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1.
Air‐ and moisture‐stable coordination compounds of late first row transition metals, i.e. Co(III), Ni(II), Cu(II) and Zn(II), derived from the ligand (E)‐4‐(4‐chlorophenyl)‐1‐(1‐hydroxypropan‐2‐ylidene)thiosemicarbazide were prepared and successfully characterized using various spectro‐analytical techniques. The molecular structures of the ligand LH and complexes C1 and C2 were determined using single‐crystal X‐ray diffraction. The complexes C1 and C2 are stabilized by weak intermolecular CH???π stacking interactions: C1 between phenyl rings (C2–H21???C2) with a contact distance of 2.855 Å and C2 between phenyl ring and thione sulfur (C13???S1) with a contact distance of 3.366(6) Å. Complex C3 is found to be electrochemically active in the working potential range, showing a quasi‐reversible redox process. The interactions of all the compounds with calf thymus DNA were comprehensively investigated using electronic absorption spectroscopy, viscosity and thermal denaturation studies. Cleavage studies of Escherichia coli DNA were monitored using agarose gel electrophoresis. The results show that LH and complex C4 bind to calf thymus DNA through partial intercalation, while remaining complexes bind electrostatically. Further, C1, C2 and C4 complexes show better cleavage potential towards E. coli DNA. Copyright © 2015 John Wiley & Sons, Ltd.  相似文献   

2.
A new series of DNA binding 5,10,15-tri(N-methyl-4-pyridiniumyl)porphyrin (TrisMPyP)-platinum(II) conjugates was synthesized, in which different spacer ligands were used for appropriate coordination to platinum(II) complexes. Compound 9b exhibited in vivo antitumor activity (T/C%, 294) superior to cisplatin (T/C%, 184) against the leukemia L1210 cell line.  相似文献   

3.
A series of half‐sandwich iridium complexes ( 1 – 4 ) with thiosemicarbazone ligands in two types of coordination modes were synthesized and characterized. The molecular structures of compounds 1 , 2 and 3 were determined using single‐crystal X‐ray diffraction analysis. The nature of the complexes was studied using density functional theory calculations. The stability of the complexes was investigated using UV–visible absorption spectroscopy. The compounds were further evaluated for their in vitro antiproliferative activities against HeLa, HepG2, CNE‐2, SGC‐7901, KB and HEK‐293 T cell lines. Compound 2 displays the highest antiproliferative activity among the other analogues and cisplatin.  相似文献   

4.
A new ligand L, 6-hydroxy chromone-3-carbaldehyde thiosemicarbazone, and its Ni(II) complex have been synthesized and characterized. The crystal structure of Ni(II) complex was determined by single crystal X-ray diffraction. Ni(II) complex and ligand L were subjected to biological tests in vitro using THP-1, Raji and Hela cancer cell lines. Compared with the ligand, Ni(II) complex showed significant cytotoxic activity against these three cancer cell lines. The interactions of Ni(II) complex and ligand L with calf thymus DNA were then investigated by spectrometric titration, ethidium bromide displacement experiments and viscosity measurements methods. The experimental results indicated that Ni(II) complex bound to DNA by intercalative mode via the ligand L. The intrinsic binding constants of Ni(II) complex and ligand L with DNA were (1.10 ± 0.65) × 106 M−1 and (1.48 ± 0.57) × 105 M−1, respectively.  相似文献   

5.
采用自然蒸发法,合成了2个新颖的有机-无机杂化配合物[C_8H_6N_3S]_2[H_2Mo_2O_7](1)和[CoⅡ(C_8H_8N_3OS)_2]_2[H_3PW_(12)O_(40)]·4DMF(2),并对其进行了元素分析、IR、TG和单晶X-射线衍射表征.结果表明:化合物1是由1个双核多阴离子[H2Mo2O7]2-与2个有机组分[C_8H_6N_3S]+通过共价键形成的一维链状结构;化合物2是由水杨醛缩氨基合钴与DMF分子及多酸阴离子通过氢键作用形成的三维网状结构,其中水杨醛缩氨基硫脲合钴呈风车型.  相似文献   

6.
Wang  Min  Wang  Liu-Fang  Li  Yi-Zhi  Li  Qin-Xi  Xu  Zhi-Dong  Qu  Dong-Ming 《Transition Metal Chemistry》2001,26(3):307-310
Metal complexes of a new thiosemicarbazone derived from 3-acetylumbelliferone (HL) have been prepared and characterized. The complexes have the general formula ML2 · nH2O where MII = Co, Ni, Cu and Zn; n = 0 and 2. The ligand and its complexes have been studied for their possible antitumour activity against HL-60 human leukemia in vitro.  相似文献   

7.
In this paper we describe the synthesis and chemical characterization of three new Pd(II)–imidazoline complexes: [PdCl2 (C6H5–CH2–C3H5N2)2] (2), [PdCl(SEt2) (C6H4-C3H5N2)] (5) and [Pd(C6H4-C3H5N2) (μ-Br)]2 (6). We have also analyzed the DNA modifications and in vitro antileukaemic activity of these compounds and of their previously reported analogs [Pd Cl2 (C6H5–C3H5N2)2] (1), [Pd (C6H4–C3H5N2) (μ-OAc)]2 (3), [Pd (C6H4–C3H5N2) (μ-Cl)]2 (4) and [Pt(C6H4–C3H5N2)(μ-Cl] (7). All these compounds modify the DNA secondary structure since they alter the melting temperature (Tm) of the DNA. Circular dichroism spectra indicated, moreover, that compounds 3, 5 and 6 induced higher modification on the double helix than compounds 1, 2 and 4. While compounds 1, 2 and 5 seem to induce slight changes in the electrophoretic mobility of the open and covalently closed circular forms of pUC8 DNA at high ri (input molar ratio of Pd or Pt to nucleotides), compounds 3, 6 and 7 do not modify at any ri the tertiary structure of the plasmid DNA. Antileukaemic tests suggest that compounds 1, 4 and 7 exhibit important cytotoxic activity since their IC50 values against HL-60 human leukaemic cells were below 10 μg ml−1. © 1997 John Wiley & Sons, Ltd.  相似文献   

