Density functional theory (DFT) and ab initio methods were used to study gas phase pyrolytic reaction mechanisms of N ethyl, N isopropyl and N t butyl substituted 2 aminopyrazine at B3LYP/6 31G ...Density functional theory (DFT) and ab initio methods were used to study gas phase pyrolytic reaction mechanisms of N ethyl, N isopropyl and N t butyl substituted 2 aminopyrazine at B3LYP/6 31G * and MP2/6 31G *, respectively. Single point energies of all optimized molecular geometries were calculated at B3LYP/6 311+G(2d,p) level. Results show that the pyrolytic reactions were carried out through a unimolecular first order mechanism which were caused by the migration of atom H(17) via a six member ring transition state. The activation energies which were verified by vibrational analysis and correlated with zero point energies along the reaction channel at B3LYP/6 311+G(2d,p) level were 252.02 kJ·mol -1 ( N ethyl substituted), 235.92 kJ·mol -1 ( N isopropyl substituted) and 234.27 kJ·mol -1 ( N t butyl substituted), respectively. The results were in good agreement with available experimental data.展开更多
New chelates derived from the novel ligand, (Z)-3-amino-N-(3-amino pyrazine-2-carbonyl)pyrazine-2-carbohydrazonic acid (<strong>APA</strong>, <strong>L</strong>), with Cu<sup>2+</sup&g...New chelates derived from the novel ligand, (Z)-3-amino-N-(3-amino pyrazine-2-carbonyl)pyrazine-2-carbohydrazonic acid (<strong>APA</strong>, <strong>L</strong>), with Cu<sup>2+</sup>, Co<sup>2+</sup>, Pt<sup>4+</sup> and Pd<sup>2+</sup> salts were investigated. The results suggest that APA acts as mononegative tridentate in the case of Cu<sup>2+</sup>, binegative tetradentate in the case of Co<sup>2+</sup> and as mononegative bidentate towards Pt<sup>4+</sup> and Pd<sup>2+</sup> chelates. The results of the corrected <i>μ<sub>eff</sub></i>. and spectral suggest the structures of the isolated chelates. The results of the corrected <i>μ<sub>eff</sub></i>. and spectral suggest the geometries of the isolated chelates. Molecular modeling is deduced and chemical reactivity, energy components for chelates and also MEP for <strong>APA</strong> is illustrated. <i>In Vitro</i>, the SOD and radical scavengers like activity of the synthesized compounds Hep G2 liver cancer cells and cytotoxic activity were checked. Metal chelates show potent anti-oxidative activity. The results of cytotoxic activity assay against hepatocellular carcinoma cell line Hep G2 confirmed that Pt<sup>4+</sup> complex has the highest value, while <strong>APA</strong>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Pd<sup>2+</sup> chelates have no significant cytotoxic activity.展开更多
文摘Density functional theory (DFT) and ab initio methods were used to study gas phase pyrolytic reaction mechanisms of N ethyl, N isopropyl and N t butyl substituted 2 aminopyrazine at B3LYP/6 31G * and MP2/6 31G *, respectively. Single point energies of all optimized molecular geometries were calculated at B3LYP/6 311+G(2d,p) level. Results show that the pyrolytic reactions were carried out through a unimolecular first order mechanism which were caused by the migration of atom H(17) via a six member ring transition state. The activation energies which were verified by vibrational analysis and correlated with zero point energies along the reaction channel at B3LYP/6 311+G(2d,p) level were 252.02 kJ·mol -1 ( N ethyl substituted), 235.92 kJ·mol -1 ( N isopropyl substituted) and 234.27 kJ·mol -1 ( N t butyl substituted), respectively. The results were in good agreement with available experimental data.
文摘New chelates derived from the novel ligand, (Z)-3-amino-N-(3-amino pyrazine-2-carbonyl)pyrazine-2-carbohydrazonic acid (<strong>APA</strong>, <strong>L</strong>), with Cu<sup>2+</sup>, Co<sup>2+</sup>, Pt<sup>4+</sup> and Pd<sup>2+</sup> salts were investigated. The results suggest that APA acts as mononegative tridentate in the case of Cu<sup>2+</sup>, binegative tetradentate in the case of Co<sup>2+</sup> and as mononegative bidentate towards Pt<sup>4+</sup> and Pd<sup>2+</sup> chelates. The results of the corrected <i>μ<sub>eff</sub></i>. and spectral suggest the structures of the isolated chelates. The results of the corrected <i>μ<sub>eff</sub></i>. and spectral suggest the geometries of the isolated chelates. Molecular modeling is deduced and chemical reactivity, energy components for chelates and also MEP for <strong>APA</strong> is illustrated. <i>In Vitro</i>, the SOD and radical scavengers like activity of the synthesized compounds Hep G2 liver cancer cells and cytotoxic activity were checked. Metal chelates show potent anti-oxidative activity. The results of cytotoxic activity assay against hepatocellular carcinoma cell line Hep G2 confirmed that Pt<sup>4+</sup> complex has the highest value, while <strong>APA</strong>, Cu<sup>2+</sup>, Co<sup>2+</sup> and Pd<sup>2+</sup> chelates have no significant cytotoxic activity.
