Three mononuclear oxovanadium complexes [VO(Hbid)(CF3PIP)] (1) (Hbid=(E)-2-(2-hydroxybenzylideneamino) isoindoline-1,3-dione, CF3PIP=2-(2-trifluoromethyl phenyl)imidazole[4,5-f][1,10] phenanthroline), [VO(Hbid)(m-CF3P...Three mononuclear oxovanadium complexes [VO(Hbid)(CF3PIP)] (1) (Hbid=(E)-2-(2-hydroxybenzylideneamino) isoindoline-1,3-dione, CF3PIP=2-(2-trifluoromethyl phenyl)imidazole[4,5-f][1,10] phenanthroline), [VO(Hbid)(m-CF3PIP)];(2) (m-CF3PIP=2-(3-trifluoromethyl phenyl)imidazole [4, 5-f][1,10]phenanthroline) and [VO(Hbid)(p-CF3PIP)];(3) (p-CF3PIP=2-(4-trifluoromethyl phenyl) imidazole[4,5-f][1,10]phenanthroline) have been synthesized and characterized by elemental analysis, IR, molar conductance, ES-MS and 1H NMR. The DNA-binding properties of these complexes were studied by using UV-Vis absorption titration, fluorescence spectra, viscosity measurements and thermal denaturation studies. The results show that 1, 2 and 3 interact with calf thymus DNA (CT-DNA) by intercalation modes and the magnitude of their intrinsic binding constants (Kb values) follows the order: 2 < 1 < 3. Furthermore, their photocleavage properties with pBR322 plasmid DNA were investigated by agarose gel electrophoresis experiments. The DNA cleavage capacity of complex 3 is also stronger than that of 1 and 2.展开更多
A hydrazone compound 3-chloro-N＇-（3,5-dichloro-2-hydroxybenzylidene）benzo-hydrazide（H2L） derived from the condensation of 3,5-dichlorosalicylaldehyde with 3-chloro-benzohydrazide and its oxovanadium（V） complex ...A hydrazone compound 3-chloro-N＇-（3,5-dichloro-2-hydroxybenzylidene）benzo-hydrazide（H2L） derived from the condensation of 3,5-dichlorosalicylaldehyde with 3-chloro-benzohydrazide and its oxovanadium（V） complex [VOL（CH3OH）（OCH3）] have been successfully prepared and characterized by physico-chemical methods and single-crystal X-ray diffraction.The hydrazone ligand coordinates to the V atom through the phenolate O,imine N,and enolic O atoms.The V atom is hexa-coordinated in a distorted octahedral geometry.The antimicrobial activities（MIC） of the hydrazone ligand and the oxovanadium（V） complex have been evaluated against the bacteria Staphylococcus aureus,Baccilus subtilis,Pseudomonas aeruginosa,and Escherichia coli.展开更多
At room temperature, two new different oxovanadium complexes with simple pyrazole (C3H4N2) as ligand were synthesized. VO(pz)4(SO4)? H2O (1) (pz: pyrazole) is a mono-nuclear oxovana- dium complex with pyrazole as term...At room temperature, two new different oxovanadium complexes with simple pyrazole (C3H4N2) as ligand were synthesized. VO(pz)4(SO4)? H2O (1) (pz: pyrazole) is a mono-nuclear oxovana- dium complex with pyrazole as terminal ligands. V2O2(μ-pz)(μ-OOSO2)(μ-OCH3)(pz)4 (2) is bi-nuclear oxovanadium complex containing three different bridges, which are pyrazolate, sulphate and methoxy, respectively. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The crystal structural data of the complexes 1 and 2 are given as follows: Complex 1, orthorhombic, Pna21, a = 14.547(2) ?, b =10.895(2) ?, c =11.835(2) ?; α=β=γ=90°, V=1875.8(5) ?3, Z = 4, R1 = 0.0485, WR2 = 0.1092. Complex 2, triclinic, P1 , a =8.377(2) ?, b =9.928(2) ?, c = 16.527(3) ?, α = 85.54(3)°, β = 80.92(3)°, γ = 87.92(3)°, R1 = 0.1461, WR2 = 0.4444. The study of non-thermal kinetic de- composition shows that, for complex 1, the possible reaction mechanisms of the two steps are nucleation and growth n=1/3, and three-dimensional pervasion n=2, respectively, and the kinetic equations may be expressed as dα/dT = (A/β)exp(?E/RT){1/3(1?α) [?In(1?α)]?2} and dα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3 [1?(1?α)1/3] ?1}, respectively; for complex 2, the pos- sible reaction mechanisms of the two steps are chemical reaction, and three-dimensional pervasion n=2, respectively; the kinetic equations may be ex- pressed as dα/dT = (A/β)exp(?E/RT)[(1?α)2], anddα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3[1?(1?α)1/3] ?1}, respectively.展开更多
