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1.

The chemistry of saccharides has emerged as a new subarea of pharmaceuticals. Condensation reactions of D‐gluconic acid with [M(en)2]Cl2/[M(ea)2]Cl2 where M=Cu, Ni, en=ethylenediamine, and ea=ethanolamine were carried out and a new series of chiral complexes have been isolated and characterized. Molar conductance measurements show that the complexes are ionic, and the spectral data are indicative of octahedral geometry of the complexes [Cu(D‐GlcCO2H en*)2 (H2O)2] · Cl2 (1b), [Cu(D‐GlcCO2H ea*) (H2O)2] · Cl2 (3b) and [Ni(D‐GlcCO2H ea*) (H2O)2] · Cl2 (4), and the square planar geometry of complex [Ni(D‐GlcCO2H en*)2] · Cl2 (2b). Polarimetric data along with CD spectra establish the chiral nature of complexes. Solution stabilities of these complexes were evaluated by cyclic voltammetric techniques as a function of pH. Electrochemical behavior of the complexes was studied in aqueous solution and showed an irreversible CuII/CuI couple. Kinetic studies of complex 1b and 3b with calf thymus DNA have been investigated spectrophotometrically under pseudo‐first order conditions, and k obs values have been evaluated. Circular dichroism, cyclic voltammetry determinations, and viscosity measurements have also been carried out to authenticate the binding of DNA with metal complexes. Complexes 1b and 3b bind to DNA by covalent bond formation.  相似文献   

2.
合成并表征了2个不对称大环双核铜配合物[Cu2(L1)Cl2]·CH3CN(1)和[Cu2(L2)Br2]·CH3CN·H2O(2)。配合物与CT-DNA的作用通过紫外-可见光谱,粘度实验,圆二色谱和凝胶电泳实验进行了研究。紫外-可见光谱的结果表明配合物与DNA的结合常数分别为6.2×105和7.2×105,圆二色谱的实验表明配合物能与DNA较好的结合,粘度实验表明配合物与DNA的结合为非典型的插入模式,凝胶电泳实验显示配合物通过氧化机理对DNA有较强的切割活性。  相似文献   

3.
Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL1), N-(3-hydroxybenzyl)-alanine acid (HL2), N-(3-hydroxybenzyl)-phenylalanine acid (HL3), and N-(3-hydroxybenzyl)-leucine acid (HL4), were synthesized and characterized on the basis of 1H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L1)2]·2H2O (1), [Cu(L2)2(H2O)] (2), [Cu(L3)2(CH3OH)] (3), and [Cu(L4)2(H2O)]·H2O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?106?M?1, 4.32?×?105?M?1, 5.00?×?105?M?1, and 5.70?×?104?M?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.  相似文献   

4.
Two new Cu(II)–hydrazone complexes, [Cu(L)(Hbpe)ClO4]·ClO4·[Cu(L)Cl] (1) and [Cu(HL)2]·1.5ClO4·0.5OH (2) (where HL?=?(E)-N′-(1-(pyridine-2-yl)ethylidene)benzohydrazide and bpe = trans-1-(2-pyridyl)-2-(4-pyridyl)ethylene), have been synthesized and characterized by physicochemical methods. The structures of the complexes have been established by single-crystal X-ray diffraction direct methods, which reveal that the metal ions have distorted square-pyramidal and square-planar geometries in 1, and a distorted octahedral geometry in 2. DNA binding of HL, 1, and 2, performed by UV–vis titration in tris-buffer medium, yielded binding constants, which are 9.5 × 103, 1.88 × 104, and 4.66 × 104 M?1, respectively. Viscosity measurements suggest a surface or groove-binding mode of interaction between CT-DNA with HL, 1, and 2.  相似文献   

5.
Two new Keggin-based hybrid compounds, [Cu2(pdon)3][PMoVI 11MoVO40]·3H2O (1) and [Mn2Cl(H2O)2(pdon)4][PMo12O40]·2H2O (2) (pdon = l, l0-phenanthroline-5,6-dione) (pdon), were synthesized under hydrothermal conditions. By using different metal ions and tuning the ratio of metal to ligand, pdon shows different coordination modes. In compound 1, pdon with three kinds of coordination modes link CuII ions to form a 1D wave chain and Keggin-type polyanions [PMoVI 11MoVO40]4? fringe this 1D chain; hydrogen bonding interactions extend these 1D chains into a 2D supramolecular network. Compound 2 exhibits a discrete structure, in which pdon shows a single chelating coordination. Electrochemical properties of the title compounds have been investigated.  相似文献   

