The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and therma...The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and thermal analysis. Its crystal structure was determined by single crystal X ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The cell parameters are: a=0.82510(11)nm, b=0.68870(9)nm, c=2.3007(3)nm, β =100.847(2)° , V=1.2840(3)nm3, Z=2, Dc=1.742Mg· m- 3, μ (MoKα )=1.723mm- 1, F(000)=684. The structure was refined to final R1=0.0267, wR2=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu2O2 core features. The ligand N (2,4 dihydroxybenzalidene) o aminobenzoic acid dianion is μ 2 tridentate, chelating one copper? ion via one nitrogen, one hydroxy oxygen atom and one carboxylate oxygen atom, and the hydroxy oxygen atom simultaneously coordinates to the other copper? ion of the dimer. In the structure the copper? ion rendered four coordination in a distorted square planar geometry structure. CCDC: 212695.展开更多
A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes i...A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes in the triclinic system, space group P1 with cell parameters a=0.846 0(17) nm, b=1.289 5(3) nm, c=1.452 7(3) nm, α=77.42(3)°, β=79.11(3)°, γ=87.08(3)°, and V=1.518 8(6) nm3. The dinuclear complex shows potential DNA cleavage activity at micromolar concentration in the presence of H2O2 and exhibits higher nuclease efficiency than mononuclear complex [Cu(dipic)(H2dipic)]·H2O. Without external reductants, the added H2O2 may contribute to the generation of hydroxyl radicals that result in DNA strand scission.CCDC:291786.展开更多
Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is ...Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is Pt-S.When the aqueous solution of the complex was stored for one week,an orange-yellow precipitation appeared,different from the complex with light yellow color.Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)2(NH3)2],the linkage isomerism of cis-[Pt(SCN)2(NH3)2].The mechanism of the isomerism reaction is also discussed.展开更多
A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively w...A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively was synthesized and its DNA binding behavior was studied by photophysical methods. It has been found that calf thymus DNA could result in significant decrease both in electronic absorption and fluorescent emission of the complex. The fluorescence quenching by ferrocyanide could be reduced to some extent for the complexin presence of DNA. These facts suggest that this dicopper?complex binds to double helix DNA by partial intercalation.展开更多
The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqu...The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqueous ethanal(I=0.1mol·L -1 ,KNO 3;25℃).The difference of stability among the different complexes was compared and discussed,and the percentages of the stacked isomers in the ternary mixed ligand complexes Pt(Phen)(PCA) +(PCA=2 phenylacetate and 3 phenylpropionate) was calculated.The experimental results indicate that the extent of the intramolecular aromatic ring stacking interaction in the ternary mixed ligand Pt(Phen)(PCA) + complexes depends on the polarity of the solution.The weaker the polarity of the solution,the more notable the intramolecular aromatic ring stacking interaction,the larger the percentage of the stacked isomers in the ternary complexes,and the more stable the ternary mixed ligand complexes.展开更多
The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic flu...The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).展开更多
In the synthetic plasma, the uptake kinetics of sulfato 1,2 cyclohexanediamine platinum(Ⅱ) , selenato 1,2 cyclohexanediamine platinum(Ⅱ) , squarato 1,2 cyclohexanediamine platinum(Ⅱ) , demethylcantharato 1,2 cycloh...In the synthetic plasma, the uptake kinetics of sulfato 1,2 cyclohexanediamine platinum(Ⅱ) , selenato 1,2 cyclohexanediamine platinum(Ⅱ) , squarato 1,2 cyclohexanediamine platinum(Ⅱ) , demethylcantharato 1,2 cyclohexanediamine platinum(Ⅱ) , oxalato 1,2 cyclohexanediamine platinum(Ⅱ) , malonato 1,2 cyclohexanediamine platinum(Ⅱ) , butanedioicato 1,2 cyclohexanediamine platinum(Ⅱ) across human erythrocyte membrane transport have been studied. The experiment results showed that the across membrance transport of all the platinum? complexes followed a first order kinetic process. The rate constants of seven 1,2 cyclohexanediamine platinum? were determined. The uptake rates were related to the hydrolysis rate. The complexes of larger hydrolysis rate have the larger rate constant. The hydrolysis complexes with charge is considered to differ from the neutral complexes in the passages across erythrocyte membranes.展开更多
文摘The novel dinuclear copper(Ⅱ) complex with with N (2,4 dihydroxybenzalidene) o aminobenzoic acid ligand, [Cu(C14H9NO4)]2· 2H2O, has been synthesized and characterized by elemental analysis, IR, UV Vis and thermal analysis. Its crystal structure was determined by single crystal X ray diffraction techniques. The crystal belongs to monoclinic with space group P21/c. The cell parameters are: a=0.82510(11)nm, b=0.68870(9)nm, c=2.3007(3)nm, β =100.847(2)° , V=1.2840(3)nm3, Z=2, Dc=1.742Mg· m- 3, μ (MoKα )=1.723mm- 1, F(000)=684. The structure was refined to final R1=0.0267, wR2=0.0735. The complex molecule structure has dinuclear centrosymmetric dimeric structure in which a planar Cu2O2 core features. The ligand N (2,4 dihydroxybenzalidene) o aminobenzoic acid dianion is μ 2 tridentate, chelating one copper? ion via one nitrogen, one hydroxy oxygen atom and one carboxylate oxygen atom, and the hydroxy oxygen atom simultaneously coordinates to the other copper? ion of the dimer. In the structure the copper? ion rendered four coordination in a distorted square planar geometry structure. CCDC: 212695.