Two novel oxo-vanadium complexes of VO(HB(pz)3)(pzH)(SCN) (1) and VO(HB(3,5-Me2pz)3) (3,5-Me2pzH)(SCN)(SCNH)2 (2) with tris(pyrazolyl) hydroborate ligands were prepared by the reaction of VOSO4?nH2O, KSCN with Na(HB(p...Two novel oxo-vanadium complexes of VO(HB(pz)3)(pzH)(SCN) (1) and VO(HB(3,5-Me2pz)3) (3,5-Me2pzH)(SCN)(SCNH)2 (2) with tris(pyrazolyl) hydroborate ligands were prepared by the reaction of VOSO4?nH2O, KSCN with Na(HB(pz)3), pyrazole, or Na(HB(3,5-Me2pz)3) and methyl-substituted pyrazole in the solution of MeOH, respectively. The complexes were characterized by element analysis, IR, and UV- vis spectra. In the mean time, the fluorescence spec-trum was studied too, and the result indicates that the luminescence of the complexes is related to the in-teraction between oxovanadium ion and tris(pyra- zolyl) hydroborate ligands. In addition, structures of oxovanadium complexes 1 and 2 were determined by X-ray diffraction. The electronic structures and the bonding characters of the two complexes were ana-lyzed with ab initio calculations.展开更多
New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L<sup>1</sup>) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnet...New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L<sup>1</sup>) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnetic moment, thermal and cyclic voltammetry measurements. The results demonstrate that L<sup>1</sup> acts in various styles of chelation with [V<sub>3</sub>O<sub>3</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>3</sub>(EtOH)<sub>1/2</sub>(H<sub>2</sub>O)<sub>3/2</sub>] 1), [VO(L<sup>1</sup>)(2,4-pentadionate)]·Cl·4HCl 2), [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(EtOH)<sub>5/2</sub>] 3), [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(EtOH)<sub>3/2</sub>(H<sub>2</sub>O)<sub>1/2</sub>] 4), [VO(L<sup>1</sup>)SO<sub>4</sub> (H<sub>2</sub>O)<sub>3/2</sub>]·2.5H<sub>2</sub>O 5) and [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)]·H<sub>2</sub>O 6). The values of magnetic moments and spectral studies suggest a square-pyramidal geometry around the V (IV) ion for all complexes. The molar conductance values suggest that the complexes are non-electrolyte, except the [VO(L<sup>1</sup>) (2,4-pentadionate)] Cl·4HCl. Molecular modeling calculates the bond length, bond angle, chemical reactivity, energy components (Kcal/mol) and binding energy (Kcal/mol) for the isolated complexes. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria prove them as growth inhibiting agents. Antitumor activity is carried out in vitro on human mammary gland (breast) MCF-7 and cervical cancer cell-HeLa has shown that [VO(L<sup>1</sup>)SO<sub>4</sub>(H<sub>2</sub>O)<sub>3/2</sub>]·2.5 H<sub>2</sub>O and [VO(L<sup>1</sup>)(2,4-pentadionate)] Cl·4HCl complexes display the highest powerful activity between all of the investigated complexes.展开更多
Complex VO(C 10H 9NO 3)(C 13H 10NO 2)(C 10H 9NO 2- 3=N-salicylidene-L-alaninate, C 13H 10NO- 2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, U...Complex VO(C 10H 9NO 3)(C 13H 10NO 2)(C 10H 9NO 2- 3=N-salicylidene-L-alaninate, C 13H 10NO- 2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P2 1 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, M r=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl 3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E 1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH 2Cl 2<CH 3CN<DMF.展开更多
Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized a...Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis,IR and UV spectroscopies,cyclic voltammetry and single crystal X\|ray diffraction. The complex crystallized in the monoclinic system with space group \%P\%2\-1/\%n\% and the crystal cell parameters \%a\%=1\^3003(1) nm,\%b\%=0\^88836(6) nm,\%c\%=2\^0196(2) nm,\%β\%=95\^065(8)°,\%V\%=2\^3238(3) nm\+3,\%M\%\-r=495\^40 and \%Z\%=4. The two oxygen and one nitrogen atoms of the tridentate hydrazone ligand coordinate to the vanadium atom,forming an equatorial plane. And the coordinated vanadium atom exhibits a distorted octahedral geometry. The atom in the transposition to the oxo O atom is the carbonyl oxygen atom of the hydroxamate ligand in the complex. The half\|wave redox potential of the title complex in the three different solvents positively shifts in the order of CH\-2Cl\-2<CH\-3CN<DMF.展开更多