6.
Two Cu coordination polymers [Cu(bpmt)Cl2 · 2DMF]n ( 1 ), [Cu(bpmt)(μ-Cl) · DMSO]n ( 2 ) [bpmt = N1,N4-bis(pyridin-2-ylmethyl)terephthalamide)], were synthesized and characterized. X-ray single-crystal diffractions revealed complex 1 exhibits a one-dimensional (1D) chain in which central CuII ions are located in a six-coordinate slightly distorted octahedral structure. Complex 2 features 1D chain composed of CuI–Cl bridges and all the central CuI ions are situated a twisted tetrahedral configurations. Multi-spectroscopic DNA interaction studies indicate that the two complexes may bind to DNA via groove binding modes, and the calculated binding constants are 1.42 × 104 ( 1 -CT-DNA) and 1.41 × 104 ( 2 -CT-DNA). Both complexes are also capable of efficiently cleaving plasmid pBR322 DNA in the presence of H2O2 via an oxidative mechanism. Furthermore, 1 and 2 are employed as catalysts for the oxidation of 1-phenylethanol to acetophenone. Complex 1 displays good catalytic potential with the conversion rate reaches 99 % using tert-butyl hydroperoxide (TBHP) as oxidant and CH3CN as solvent at 60 °C for 2.0 h.  相似文献   

7.
A bidentate ligand, 5-chloro-2-(phenylazo)pyridine (Clazpy), and its two polypyridyl ruthenium(II) complexes, [Ru(Clazpy)2bpy]Cl2·7H2O (1) and [Ru(Clazpy)2phen]Cl2·8H2O (2), were synthesized and characterized. The DNA-binding properties of these complexes with DNA, the breast cancer susceptibility gene 1 (BRCA1), and the pBIND plasmid DNA were probed by photocleavage, electronic absorption titration, ethidium bromide quenching, and thermal denaturation. Both complexes were found to bind to the BRCA1 fragment through the intercalative mode into the base pairs of DNA, and the DNA-binding constants (Kb) for 1 and 2 were 7.0 × 104 M−1 and 5.1 × 105 M−1, respectively. In addition, both complexes enhanced the single-stranded cleavage of the plasmid DNA. Under comparable experimental conditions, 2 cleaved DNA more effectively than 1, in a dose–response manner. The data indicated that the binding affinity of these two complexes to DNA was dependent on the aromatic planarity and hydrophobicity of the intercalative polypyridyl ligand.  相似文献   

8.
Synthesis and pH-sensitive electrochemical properties of three complexes, [Cu(PD)3] · (ClO4)2 · 2.25CH3CN · 6H2O (1), [Cu(PD)(DMSO)Cl2] · DMSO · H2O (2) and [Co(PD)3] · (ClO4)2 · CH3CN · 2H2O (3) (PD=1,10-phenanthroline-5,6-dione), are reported. Single-crystal X-ray diffraction of the complexes suggest that the structure of 1 is orthorhombic, 2 triclinic and 3 orthorhombic. The electrochemical properties of free PD and the three complexes in phosphate buffer solutions in a pH range between 2 and 9 have been investigated using cyclic voltammetry. The redox potentials of these compounds are strongly dependent on the proton concentration in the range ?0.3 V ~ 0.4 V versus SCE (saturated calomel reference electrode). The reduction behavior of PD can be described from quinone species to semiquinone anion then to the fully reduced dianion. At pH < 4, the reduction of PD proceeds via 2e?/3H+ processes, while at pH > 4, the reduction of PD proceeds via 2e?/2H+. For all complexes, the N–N chelate PD ligand is electrochemically active and underwent step reduction via 2e?/2H+.  相似文献   

