Theoretical Investigation of Detailed Thermodynamic Character of Possible Difunctional Adducts Model  

作　　者：CHANG Guan-Ru ZHOU Li-Xin CHEN Dong 

机构地区：[1]Department of Chemistry, Jinan University, Guangzhou, Guangdong 510632, China

出　　处：《Chinese Journal of Structural Chemistry》2006年第5期533-542,共10页结构化学（英文）

基　　金：This work was supported by the Science Foundation of Jinan University (639)

摘　　要：The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.The B3LYP/6-31G^＊ level of theory was used to optimize trans-[Pt（NH3）（Am）G-L], where Am = quinoline or thiazole and L is chosen as the model for functional groups of peptide side chains, and for adenine and guanine sites of DNA as the ultimate target of platinum anticancer drugs. Bond dissociating energy and stability energy of complexes are chosen to study detailedly thermodynamic character of possible difunctional adducts model. In order to investigate the influence of a polarizable environment on the energy of the Pt-L bond formation, we adopt a new bonding energy formula brought forward by Lippard and his coworkers： △H（Sol） = △H（SCF） ＋ △G（Solv）, which is quite appropriate to compare with what is found in experimental studies. Our calculated results demonstrate that N-containing ligands are more favored in view of thermodynamics both in gas phrase and in solution. However, it is worthly to be noted that addition of solvation free energies result in moderate correction of bonding energy in relative ordering, and the largest ones both present in imidazole ligand, not in guanine ligand. Finally, the nature of bond is analyzed in terms of partial charges distribution based on NBO population.

关 键 词：nonclassical transplatin antitumor drug difunctional adduct DFT 

分 类 号：R979.1[医药卫生—药品]