车立新, 张雪娇, 刘芳, 徐锐英, 马宏源, 潘宇, 佟华, 王佐成. 气相α-丙氨酸二价锌配合物手性转变的密度泛函理论研究[J]. 云南大学学报(自然科学版), 2020, 42(5): 966-976. doi: 10.7540/j.ynu.20200038
引用本文: 车立新, 张雪娇, 刘芳, 徐锐英, 马宏源, 潘宇, 佟华, 王佐成. 气相α-丙氨酸二价锌配合物手性转变的密度泛函理论研究[J]. 云南大学学报(自然科学版), 2020, 42(5): 966-976. doi: 10.7540/j.ynu.20200038
CHE Li-xin, ZHANG Xue-jiao, LIU Fang, XU Rui-ying, MA Hong-yuan, PAN Yu, TONG Hua, WANG Zuo-cheng. Chiral transition mechanism of Zn(Ⅱ) and α-Ala complexes in gas phase: A density functional theory study[J]. Journal of Yunnan University: Natural Sciences Edition, 2020, 42(5): 966-976. DOI: 10.7540/j.ynu.20200038
Citation: CHE Li-xin, ZHANG Xue-jiao, LIU Fang, XU Rui-ying, MA Hong-yuan, PAN Yu, TONG Hua, WANG Zuo-cheng. Chiral transition mechanism of Zn(Ⅱ) and α-Ala complexes in gas phase: A density functional theory study[J]. Journal of Yunnan University: Natural Sciences Edition, 2020, 42(5): 966-976. DOI: 10.7540/j.ynu.20200038

气相α-丙氨酸二价锌配合物手性转变的密度泛函理论研究

Chiral transition mechanism of Zn(Ⅱ) and α-Ala complexes in gas phase: A density functional theory study

  • 摘要: 采用密度泛函理论的M06和MN15方法,研究了气相α-丙氨酸二价锌(α-Ala·Zn2+)配合物的2种稳定构型(两性的A_1和中性的A_2)的手性转变. 研究发现,A_1可通过以氧为桥、氮为桥、锌为桥、氧与氮联合为桥以及氧与甲基碳联合为桥等多种途径进行氢迁移,实现手性转变;A_2可通过以氧为桥进行氢迁移,实现手性转变,还可以打开螯合环向A_1异构,按A_1手性转变的多种途径实现手性转变. 势能面研究表明,A_1以锌为桥进行氢迁移的手性转变反应具有优势,活化自由能垒是197.2 kJ·mol−1,A_2打开螯合环向A_1异构后,再以锌为桥进行氢迁移的手性转变反应具有优势,活化自由能垒是228.7 kJ·mol−1. 结果表明:气相丙氨酸锌可以很好地保持其手性特征.

     

    Abstract: The chiral transition of two stable conformations (amphoteric A_1 and neutral A_2) of α-Ala·Zn2+ complex were investigated by means of M06 and MN15 method based on density functional theory. The study reveals that H of A_1 can migrated to realize chiral transition with oxygen, nitrogen, zinc, oxygen with nitrogen and oxygen with methyl carbon as the bridge, respectively. As for A_2, the chiral transition can be realized by H migration with oxygen as the bridge, and that can also be realized by various ways of A_1 chiral transition after opening the chelate ring to A_1 isomerism. The potential energy surface studies indicate that the chiral transition reaction of A_1 with Zn atom as a bridge to realize H migration has advantage, and the activation energy is 197.2 kJ·mol−1. The chiral transition reaction with A_2 opening chelating ring to realize isomerization to A_1 and then using Zn atom as a bridge to realize H migration has advantage, and the activation energy is 228.7 kJ·mol−1. The results show that Ala·Zn2+ can maintain its chiral characteristics well.

     

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