9.
Naphthaldimines containing N2O2 donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H2L1)PtCl2]·3H2O (1) and [(H2L3)2Pt2Cl4]·5H2O (3), or monobasic [(HL2)2Pt2Cl2]·2H2O (2) and [(HL4)2Pt]·2H2O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L1)Pt2Cl4(OH)2]·2H2O (5), [(L2)Pt3Cl10]·3H2O (6), [(L3)Pt2Cl4(OH)2]·C2H5OH (7) and [(L4)Pt2Cl6]·H2O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.  相似文献   

10.
The rhenium(II) dinitrosyl and mononitrosyl complexes, i.e. [Re(NO)2(CN)4]·(Phen)2·2H2O (1) and PhenH[Re(NO)(CN)4(H2O)]·(Phen)·3H2O (2) have been isolated and characterized. The X-ray crystal structure of 2 reveals that Re(II) is octahedrally coordinated with one nitrosyl, four cyanides, and one water, with one phenanthroline protonated to compensate the charge of the Re(II) center. The crystal structure shows chemically significant non-covalent interactions like hydrogen bonding involving the uncoordinated water and ππ interactions between phenanthrolinium and phen. The structures of both complexes have been optimized by DFT. Absorption and emission spectral studies and viscosity measurements indicate that both 1 and 2 interact with calf thymus DNA through partial intercalation of DNA bases. The intrinsic-binding constants, obtained from UV–vis spectroscopic studies, are 1.2?×?104 and 7.2?×?104?M?1 for 1 and 2, respectively. Both 1 and 2 are capable of inducing cleavage of plasmid DNA in the presence of H2O2 to form the supercoiled form to nicked circular form. The spectroscopic results of DNA binding are supported by molecular docking studies.  相似文献   

11.
Two new mononuclear iron(III) complexes, [Fe(HL)2](ClO4) · (H2O)1.75· CH3CN (1) and [Fe(HL)Cl2] · DMF (2) [H2L = 3‐(2‐phenol)‐5‐(pyridin‐2‐yl)‐1,2,4‐triazole] have been synthesized and characterized by X‐ray single‐crystal structure analysis. The single crystal X‐ray crystallographic studies reveal that the central iron atom has a distorted octahedral environment for 1 and a distorted square pyramidal geometry for 2. The DNA cleavage activity of the iron(III) complexes was measured, indicating that the six‐coordinated iron(III) (complex 1) was cleavage inactive and only five‐coordinated complex 2 effectively promoted the cleavage of plasmid DNA in the presence and/or absence of activating agents (peroxide oxygen) at physiological pH and temperature. The mechanism of plasmid DNA cleavage was also studied by adding standard radical scavengers. Copyright © 2010 John Wiley & Sons, Ltd.  相似文献   

12.
Three novel complexes, [Zn (tib)2·(H2O)2]·(NO3)2 ( 1 ), [Co (tib)2]·2NO3 ( 2 ) and [Co2(tib)2(btc)]·H2O ( 3 ) [H4btc = 1,2,4,5‐benzenetetracarboxylic acid; H2tib = 1,3,5‐tris(1‐imidazolyl)benzene], were synthesized and characterized by single‐crystal X‐ray, IR and elemental analysis. The interaction of these complexes with FS‐DNA (fish sperm DNA) was monitored, and binding constants were determined using UV/Vis, which revealed that they have the ability to bind to FS‐DNA. DNA‐binding constants (K) for the three complexes were 2.2 × 104 m ?1, 0.7 × 104 m ?1 and 0.09 × 104 m ?1, respectively. The interaction capacity of the complexes with FS‐DNA has been investigated by fluorescence spectroscopy. Stern–Volmer quenching plot values for complexes 1 , 2 and 3 were 0.3784, 0.1028 and 0.076, respectively. The viscosity measurement suggested that complexes 1 , 2 and 3 interact with DNA in an intercalation mode. In addition, anti‐cancer activities of these complexes investigated through MTT assays in vitro indicated that the complexes showed good cytotoxic activity against cancer cell lines. Cytotoxic activity of test complexes against two different cancer cell lines (HeLa and KB cells) showed significant cancer cell inhibition rates. Flow cytometry experiments and morphological apoptosis studies showed that the complexes induced apoptosis of HeLa tumor cell lines. Finally, a further molecular docking technique was employed to confirm the binding of the complexes toward the molecular target DNA.  相似文献   