文摘Three mononuclear oxovanadium complexes [VO(Hbid)(CF3PIP)] (1) (Hbid=(E)-2-(2-hydroxybenzylideneamino) isoindoline-1,3-dione, CF3PIP=2-(2-trifluoromethyl phenyl)imidazole[4,5-f][1,10] phenanthroline), [VO(Hbid)(m-CF3PIP)];(2) (m-CF3PIP=2-(3-trifluoromethyl phenyl)imidazole [4, 5-f][1,10]phenanthroline) and [VO(Hbid)(p-CF3PIP)];(3) (p-CF3PIP=2-(4-trifluoromethyl phenyl) imidazole[4,5-f][1,10]phenanthroline) have been synthesized and characterized by elemental analysis, IR, molar conductance, ES-MS and 1H NMR. The DNA-binding properties of these complexes were studied by using UV-Vis absorption titration, fluorescence spectra, viscosity measurements and thermal denaturation studies. The results show that 1, 2 and 3 interact with calf thymus DNA (CT-DNA) by intercalation modes and the magnitude of their intrinsic binding constants (Kb values) follows the order: 2 < 1 < 3. Furthermore, their photocleavage properties with pBR322 plasmid DNA were investigated by agarose gel electrophoresis experiments. The DNA cleavage capacity of complex 3 is also stronger than that of 1 and 2.
基金supported by the Key Program of the Baoji University of Arts and Sciences (No. ZK1018)
文摘A hydrazone compound 3-chloro-N＇-（3,5-dichloro-2-hydroxybenzylidene）benzo-hydrazide（H2L） derived from the condensation of 3,5-dichlorosalicylaldehyde with 3-chloro-benzohydrazide and its oxovanadium（V） complex [VOL（CH3OH）（OCH3）] have been successfully prepared and characterized by physico-chemical methods and single-crystal X-ray diffraction.The hydrazone ligand coordinates to the V atom through the phenolate O,imine N,and enolic O atoms.The V atom is hexa-coordinated in a distorted octahedral geometry.The antimicrobial activities（MIC） of the hydrazone ligand and the oxovanadium（V） complex have been evaluated against the bacteria Staphylococcus aureus,Baccilus subtilis,Pseudomonas aeruginosa,and Escherichia coli.
基金the National Natural Science Foundation of China （Grant No. 20571036）, SPF（2004-2007） for R0CS SEM and Education Foundation of Liaoning Province （Grant No. 05L212）.
文摘At room temperature, two new different oxovanadium complexes with simple pyrazole (C3H4N2) as ligand were synthesized. VO(pz)4(SO4)? H2O (1) (pz: pyrazole) is a mono-nuclear oxovana- dium complex with pyrazole as terminal ligands. V2O2(μ-pz)(μ-OOSO2)(μ-OCH3)(pz)4 (2) is bi-nuclear oxovanadium complex containing three different bridges, which are pyrazolate, sulphate and methoxy, respectively. The two complexes were characterized by IR, elemental analyses, thermal analyses and X-ray diffraction. The crystal structural data of the complexes 1 and 2 are given as follows: Complex 1, orthorhombic, Pna21, a = 14.547(2) ?, b =10.895(2) ?, c =11.835(2) ?; α=β=γ=90°, V=1875.8(5) ?3, Z = 4, R1 = 0.0485, WR2 = 0.1092. Complex 2, triclinic, P1 , a =8.377(2) ?, b =9.928(2) ?, c = 16.527(3) ?, α = 85.54(3)°, β = 80.92(3)°, γ = 87.92(3)°, R1 = 0.1461, WR2 = 0.4444. The study of non-thermal kinetic de- composition shows that, for complex 1, the possible reaction mechanisms of the two steps are nucleation and growth n=1/3, and three-dimensional pervasion n=2, respectively, and the kinetic equations may be expressed as dα/dT = (A/β)exp(?E/RT){1/3(1?α) [?In(1?α)]?2} and dα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3 [1?(1?α)1/3] ?1}, respectively; for complex 2, the pos- sible reaction mechanisms of the two steps are chemical reaction, and three-dimensional pervasion n=2, respectively; the kinetic equations may be ex- pressed as dα/dT = (A/β)exp(?E/RT)[(1?α)2], anddα/dT = (A/β)exp(?E/RT){3/2(1?α)2/3[1?(1?α)1/3] ?1}, respectively.