基金supported by the National Natural Science Foundation of China(21073143)“Chunhui Project”from the Ministry of Education of China(Z2009-1-71002,Z2009-1-71006)+2 种基金Graduate Starting Seed Fund of Northwestern Polytechnical University(NPU),China(Z2015152)NPU Foundation for Graduate InnovationChina~~
文摘A novel dinuclear copper(Ⅱ) complex, [Cu2(phen)(dipic)2(H2O)2]·2H2O (phen=1,10-phenanthroline, dipicH2=2,6-pyridinedicarboxylic acid), has been prepared and structurally characterized. The complex crystallizes in the triclinic system, space group P1 with cell parameters a=0.846 0(17) nm, b=1.289 5(3) nm, c=1.452 7(3) nm, α=77.42(3)°, β=79.11(3)°, γ=87.08(3)°, and V=1.518 8(6) nm3. The dinuclear complex shows potential DNA cleavage activity at micromolar concentration in the presence of H2O2 and exhibits higher nuclease efficiency than mononuclear complex [Cu(dipic)(H2dipic)]·H2O. Without external reductants, the added H2O2 may contribute to the generation of hydroxyl radicals that result in DNA strand scission.CCDC:291786.
文摘Cis-diaminedithiocyanatoplatinum(Ⅱ)(cis-[Pt(SCN)2(NH3)2])was prepared and characterized through content analysis of Pt,MS,IR.The results show that the complex has cis configuration and the bond type of Pt and SCN-is Pt-S.When the aqueous solution of the complex was stored for one week,an orange-yellow precipitation appeared,different from the complex with light yellow color.Further comparative studies of these two complexes suggested that the precipitation is cis-[Pt(NCS)2(NH3)2],the linkage isomerism of cis-[Pt(SCN)2(NH3)2].The mechanism of the isomerism reaction is also discussed.
文摘A new bimetallic Cu?complex, [(phen)Cu(μ bdmp)Cu(phen)](ClO4)4·2H2O, where phen and bdmp denote 1,10 phenanthroline and 1,1′ bis(nitrilomethylidyne 4,5 diazafluoren) 4,4′ (μ methylene)bisphenyl respectively was synthesized and its DNA binding behavior was studied by photophysical methods. It has been found that calf thymus DNA could result in significant decrease both in electronic absorption and fluorescent emission of the complex. The fluorescence quenching by ferrocyanide could be reduced to some extent for the complexin presence of DNA. These facts suggest that this dicopper?complex binds to double helix DNA by partial intercalation.
文摘The stability constants of the ternary mixed ligand complexes Pt(Phen)(CA) +(Phen=1,10 Phenanathroline,CA=carboxylate Ligands) were determined by potentiometric pH titration in aqueous solution and in 30～90%(V/V) aqueous ethanal(I=0.1mol·L -1 ,KNO 3;25℃).The difference of stability among the different complexes was compared and discussed,and the percentages of the stacked isomers in the ternary mixed ligand complexes Pt(Phen)(PCA) +(PCA=2 phenylacetate and 3 phenylpropionate) was calculated.The experimental results indicate that the extent of the intramolecular aromatic ring stacking interaction in the ternary mixed ligand Pt(Phen)(PCA) + complexes depends on the polarity of the solution.The weaker the polarity of the solution,the more notable the intramolecular aromatic ring stacking interaction,the larger the percentage of the stacked isomers in the ternary complexes,and the more stable the ternary mixed ligand complexes.
文摘The cyclohexamethylene-diamine squaric acid platinum(Ⅱ) complexs(R,R, S,S) binding to G-actin and the consquence conformation change were studied by N-(1-pyrenyl) maleimide(NPM) labeled fluorescence and intrinsic fluorescence. The binding and chemical kinetics were determined by fluorometry. The results showed that when R (Pt/actin molar ratio) was lower than 30, the Pt binded to G-actin strong binding sites(-SH), when R was larger than 30, the Pt binded to G-actin weaker binding sites. The consquence conformation changes were determined by CD. The CD results showed that R was smaller than 60, G-actin α-helix contents decreased slowly, R was larger than 60, G-actin conformation changed obviously. The reaction of R,R complex of platinum(Ⅱ) S,S complex of platinum(Ⅱ) with G-actin was similar to that of with S,S complex of platinum(Ⅱ).
文摘In the synthetic plasma, the uptake kinetics of sulfato 1,2 cyclohexanediamine platinum(Ⅱ) , selenato 1,2 cyclohexanediamine platinum(Ⅱ) , squarato 1,2 cyclohexanediamine platinum(Ⅱ) , demethylcantharato 1,2 cyclohexanediamine platinum(Ⅱ) , oxalato 1,2 cyclohexanediamine platinum(Ⅱ) , malonato 1,2 cyclohexanediamine platinum(Ⅱ) , butanedioicato 1,2 cyclohexanediamine platinum(Ⅱ) across human erythrocyte membrane transport have been studied. The experiment results showed that the across membrance transport of all the platinum? complexes followed a first order kinetic process. The rate constants of seven 1,2 cyclohexanediamine platinum? were determined. The uptake rates were related to the hydrolysis rate. The complexes of larger hydrolysis rate have the larger rate constant. The hydrolysis complexes with charge is considered to differ from the neutral complexes in the passages across erythrocyte membranes.