13.
Two copper(II) complexes of disubstituted 2,2′-bipyridine (bpy = 2, 2′-bipyridine) with tetraalkylammonium groups, [Cu(L1)2Br](ClO4)5·2H2O (1) and [Cu(L2)2Br](ClO4)5·H2O (2) (L1 = [4, 4′-(Et3NCH2)2-bpy]2+, L2 = [4, 4′-((n-Bu)3NCH2)2-bpy]2+), have been synthesized and characterized. X-ray crystallographic study of 1 indicates that Cu(II) is a distorted trigonal bipyramidal or square pyramid. DNA binding of both complexes was studied by UV spectroscopic titration. In the presence of reducing reagents, the cleavage of plasmid pBR322 DNA mediated by both complexes was investigated and efficient oxidative cleavage of DNA was observed. Mechanistic study with reactive oxygen scavengers indicates that hydrogen peroxide and singlet oxygen participate in DNA cleavage.  相似文献   

14.
This work examines transition metal ion complexes which have been synthesized from 3-acetylpyridine 4 N-(2-pyridyl)thiosemicarbazone (HAPS) (1). [Cu(HAPS)2Cl2]?·?H2O (2), [Hg(HAPS)2Cl2] (3), [Ni(HAPS)Cl2]?·?2H2O (4), [UO2(APS)2]?·?2H2O (5), [VO(HAPS)2]SO4?·?H2O (6), and [Zn(HAPS)2Cl2] (7) were characterized by elemental analysis, spectral (IR, 1H-NMR, and UV-Vis), magnetic, and molar conductance measurements. The biochemical studies showed that 2 and 3 have powerful and complete degradation on both DNA and protein. Complexes 2, 4, and 7 showed significant antioxidant properties, especially scavenging on superoxide and hydroxyl radicals. The antibacterial screening demonstrated that all studied complexes have maximum and broad range activities against Gram-positive and Gram-negative bacterial strains.  相似文献   

15.
The new homodinuclear complexes 1–4 of the type [LMII 2Cl2], heterotrinuclear complexes 5 and 6 of the type [LMII 2SnIVCl6] where M = CuII, MnII, CoII, NiII and CuII and NiII, respectively have been synthesized and characterized by elemental analysis and various spectroscopic techniques. The homodinuclear complexes possess two different environments (N2 and N2O2donor sets) for holding the metal ions. The metal ion in N2 set exhibits square planar geometry with two chloride ions in the inner sphere but rhombic structure is found in tetradentate N2O2 Schiff base cavity while in heterotrinuclear complexes SnIV atom is in the octahedral environment. The interaction of complexes 1 and 5 with calf thymus DNA was carried out by absorption spectroscopy and cyclic voltammetry. The intrinsic binding constants (K b ) of complex 1 and 5 were determined as 3.2 × 103 M−1 and 9.6 × 103 M−1, respectively suggesting that complex 5 binds more strongly to CT-DNA than complex 1. Fluorescence studies along with viscosity measurements have also been checked to authenticate the binding of metal complexes with DNA.  相似文献   

16.
Interaction of cobalt cysteinylglycine with histidylserine and histidylphenylalanine was investigated in a 1 : 1 : 1 ratio at 35°C and 0·10 mol dm−3 ionic strength. Their stabilities and geometries were determined. Their DNA binding and cleavage properties were investigated. The intrinsic binding constants (K b ) for DNA bound 1 and 2 (3·03 × 103 M−1 for 1 and 3·87 × 103 M−1 for 2) were determined. Even though the negative charge on the complexes reduced their affinity for DNA, there was an enhancement of binding through specificity. The degradation of plasmid DNA was achieved by cobalt dipeptide complexes [CoII(CysGly)(HisSer)] (1) and [CoII(CysGly)(HisPhe)] (2). Cleavage experiments revealed that 1 and 2 cleave supercoiled DNA (form I) to nicked circular (form II) through hydrolytic pathway at physiological pH. The DNA hydrolytic cleavage rate constants for complexes 1 and 2 were determined to be 0·62 h−1, for 1 and 0·38 h−1 for 2 respectively.  相似文献   

