u(Ⅰ), Zn(Ⅱ), Fe(Ⅱ), Sn(Ⅱ), Pb(Ⅱ) complexes of 1,5 bis(3 nitroacetophenone) thiocarbohydrazone were synthesized by the electrochemical oxidation of anodic metal in non aqueous solvents. The complexes were characte...u(Ⅰ), Zn(Ⅱ), Fe(Ⅱ), Sn(Ⅱ), Pb(Ⅱ) complexes of 1,5 bis(3 nitroacetophenone) thiocarbohydrazone were synthesized by the electrochemical oxidation of anodic metal in non aqueous solvents. The complexes were characterized by elemental analysis, IR UV, magnetic measurement, and molar conductivity etc.展开更多
Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ...Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.展开更多
The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for ...The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for Cu(II) were polarographically determined.The standard Gibbs energies of transfer of Cu(II) from water to sucrosewater solutions,ΔGt,were obtained from the reversible halfwave potentials.The measured values are negative with increasing concentration of sucrose,indicating increasing stability of Cu(II) in sucrosewater solutions.The ΔGt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.展开更多
The search of highly efficient drugs for overcoming cancer drug resistance continues to be a challenge for scientists.Constructing a metal drug based in situ oxidation-state transition system to disturb the redox bala...The search of highly efficient drugs for overcoming cancer drug resistance continues to be a challenge for scientists.Constructing a metal drug based in situ oxidation-state transition system to disturb the redox balance in cancer cells is a promising approach for overcoming cancer drug resistance.Inspired by natural redox-active copper enzyme centers,we developed a Cu(Ⅰ)-Cu(Ⅱ) in situ transition system in this work.Through atom engineering,we fine-tuned the thermodynamic stability of this system to investigate its anticancer activity.The results indicated that the synthetic Cu(Ⅰ)-Cu(Ⅱ) system could under-go in situ transition in vitro and in vivo,to disrupt the intracellular redox balance and trigger mitochondrial dysfunction and G2/M arrest,leading to apoptosis and overcoming cancer drug resistance.This study presents a feasible way to overcome cancer drug resistance by designing an in situ oxidation-state transition metal drug system.展开更多
文摘u(Ⅰ), Zn(Ⅱ), Fe(Ⅱ), Sn(Ⅱ), Pb(Ⅱ) complexes of 1,5 bis(3 nitroacetophenone) thiocarbohydrazone were synthesized by the electrochemical oxidation of anodic metal in non aqueous solvents. The complexes were characterized by elemental analysis, IR UV, magnetic measurement, and molar conductivity etc.
基金Supported by the Science and Technology Planning Project of Shengli College China University of Petroleum(No.13070316)
文摘Reaction of the ligand dmpt（dmpt=6,7-dimethylbenzo[f][1,10]phenanthroline）with CuCl2 afforded mixed valent Cu（Ⅰ）/Cu（Ⅱ） discrete tetranuclear complexes[Cu（Ⅱ）Cl2（dmpt）Cu（Ⅰ）Cl]（1）,while the reaction of ligand dppz（dppz = dipyrido[3,2-a：20,30-c]phenazine） with divalent halogen copper salt CuX2（X=Cl,Br） gave one-dimensional chain mixed valent Cu（Ⅰ）/Cu（Ⅱ） complexes [Cu（Ⅱ）Cl2（dppz）Cu（Ⅰ）Cl]n（2） and discrete mixed valent Cu（Ⅰ）/Cu（Ⅱ）complexes [Cu（Ⅱ）Br2（dppz）（DMF）Cu（Ⅰ）Br]（3）. Complex 2 consists of a one-dimensional chain-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-Cl-dppzC u（Ⅱ）-Clμ2-Cu（Ⅰ）-with Cu（Ⅱ） and Cu（Ⅰ） atoms linked together by chloride anion. Complex 3 is a discrete complex,which is the same as complexes 1 and 2 involving two different copper valent Cu（Ⅰ） and Cu（Ⅱ）. The Cu（Ⅰ） ion presents a pseudo-trihedral geometry,while the Cu（Ⅱ） ion presents a slightly distorted square-pyramidal geometry. This fact proved that halogen ions play a vital role in the assembly procedure. Our research results demonstrate the structural diversification that can be achieved by halogen ions mediated. Moreover,halogen ions-mediated self-assembly may provide useful information for further design of compounds with novel structures and properties.
文摘The electrochemical behavior of Cu(II)Cu(Hg)system in aqueous sucrose solutions was studied by polarography and cyclic squarewave voltammetry.The reversible halfwave potential and the diffusion coefficients for Cu(II) were polarographically determined.The standard Gibbs energies of transfer of Cu(II) from water to sucrosewater solutions,ΔGt,were obtained from the reversible halfwave potentials.The measured values are negative with increasing concentration of sucrose,indicating increasing stability of Cu(II) in sucrosewater solutions.The ΔGt values were split into electrostatic and chemical contributions.The decreased chemical contribution shows that the mixtures are more basic than pure water.
基金supported by National Natural Science Foundation of China (21877049,22177038,32171296)Guangdong Natural Science Foundation (2020B1515120043,2022A1515012235)+2 种基金the Major Program for Tackling Key Problems of Industrial Technology in Guangzhou (201902020013)Guangdong Pearl River Talent Program(2017GC010354)the Innovation Team Project in Guangdong Colleges and Universities (2019KCXTD008,2019KTSCX012)
文摘The search of highly efficient drugs for overcoming cancer drug resistance continues to be a challenge for scientists.Constructing a metal drug based in situ oxidation-state transition system to disturb the redox balance in cancer cells is a promising approach for overcoming cancer drug resistance.Inspired by natural redox-active copper enzyme centers,we developed a Cu(Ⅰ)-Cu(Ⅱ) in situ transition system in this work.Through atom engineering,we fine-tuned the thermodynamic stability of this system to investigate its anticancer activity.The results indicated that the synthetic Cu(Ⅰ)-Cu(Ⅱ) system could under-go in situ transition in vitro and in vivo,to disrupt the intracellular redox balance and trigger mitochondrial dysfunction and G2/M arrest,leading to apoptosis and overcoming cancer drug resistance.This study presents a feasible way to overcome cancer drug resistance by designing an in situ oxidation-state transition metal drug system.