文摘Two novel oxo-vanadium complexes of VO(HB(pz)3)(pzH)(SCN) (1) and VO(HB(3,5-Me2pz)3) (3,5-Me2pzH)(SCN)(SCNH)2 (2) with tris(pyrazolyl) hydroborate ligands were prepared by the reaction of VOSO4?nH2O, KSCN with Na(HB(pz)3), pyrazole, or Na(HB(3,5-Me2pz)3) and methyl-substituted pyrazole in the solution of MeOH, respectively. The complexes were characterized by element analysis, IR, and UV- vis spectra. In the mean time, the fluorescence spec-trum was studied too, and the result indicates that the luminescence of the complexes is related to the in-teraction between oxovanadium ion and tris(pyra- zolyl) hydroborate ligands. In addition, structures of oxovanadium complexes 1 and 2 were determined by X-ray diffraction. The electronic structures and the bonding characters of the two complexes were ana-lyzed with ab initio calculations.
文摘New series of oxovanadium (IV) complexes isolated from 2,4,6-tris-(2-pyridyl)-1,3,5-triazine (L<sup>1</sup>) are incorporated and portrayed using spectroscopic (IR, UV-Vis, ESR, mass spectrometric), magnetic moment, thermal and cyclic voltammetry measurements. The results demonstrate that L<sup>1</sup> acts in various styles of chelation with [V<sub>3</sub>O<sub>3</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>3</sub>(EtOH)<sub>1/2</sub>(H<sub>2</sub>O)<sub>3/2</sub>] 1), [VO(L<sup>1</sup>)(2,4-pentadionate)]·Cl·4HCl 2), [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(EtOH)<sub>5/2</sub>] 3), [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(EtOH)<sub>3/2</sub>(H<sub>2</sub>O)<sub>1/2</sub>] 4), [VO(L<sup>1</sup>)SO<sub>4</sub> (H<sub>2</sub>O)<sub>3/2</sub>]·2.5H<sub>2</sub>O 5) and [V<sub>2</sub>O<sub>2</sub>(L<sup>1</sup>)(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)]·H<sub>2</sub>O 6). The values of magnetic moments and spectral studies suggest a square-pyramidal geometry around the V (IV) ion for all complexes. The molar conductance values suggest that the complexes are non-electrolyte, except the [VO(L<sup>1</sup>) (2,4-pentadionate)] Cl·4HCl. Molecular modeling calculates the bond length, bond angle, chemical reactivity, energy components (Kcal/mol) and binding energy (Kcal/mol) for the isolated complexes. The in vitro antibacterial studies of these complexes screened against pathogenic bacteria prove them as growth inhibiting agents. Antitumor activity is carried out in vitro on human mammary gland (breast) MCF-7 and cervical cancer cell-HeLa has shown that [VO(L<sup>1</sup>)SO<sub>4</sub>(H<sub>2</sub>O)<sub>3/2</sub>]·2.5 H<sub>2</sub>O and [VO(L<sup>1</sup>)(2,4-pentadionate)] Cl·4HCl complexes display the highest powerful activity between all of the investigated complexes.
文摘Complex VO(C 10H 9NO 3)(C 13H 10NO 2)(C 10H 9NO 2- 3=N-salicylidene-L-alaninate, C 13H 10NO- 2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P2 1 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, M r=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl 3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E 1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH 2Cl 2<CH 3CN<DMF.
文摘Complex VO(C\-\{12\}H\-\{12\}N\-2O\-2)(C\-\{13\}H\-\{10\}NO\-2)(C\-\{12\}H\-\{12\}N\-2O\+\{\{\}\+\{2-\}\}\-2=acetylacetone benzoylhydrozanate,C\-\{13\}H\-\{10\}NO\+_\-2=\%N\%\|phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis,IR and UV spectroscopies,cyclic voltammetry and single crystal X\|ray diffraction. The complex crystallized in the monoclinic system with space group \%P\%2\-1/\%n\% and the crystal cell parameters \%a\%=1\^3003(1) nm,\%b\%=0\^88836(6) nm,\%c\%=2\^0196(2) nm,\%β\%=95\^065(8)°,\%V\%=2\^3238(3) nm\+3,\%M\%\-r=495\^40 and \%Z\%=4. The two oxygen and one nitrogen atoms of the tridentate hydrazone ligand coordinate to the vanadium atom,forming an equatorial plane. And the coordinated vanadium atom exhibits a distorted octahedral geometry. The atom in the transposition to the oxo O atom is the carbonyl oxygen atom of the hydroxamate ligand in the complex. The half\|wave redox potential of the title complex in the three different solvents positively shifts in the order of CH\-2Cl\-2<CH\-3CN<DMF.