17.
Three novel complexes, namely [Nd·L1·HCOO·(H2O)4] ( 1 ), [Pr·L1·HCOO·(H2O)4] ( 2 ) and [In·L2·Cl·(H2O)2] ( 3 ) (L1 = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)methane, L2 = 1,1-bis(5-(pyrazin-2-yl)-1,2,4-triazol-3-yl)ketone), were synthesized and characterized. The molecular structures of 1 – 3 were confirmed using single-crystal X-ray diffraction. All three obtained complexes are zero-dimensional and connected to each other by hydrogen bonds. In 1 and 2 the metal is surrounded by nine donors and 3 has seven coordination sites. The interaction of 1 – 3 with calf thymus DNA (CT-DNA) was explored using UV absorption spectra and fluorescence spectra. The intrinsic binding constants of 1 – 3 with CT-DNA are about 1.9 × 104, 1.4 × 104 and 1.1 × 104, respectively. Stern–Volmer quenching plots of 1 – 3 have slopes of 0.1508, 0.134 and 0.1205, respectively. The ability of these complexes to cleave pBR322 plasmid DNA was demonstrated using gel electrophoresis assay. Apoptosis studies of the three novel complexes showed a significant inhibitory effect on HeLa cells. Furthermore, MTT assays were used to evaluate the anticancer activity of the three complexes. The cytotoxicity study indicated that complex 1 possesses a higher inhibitory rate of HeLa cells than the other complexes. Especially, the efficacy of 1 was shown to be the highest for cisplatin at 24 h. A further molecular docking technique was introduced to understand the binding of the complexes toward the target DNA.  相似文献   

18.
《Analytical letters》2012,45(12):2182-2193
K[Pt(NH3)Cl3], a valuable precursor for the preparation of platinum complexes with cytostatic activity, e.g. satraplatin, picoplatin, LA-12 and cycloplatam, is currently prepared from cis-[Pt(NH3)2Cl2] or K2[PtCl4] and these are the usual impurities in the final product. A simple, selective and sensitive HPLC-UV analytical method for the determination of the purity of K[Pt(NH3)Cl3] and the quantification of the impurities has been developed and validated. The platinum complexes present in the final product were separated on a strong base ion exchange column by the gradient elution with detection at 213 nm. Intra-assay precisions for the platinum complexes respective to their ions ([PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2]) were between 0.1 and 2.0% (relative standard deviation); intermediate precisions were between 1.4 and 2.0% and accuracies were between 98.6 and 101.4%. Limits of detection of [PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2] were 6 µg · ml?1, 13 mg · ml?1 and 5 µg · ml?1 respectively, limits of quantification of [PtCl4]2?, [Pt(NH3)Cl3]? and cis-[Pt(NH3)2Cl2] were 51 µg · ml?1, 55 mg · ml?1 and 20 µg · ml?1 respectively.  相似文献   

19.
合成并表征了2个不对称大环双核铜配合物[Cu2(L1)Cl2]·CH3CN(1)和[Cu2(L2)Br2]·CH3CN·H2O(2)。配合物与CT-DNA的作用通过紫外-可见光谱,粘度实验,圆二色谱和凝胶电泳实验进行了研究。紫外-可见光谱的结果表明配合物与DNA的结合常数分别为6.2×105和7.2×105,圆二色谱的实验表明配合物能与DNA较好的结合,粘度实验表明配合物与DNA的结合为非典型的插入模式,凝胶电泳实验显示配合物通过氧化机理对DNA有较强的切割活性。  相似文献   

20.
Wang  Cong  Wu  Yancong  Qu  Yao  Zhao  Kun  Xu  Jianhua  Xia  Xinzhao  Wu  Huilu 《Transition Metal Chemistry》2020,45(8):523-529

Three new metal complexes, namely: [Mn(AIDB)Cl2]·DMF (1), [Zn(AIDB)Br2]·CH3OH (2) and [Co(AIDB)Cl2]·CH3OH (3) having a ligand bis(benzimidazol-2-ylmethyl)allylamine (AIDB), have been synthesized in high yields and characterized by elemental analyses, molar conductivities, IR, UV–Vis spectra and single-crystal X-ray diffraction. The structural analysis revealed that all the three complexes 13 have five-coordinated trigonal bipyramid geometry where the degree of distorting is 1>3>2. In vitro antioxidant activity assay demonstrates that the complexes 1 and 3 display high scavenging activity against hydroxyl (OH·) and superoxide (O2−·) radicals.

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