李忠,等.α-Ala限域在螺旋SWBNNT(10,5)与水复合环境的手性转变机理—基于氨基作H迁移桥梁[J].吉林大学学报(理学版),2015,53(6):1299-1307.ZHAO Yanhui,CHENG Yanming,LI Zhong,et al.Chiral transition mechanism ofα-Ala molecule confined in the complex environment SWBNNT(10,5)and water[J].Journal of Jilin University(Science Edition),2015,53(6):1299-1307.
[15]孙永清,王佐成,高峰,等.水与MOR分子筛复合环境对布洛芬分子手性转变反应共催化的理论研究[J].复旦学报(自然科学版),2016,55(5):818-828.SUN Yongqing,WANG Zuocheng,GAO Feng,et al.Theoretical research on the co-catalysis of water and MOR zeolite combined environment on the chiral transition of ibuprofen molecules[J].Journal of Fudan University(Science Edition),2016,55(5):818-828.
[16]李惊鸿,周丹红,任珏.Ga/HZSM-5分子筛上乙烯二聚反应的理论研究[J].物理化学学报,2011,27(6):1393-1399.LI Jinghong,ZHOU Danhong,REN Jue.Theoretical study of ethylene dimerization on the Ga/HZSM-5 zeolite[J].Acta Phys-Chim Sin,2011,27(6):1393-1399.
[17]SVENSSON M,HUMBEL S,FROESE R D J,et al.ONIOM:A multilayered integrated MO+MM method for geometry optimizations and single point energy predictions.A test for Diels-Alder reactions and Pt(P(tBu)3)2+H2oxidtivae addition[J].Physical Chemistry,1996,100(50):19357-19363.
[18]KOBAYASHI R,AMOS R D.Erratum to The application of CAM-B3LYP to the charge-transfer band problem of the zincbacteriochlorin-bacteriochlorin complex[J].Chem Phys Letts,2006,420:106-109.
[19]YIN S W,DAHLBOM M G,CANFIELD P J,et al.Assignment of the Qy absorption spectrum of photosystem-I from thermosynechococcus elongatus based on CAMB3LYP calculations at the PW91-optimized protein structure[J].Phys Chem B,2007,111(33):9923-9930.
[20]RAPPE A K,CASEWIT C J,COLWELL K S,et al.UFF,a full periodic table force field for molecular mechanics and molecular dynamics simulations[J].Journal of the American Chemical Society,1992,114(25):10024-10053.
[21]GARRETT B C,TRUHLAR D G.Generalized transition state theory.Classical mechanical theory and applications to collinear reactions of hydrogen molecules[J].Journal of Physical Chemistry,1979,83(8):1052-1079.
[22]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.
[23]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.
[24]BINKLEY J S,POPLE J A.Moeller-Plesset theory for atomic ground state energies[J].Int J Quantum Chem,1975,9(2):229-236.
[25]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.
[26]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09.Revision D.01[CP].Pittsburgh U S A:Gaussian,Inc,Wallingford CT,2013.
[2]李菁,刘骞,孔保华,等.L-赖氨酸与三种还原糖美拉德反应产物的理化特性及抗氧化活性的研究[J].食品科学,2013,34(3):80-85.LI Jing,LIU Qian,KONG Baohua,et al.Research on the physicochemical properties and antioxidant activity of L-lysine and three reaction products of sugar Maillard[J].Food Science,2013,34(3):80-85.
[3]MNNISTM,VANDERKERKEN S,TONCHEVA V,et al.Structure-activity relationships of poly(L-lysines):effects of pegylation and molecular shape on physicochemical and biological properties in gene delivery[J].Journal of Controlled Release,2002,83(1):169-182.
[4]KIM S C,SPRUNG R,ZHAO Y M.Substrate and functional diversity of lysine acetylation revealed by a proteomics survey[J].Molecular Cell,2006,23(4):607-618.
[5]PAINTER P C,KOENIG J L.The solution conformation of poly(L-lysine):a Raman and infrared spectroscopic study[J].Biopolymers,1976,15(2):229-240.
[6]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.
[7]刘凤阁,王佐成,梅泽民,等.水环境下赖氨酸分子的手性转变机理[J].武汉大学学报(理学版),2015,61(5):491-496.LIU Fengge,WANG Zuocheng,MEI Zemin,et al.Chiral shift mechanism of lysine molecules under water enviroment[J].J Wuhan Univ(Nat Sci Ed),2015,61(5):491-496.
[8]王晓玲,高峰,佟华,等.基于氨基作为质子转移桥梁的赖氨酸分子手性转变机理[J].吉林大学学报(理学版),2016,54(5):1161-1167.WANG Xiaoling,GAO Feng,TONG Hua,et al.Chiral transition mechanism of lysine molecules based on amino as proton transfer bridge[J].Journal of Jilin University(Science Edition),2016,54(5):1161-1167.
