[1]柳国洪,彭国强,张栩宾,等.水液相下赖氨酸钙(II)配合物旋光异构的DFT研究[J].江西师范大学学报(自然科学版),2022,(06):558-567.[doi:10.16357/j.cnki.issn1000-5862.2022.06.02]
　LIU Guohong,PENG Guoqiang,ZHANG Yubin,et al.The Density Function Theoretical Study on the Optical Isomerism of Lysine Ca(II)Complex in Water-Liquid Phase Environment[J].Journal of Jiangxi Normal University:Natural Science Edition,2022,(06):558-567.[doi:10.16357/j.cnki.issn1000-5862.2022.06.02]
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水液相下赖氨酸钙(II)配合物旋光异构的DFT研究()
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《江西师范大学学报》（自然科学版）[ISSN:1006-6977/CN:61-1281/TN]

卷:
期数:
2022年06期
页码:
558-567
栏目:
化学
出版日期:
2022-11-25

文章信息/Info

Title:
The Density Function Theoretical Study on the Optical Isomerism of Lysine Ca(II)Complex in Water-Liquid Phase Environment
文章编号:
1000-5862(2022)06-0558-10
作者:
柳国洪1; 彭国强1; 张栩宾2; 郝成欣1; 刘 芳2; 王佐成2; 潘 宇2*; 赵丽红1*
1.白城医学高等专科学校基础医学院,吉林 白城 137000; 2.白城师范学院理论计算中心,吉林 白城 137000)
Author(s):
LIU Guohong1; PENG Guoqiang1; ZHANG Yubin2; HAO Chengxin1; LIU Fang2; WANG Zuocheng2; PAN Yu2*; ZHAO Lihong1*
1.Department of Basic Medicine,Baicheng Medical College,Baicheng Jilin 137000,China; 2.Theoretical Computing Center,Baicheng Normal University,Baicheng Jilin 137000,China)
关键词:
赖氨酸;  2价钙;  密度泛函理论;  旋光异构;  自由能垒
Keywords:
lysine;  divalent calcium;  density functional theory;  optical isomerism;  free energy barrier
分类号:
O 641.12
DOI:
10.16357/j.cnki.issn1000-5862.2022.06.02
文献标志码:
A
摘要:
该文采用DFT的M06-2X和MN15方法结合极化介质的SMD模型,研究了在水液相下两性赖氨酸分子2价钙配合物(Lys·Ca(II))的旋光异构.反应通道研究发现:Lys·Ca(II)的旋光异构可在Lys从两性异构为中性后,α-H以氨基N作桥和羰基O作桥迁移的2个通道上实现.势能面计算结果表明:,α-H以氨基N作桥的反应通道最具优势,在隐性水溶剂效应下决速步能垒为220.8 kJ·mol-1,α-H从手性C向氨基N迁移的过渡态在显性水溶剂效应下的能垒降至120.5 kJ·mol-1左右.研究结果表明:在水液相下手性Lys·Ca(II)的消旋过程十分缓慢,其用于生命体同补Lys和Ca(II)具有较好的安全性.
Abstract:
The optical isomerism mechanism of amphoteric lysine(Lys)and divalent calcium(Ca(II))complexes(Lys·Ca(II))in water-liquid phase environment is studied by means of M06 and MN15 methods based on density functional theory and SMD model method of polarized continuum.The study of reaction channels shows that the optical isomerism of Lys·Ca(II)can be achieved on two channels that are α-H proton transfers with amino group N as a bridge after the amphoteric Lys isomerizes to neutral Lys,and α-H proton directly uses carbonyl O atom as the transfer bridge to achieve reaction.Investigation on the potential energy surface shows that the first reaction channel has the most advantage,the free energy barrier of the rate-determining step is 220.8 kJ·mol-1 under the effect of recessive solvent,it comes from the transient state of the proton moving from α-C to amino group N,the energy barrier is reduced to about 120.5 kJ·mol-1 under the effect of dominant solvent.The results show that chiral Lys·Ca(II)racemization process is very slow,it is relatively safe to be used to supply Lys and Ca(II)for life simultaneously.

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备注/Memo

备注/Memo:
收稿日期:2022-01-15
基金项目:吉林省自然科学基金(20160101308C),白城医学高等专科学校科研平台重点课题(BYKPT202207),白城医学高等专科学校高层次人才团队建设基金(BCYZ20220408),教育部国家级大学生创新基金(202210206034)和吉林省白城市科研规划课题(JBKX20220019)资助项目.
作者简介:柳国洪(1969—),女,吉林白城人,教授,主要从事手性药物化学研究.E-mail:942264863@qq.com
通信作者:潘 宇(1982—),男,吉林大安人,副教授,主要从事计算机应用化学研究.E-mail:115591769@qq. com
赵丽红(1970—),女,吉林大安人,教授,主要从事手性药物化学研究.E-mail:1035213648@qq.com
更新日期/Last Update: 2022-11-25