【摘要】 采用密度泛函理论的M06和MN15方法,结合自洽反应场理论的SMD模型方法,研究了水液相下两性α-丙氨酸二价锌(α-Ala·Zn²⁺)配合物的手性转变反应。主要考察了 3个反应通道a、b和c,a通道是α-H以羰基O为桥迁移,b通道是α-H以Zn为桥迁移,c通道是α-H以氨基N为桥迁移。势能面研究表明,c通道的手性转变反应最具优势,决速步自由能垒是140.7 kJ·mol^-1,来自α-H从α-C向氨基N迁移的过渡态;a通道的手性转变反应是第2优势通道,决速步自由能垒是159.9 kJ·mol^-1,来自α-H从α-C向羰基O迁移的过渡态;b通道的手性转变反应为劣势通道,决速步自由能垒是194.2 kJ·mol^-1,来自α-H从α-C向Zn迁移的过渡态。结果表明:水液相环境下的α-Ala·Zn²⁺可以较好地保持手性特征。更多还原

【Abstract】 The chiral transition of amphoteric α-alanine divalent zinc(α-Ala·Zn²⁺) complexes was studied by using the M06 and MN15 method based on SMD model method of self-consistent reaction field theory in Water/Liquid Phase.Three reaction pathways a,b and c were investigated.In pathway a,α-H is transferred using carbonyl O atom as a bridge.α-H is transferred with Zn atom and amino N atom as bridges in pathway b and c,respectively.Potential energy surface studies indicate that the chiral transition reaction in pathway c has the most advantage.The free energy barrier which comes from the transition state of α-H transfers from α-C to amino N atom is 164.9 kJ·mol^-1.The pathway a of the chiral transition reaction is the second dominant pathway.The free energy barrier which comes from the transition state of α-H transfers from α-C to Carbonyl O atom is 168.9 kJ·mol^-1.The pathway b of the chiral transition reaction is the disadvantaged pathway.The free energy barrier which comes from the transition state of α-H transfers from α-C to Zn atom is 194.2 kJ·mol^-1.The results show that α-Ala·Zn²⁺ can maintain its chiral characteristics well in Water/Liquid Phase.更多还原