[9]闫红彦,梅泽民,王佐成,等.MOR分子筛对赖氨酸手性转变反应的限域催化[J].吉林大学学报(理学版),2016,54(6):1437-1444.YAN Hongyan,MEI Zemin,WANG Zuocheng,et al.The confined catalysis of the MOR zeolite on the lysine chiral transition reaction[J].Journal of Jilin University(Science Edition),2016,54(6):1437-1444.
[10]王佐成,梅泽民,佟华,等.α-Ala限域在扶手椅型SWCNT(9,9)与水复合环境下的手性转变机制[J].复旦学报(自然科学版),2015,54(1):107-118.WANG Zuocheng,MEI Zemin,TONG Hua,et al.The chiral shift mechanism ofα-Ala confined in the complex environment of armchair SWCNT(9,9)and water[J].Journal of Fudan University(Science Edition),2015,54(1):107-118.
[11]王佐成,高峰,佟华,等.α-丙氨酸限域在螺旋手性SWCNT(12,6)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(3):261-276.WANG Zuocheng,GAO Feng,TONG Hua,et al.The chiral transition mechanism ofα-alanine confined in the chiral helicity SWCNT(12,6)/water complex environment[J].Journal of Fudan University(Science Edition),2015,54(3):261-276..
[12]梅泽民,佟华,夏立利,等.α-丙氨酸限域在扶椅型SWBNNT(9,9)与水复合环境下的手性转变机制[J].中山大学学报(自然科学版),2015,54(3):85-92.MEI Zemin,TONG Hua,XIA Lili,et al.Chiral transition mechanism ofα-alanine confined in the armchair SWBNNT(9,9)/water complex environment[J].Acta Scientiarum Naturalium Universitatis Sunyatseni,2015,54(3):85-92.
[13]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.Chiral transition mechanism ofα-alanine confined in the armchair SWBNNT(10,6)/water complex environment[J].Journal of Fudan University(Science Edition),2015,54(4):529-540.
[14]赵衍辉,程彦明,李忠,等.α-Ala限域在螺旋SWBNNT(10,5)与水复合环境的手性转变机理—基于氨基作H迁移桥梁[J].吉林大学学报(理学版),2015,53(6):1299-1307.ZHAO Yanhui,CHENG Yanming,LI Zhong,et al.Chiral transition mechanism ofα-Ala molecule confined in the complex environment SWBNNT(10,5)and water[J].Journal of Jilin University(Science Edition),2015,53(6):1299-1307.
[15]孙永清,王佐成,高峰,等.水与MOR分子筛复合环境对布洛芬分子手性转变反应共催化的理论研究[J].复旦学报(自然科学版),2016,55(5):818-828.SUN Yongqing,WANG Zuocheng,GAO Feng,et al.Theoretical research on the co-catalysis of water and MOR zeolite combined environment on the chiral transition of ibuprofen molecules[J].Journal of Fudan University(Science Edition),2016,55(5):818-828.
[16]李惊鸿,周丹红,任珏.Ga/HZSM-5分子筛上乙烯二聚反应的理论研究[J].物理化学学报,2011,27(6):1393-1399.LI Jinghong,ZHOU Danhong,REN Jue.Theoretical study of ethylene dimerization on the Ga/HZSM-5 zeolite[J].Acta Phys-Chim Sin,2011,27(6):1393-1399.
[17]SVENSSON M,HUMBEL S,FROESE R D J,et al.ONIOM:A multilayered integrated MO+MM method for geometry optimizations and single point energy predictions.A test for Diels-Alder reactions and Pt(P(tBu)3)2+H2oxidtivae addition[J].Physical Chemistry,1996,100(50):19357-19363.
[18]KOBAYASHI R,AMOS R D.Erratum to The application of CAM-B3LYP to the charge-transfer band problem of the zincbacteriochlorin-bacteriochlorin complex[J].Chem Phys Letts,2006,420:106-109.
[19]YIN S W,DAHLBOM M G,CANFIELD P J,et al.Assignment of the Qy absorption spectrum of photosystem-I from thermosynechococcus elongatus based on CAMB3LYP calculations at the PW91-optimized protein structure[J].Phys Chem B,2007,111(33):9923-9930.
[20]RAPPE A K,CASEWIT C J,COLWELL K S,et al.UFF,a full periodic table force field for molecular mechanics and molecular dynamics simulations[J].Journal of the American Chemical Society,1992,114(25):10024-10053.
[21]GARRETT B C,TRUHLAR D G.Generalized transition state theory.Classical mechanical theory and applications to collinear reactions of hydrogen molecules[J].Journal of Physical Chemistry,1979,83(8):1052-1079.
[22]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.
[23]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.
[24]BINKLEY J S,POPLE J A.Moeller-Plesset theory for atomic ground state energies[J].Int J Quantum Chem,1975,9(2):229-236.
[25]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.
[26]FRISCH M J,TRUCKS G W,SCHLEGEL H B,et al.Gaussian 09.Revision D.01[CP].Pittsburgh U S A:Gaussian,Inc,Wallingford CT,2013.