The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent ...The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.展开更多
Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-...Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.展开更多
基金supported by the National Natural Science Foundation of China(21003009)Beijing Jiaotong University,China(2009JBZ019-4 and Undergraduates Innovating Experimentation Project)the Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry,Chinese Academy of Sciences~~
基金supported by the National Natural Science Foundation of China(20773089)Scientific Research Foundation for the Returned Overseas Chinese Scholars,Ministry of Education,China(20071108-18-15)~~
基金supported by the National Natural Science Foundation of China(21003009)Beijing Jiaotong University,China(2009JBZ019-4 and Undergraduates Innovating Experimentation Project)Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry,Chinese Academy of Sciences~~
基金This work was supported by the National Natural Science Foundation of China （No.20903027）, the Natural Science Foundation of Guangdong Province （No.9452402301001941）, and the Doctor Startup Fund of Guangdong Medical College （No.XB0802 and No.XB0804）.
文摘The hydrolysis process of Ru（III） complex （HL）[trans-RuC14L（dmso-S）] （L=l-methyl-l,2,4- triazole and dmso-S=S-dimethyl sulfoxide） （1）, a potential antitumor complex similar to the well-known antitumor agent （Him）[trans-RuC14 （dmso-S）（im）] （NAMI-A, im=imidazole）, was investigated using density functional theory combined with the conductor-like polarizable continuum model approach. Tile structural characteristics and the detailed energy profiles for the hydrolysis processes of this complex were obtained. For the first hydrolysis step, complex 1 has slightly higher barrier energies than the reported anticancer drug NAMI-A, and the result is in accordance with the experimental evidence indicating larger half-life for complex 1. For the second hydrolysis step, the formation of cis-diaqua species is thermodynamic preferred to that of trans isomers. In addition, on the basis of the analysis of electronic characteristics of species in the hydrolysis process, the trend in nucleophilic attack abilities of hydrolysis products by pertinent biomolecules is revealed and predicted.
基金ACKNOWLEDGMENTS This work was supported by Young Scientists Fund of the National Natural Science Foundation of China （No.10904085）.
文摘Rotational isomerism effects on the optical spectra of a push-pull nonlinear optical chro-mophore 2-dicyanomethylen-3-cyano-4-f2-[E-（4-N,N-di（2-acetoxyethyl）-amino）-phenylene-（3,4-dibutyl）-thien-5]-E-vinylg-5,5-dimethyl-2,5-dihydrofuran （FTC） in a few solvents have been studied using the time-dependent density functional theory in combination with the polarizable continuum model. It is shown that the maximum absorption peaks of the ro-tamers have difference of nearly 30 nm both in vacuum and in solutions. The population of the rotamers changes a lot in different solvents. Based on the geometries optimized by Hartree-Fock method, the Maxwell-Boltzmann averaged absorption has been calculated and the maximum absorption peak is in good agreement with experiment. It indicates that the bond length alternation can have an important effect on the optical spectra.
