以血管紧张素I和II共同的N端三肽分子(AT)为模板分子,丙烯酸(AAc)为功能单体,采用DFT/B3LYP方法和6-31G(d,p)基组,模拟模板分子与功能单体分子印迹预作用体系的构型.通过研究AT与AAc在印迹比例不同时形成复合物的几何构型、电荷转移及...以血管紧张素I和II共同的N端三肽分子(AT)为模板分子,丙烯酸(AAc)为功能单体,采用DFT/B3LYP方法和6-31G(d,p)基组,模拟模板分子与功能单体分子印迹预作用体系的构型.通过研究AT与AAc在印迹比例不同时形成复合物的几何构型、电荷转移及结合能,对AT与AAc预作用的模式进行探讨.另外,进一步比较AT、BT和CT(BT是血管紧张素I结构中C端的三肽分子,CT是血管紧张素II结构中C端的三肽分子)分别与AAc形成最大印迹比例复合物的作用模式及结合能.计算结果表明:AT与AAc通过氢键作用形成分子结构互补的复合物,当AT与AAc印迹比例为1∶6时,电荷转移最大,氢键数目最多,复合物的结合能最低(-361.78 k J/mol),氢键作用的位置显示精氨酸(Arginine,Arg)在印迹复合物中起重要作用;而BT和CT分别与AAc形成的复合物,最大印迹比例都为1∶5,结合能分别为-324.68、-284.66 k J/mol.与BT和CT相比,AT更适合作分子印迹聚合物的模板分子.展开更多
The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations....The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations.Imidazole(Im),4-methylimidazole(4-MI)and pyridine(Py)were selected as the axial ligands.The results revealed that the axial ligand can form coordinate bond with(tpfc)MnVO in the transition state(TS)of the OAT reaction.The axial coordination favored charge transferring from(tpfc)MnVO to DMS,and weakened the Mn≡O bond in both singlet and triplet states.Furthermore,axial coordination can reduce the energy barrier of neutral(tpfc)MnVO from 23.62 kJ·mol^-1 to less than 3 kJ·mol^-1 in the triplet state,which is significantly lower than in the singlet state.This makes(tpfc)MnVO tend to direct the OAT reaction via triplet state pathway.On the other hand,the energy barriers of[(tpfc)MnVIO]+species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol^-1 in a doublet state.This suggests axial ligands were conducive for direct(tpfc)MnVO OAT reaction pathway.展开更多
文摘以血管紧张素I和II共同的N端三肽分子(AT)为模板分子,丙烯酸(AAc)为功能单体,采用DFT/B3LYP方法和6-31G(d,p)基组,模拟模板分子与功能单体分子印迹预作用体系的构型.通过研究AT与AAc在印迹比例不同时形成复合物的几何构型、电荷转移及结合能,对AT与AAc预作用的模式进行探讨.另外,进一步比较AT、BT和CT(BT是血管紧张素I结构中C端的三肽分子,CT是血管紧张素II结构中C端的三肽分子)分别与AAc形成最大印迹比例复合物的作用模式及结合能.计算结果表明:AT与AAc通过氢键作用形成分子结构互补的复合物,当AT与AAc印迹比例为1∶6时,电荷转移最大,氢键数目最多,复合物的结合能最低(-361.78 k J/mol),氢键作用的位置显示精氨酸(Arginine,Arg)在印迹复合物中起重要作用;而BT和CT分别与AAc形成的复合物,最大印迹比例都为1∶5,结合能分别为-324.68、-284.66 k J/mol.与BT和CT相比,AT更适合作分子印迹聚合物的模板分子.
基金supported by the National Natural Science Foundation of China(21275057,21671068)Natural Science Foundation of Guangdong Province(S2012010008763,2017A050506048)
文摘The effects of axial ligand on the oxygen atom transfer(OAT)reaction from 5,10,15-tris(pentafluorophenyl)corrole((tpfc)MnVO)to dimethyl sulfide(DMS)have been investigated by density functional theory(DFT)calculations.Imidazole(Im),4-methylimidazole(4-MI)and pyridine(Py)were selected as the axial ligands.The results revealed that the axial ligand can form coordinate bond with(tpfc)MnVO in the transition state(TS)of the OAT reaction.The axial coordination favored charge transferring from(tpfc)MnVO to DMS,and weakened the Mn≡O bond in both singlet and triplet states.Furthermore,axial coordination can reduce the energy barrier of neutral(tpfc)MnVO from 23.62 kJ·mol^-1 to less than 3 kJ·mol^-1 in the triplet state,which is significantly lower than in the singlet state.This makes(tpfc)MnVO tend to direct the OAT reaction via triplet state pathway.On the other hand,the energy barriers of[(tpfc)MnVIO]+species from disproportionation pathway increased from 1.26 to 33.95 kJ·mol^-1 in a doublet state.This suggests axial ligands were conducive for direct(tpfc)MnVO OAT reaction pathway.
