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[1]孙大春,王佐成*,高 峰,等.具有分子内单氢键的气相丝氨酸分子的旋光异构机理[J].厦门大学学报(自然科学版),2019,58(04):471-478.[doi:10.6043/j.issn.0438-0479.201807012]
 SUN Dachun,WANG Zuocheng*,GAO Feng,et al.Optical isomerism mechanism of gas-phase serine molecules with intramolecular single hydrogen bonds[J].Journal of Xiamen University(Natural Science),2019,58(04):471-478.[doi:10.6043/j.issn.0438-0479.201807012]
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具有分子内单氢键的气相丝氨酸分子的旋光异构机理(PDF)
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《厦门大学学报(自然科学版)》[ISSN:0438-0479/CN:35-1070/N]

卷:
58卷
期数:
2019年04期
页码:
471-478
栏目:
研究论文
出版日期:
2019-07-28

文章信息/Info

Title:
Optical isomerism mechanism of gas-phase serine molecules with intramolecular single hydrogen bonds
文章编号:
0438-0479(2019)04-0471-08
作者:
孙大春1王佐成1*高 峰1闫红彦2庄 严2杨晓翠1
1.白城师范学院物理学院,吉林 白城 137000; 2.白城师范学院计算机科学学院,吉林 白城137000
Author(s):
SUN Dachun1WANG Zuocheng1*GAO Feng1YAN Hongyan2ZHUANG Yan2YANG Xiaocui1
1.College of Physics,Baicheng Normal University,Baicheng 137000,China; 2.College of Computer Science,Baicheng Normal University,Baicheng 137000,China
关键词:
丝氨酸 旋光异构 密度泛函理论 过渡态 从头算 能垒
Keywords:
serine optical isomerism density functional theory transient state ab initio barrier
分类号:
O 641.12
DOI:
10.6043/j.issn.0438-0479.201807012
文献标志码:
A
摘要:
采用基于密度泛函理论的B3LYP-D3方法和从头算的MP2方法,在MP2/6-311++G(2df, 2pd)∥B3LYP-D3/6-31+G(d,p)双水平下对气相丝氨酸分子的旋光异构进行研究.对反应通道的研究表明:气相丝氨酸分子的旋光异构反应有a、b、c、d、e和f 6个通道,a和b通道是羧羟基旋转接着羧基内质子转移后(b通道还要经过R-基上的羟基旋转异构)α-氢以氨基氮为桥梁转移,c和e通道是羧羟基旋转后α-氢分别以氨基氮和羰基氧为桥梁转移,d通道是α-氢直接以氨基氮为桥梁转移,f通道是α-氢以羰基氧和氨基氮联合为桥梁转移.对势能面的计算显示:a和b通道具有优势,这2个通道的决速步能垒分别是247.37和249.29 kJ/mol.结果表明孤立的丝氨酸分子很难旋光异构.
Abstract:
Using the B3LYP-D3 method based on density functional theory and ab initio MP2 method,the optical isomerism of gas-phase serine molecules was studied at MP2/6-311++G(2df,2pd)∥B3LYP-D3/6-31+G(d,p)level.The study of reaction channels showed that the optical isomerism of serine molecules had six channels,namely a,b,c,d, e and f.In channels a and b, the carboxyl group rotates and then the proton transfers in the carboxyl group(and then goes through the hydroxyl rotation isomerization on the R-group in channel b),α-hydrogen is transferred with amino nitrogen as the bridge. In channels c and e, after rotation of carboxyl hydroxyl,α-hydrogen is transferred with amino nitrogen and carbonyl oxygen as the bridge, respectively. In channel d,α-hydrogen is transferred directly with amino nitrogen as the bridge, and in channel f,α-hydrogen is transferred with the combination of carbonyl oxygen and amino nitrogen as the bridge.Calculation of the potential energy surface showed that channels a and b had advantages,and the barrier of the two channels was 247.37 kJ/mol and 249.29 kJ/mol,respectively.The results indicate that optical isomerism of isolated serine molecules are difficult to occur.

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备注/Memo

备注/Memo:
收稿日期:2018-07-07录用日期:2018-08-19
基金项目:吉林省科技发展计划(20130101131JC)
*通信作者:wangzc188@163.com
更新日期/Last Update: 1900-01-01