摘要
采用密度泛函理论的M06和MN15方法,研究了两个S型α-丙氨酸分子(S-α-Ala1和S-α-Ala2)与Fe2+的配合物S-A1和S-A2的手性转变.研究发现:S-A1的手性转变可通过以氧、氮、铁、氧与氮联合以及氧与甲基碳联合为桥的氢迁移实现.S-A2的手性转变可通过打开螯合环接S-A1的异构实现,还可打开螯合环通过以氧、铁及氧与甲基碳联合为桥的氢迁移实现;还可通过羧基内氢迁移后,以羰基氧及羰基氧和甲基碳联合为桥的氢迁移实现.势能面计算表明:以铁为氢负离子迁移桥梁的S-A1和S-A2手性转变反应具有优势,活化自由能垒分别是235.0和204.4kJ·mol^-1左右.结果表明:α-Ala·Fe^2+配合物可以很好地保持其手性特征.
The chiral transition mechanism of S-α-Ala1 and S-α-Ala2 with Fe2+complexes(S-A1 and S-A2)have been studied using the M06 and MN15 methods based on density functional theory.The study shows that the chiral transformation of S-A1 can be achieved by H migration using O,N,Fe,the combination of O and N,and the combination of O and methyl C atom as a bridge.The chiral transformation of S-A2 can be achieved by opening the chelate ring to the isomerization of S-A1,and the chelate ring can also be opened by H migration using O,Fe,and the combination of O atom with methyl C atom as a bridge,and after the H migration in the carboxyl group,the H migration takes place as the bridge between the carbonyl O and the combination of the carbonyl O and the methyl C atom.Potential energy surface studies show that the chiral transition reactions of S-A1 and S-A2 with iron as a bridge for the migration of hydride ions have advantages with these activation energies are about 235.0 and 204.4 kJ·mol^-1,respectively.The results show that the alanine with Fe^2+ complexes can maintain its chiral characteristics well.
作者
姜春旭
陈凤清
张雪娇
陈静思
佟华
王佐成
JIANG Chunxü;CHEN Fengqing;ZHANG Xuejiao;CHEN Jingsi;TONG Hua;WANG Zuocheng(Theoretical Computing Center,Baicheng Normal University,Baicheng,Jilin 137000,China;College of Life Science,Baicheng Normal University,Baicheng,Jilin 137000,China;Department of Clinical Medicine,Baicheng Medical College,Baicheng,Jilin 137000,China)
出处
《复旦学报(自然科学版)》
CAS
CSCD
北大核心
2020年第5期627-638,共12页
Journal of Fudan University:Natural Science
基金
吉林省教育厅科学研究规划项目(JJKH20200002KJ)
吉林省科技发展计划项目(20160101308JC)。
关键词
丙氨酸
二价铁离子
手性转变
密度泛函理论
过渡态
能垒
α-Alanine(α-Ala)
Fe2+
chiral transition
density functional theory
transition state
energy barrier