8.
9.
The mononuclear Schiff base complexes of the type, [ML(CH3OH)2] [M = Co(II), Ni(II), Cu(II) and Zn(II)] have been synthesized by template condensation of l-leucine and glyoxal. The complexes have been characterized on the basis of the results of the elemental analysis, molar conductance, magnetic susceptibility measurements and spectroscopic studies viz, FT-IR, Mass, 1H NMR and 13C NMR spectra. The UV–vis and magnetic moment data revealed an octahedral geometry around Co(II), Ni(II) ion with distortion around Cu(II) ion complex confirmed by EPR data. The conductivity data show a non-electrolytic nature of the complexes. Absorption and fluorescence spectroscopic studies support that all the complexes exhibit a significant binding to calf thymus DNA.  相似文献   

10.
4,6-Diacetylresorcinol serves as a starting point for the generation of multidentate S/N/O or O/N/O symmetrical chelating agents by condensation with thiosemicarbazide or semicarbazide to yield the corresponding bis(thiosemicarbazone) H4L1 or bis(semicarbazone) H4L2, respectively. Reaction of H4L1 and H4L2 with M(NO3)2·6H2O (M?=?Co or Ni) afforded dimeric complexes for H4L1 and binuclear complexes for H4L2, revealing the tendency of S to form bridges. The dimeric cobalt complexes of H4L1 are very interesting in that they contain CoII/CoIII, side/side, low-spin octahedral coordinated CoIII-ions and high-spin square-planar coordinated CoII-ions. These complexes have the general formula [(H2L1)2Co2(H2O) (NO3)]·nEtOH. Arguments supporting these anomalous CoII/CoIII structures are based on a pronounced decrease in their magnetic moments, elemental and thermal analyses, visible and IR spectra, as well as their unreactivity towards organic bases such as 1,10-phenanthroline (phen), 2,2′-bipyridine (Bpy), N,N,N′,N′-tetramethylethylenediamine (Tmen) and 8-hydroxyquinoline (oxine, Ox). The dimeric octahedral NiII complex [(H2L1)2Ni2(H2O)4]·3H2O showed higher reactivity towards phen and Bpy and formed adducts; [(HL1)Ni2(B)(H2O)5] NO3 (B?=?phen or Bpy). In the presence of oxine, the dimeric brown paramagnetic octahedral complex [(H2L1)2Ni2(H2O)4]·3H2O was transformed to the dimeric brick-red diamagnetic square-planar complex [(H3L1)2Ni2](NO3)2. The latter showed dramatic behavior in its 1H NMR spectrum in DMSO-d 6, which was explained on the basis of H+-transfer. By contrast, the binuclear NiII–H4L2 complex (11) showed higher reactivity towards phen, Bpy and oxine. These reactions afforded mixed dimeric complexes having the molar ratio 2?:?2?:?1 (NiII?:?H4L2?:?base). The binuclear CoII–H4L2 complex afforded an adduct with phen and trinuclear complexes with Bpy and oxine. All complexes were found to be unreactive towards Tmen. Structural characterization was achieved by elemental and thermal analyses, spectral data (electronic, IR, mass and 1H NMR spectra) and conductivity and magnetic susceptibility measurements.  相似文献   

11.
Six novel palladium(II) complexes of a thiosemicarbazone Schiff base with isatin moiety (PdL1 to PdL6) were synthesized by the reaction of palladium(II) with the following: (Z )‐2‐(2‐oxoindolin‐3‐ylidene)‐N ‐phenylhydrazinecarbothioamide (L1H), (Z )‐2‐(5‐methyl‐2‐oxoindolin‐3‐ylidene)‐N ‐phenylhydrazinecarbothioamide (L2H), (Z )‐2‐(5‐fluoro‐2‐oxoindolin‐3‐ylidene)‐N ‐phenylhydrazinecarbothioamide (L3H), (Z )‐N ‐methyl‐2‐(5‐nitro‐2‐oxoindolin‐3‐ylidene)hydrazinecarbothioamide (L4H), (Z )‐N ‐methyl‐2‐(5‐methyl‐2‐oxoindolin‐3‐ylidene)hydrazinecarbothioamide (L5H) and (Z )‐N ‐ethyl‐2‐(5‐methyl‐2‐oxoindolin‐3‐ylidene)hydrazinecarbothioamide (L6H). The structures of these complexes were characterized using elemental analysis and infrared, UV–visible, 1H NMR and mass spectroscopies. The structure of PdL5 was further characterized using single‐crystal X‐ray diffraction. The interaction of these complexes with calf thymus DNA was characterized with a high intrinsic binding constant (K b = 5.78 × 104 to 1.79 × 106 M−1), which reflected the intercalative activity of these complexes towards calf thymus DNA. This result was also confirmed from viscosity data. Electrophoresis studies revealed that complexes PdL1 to PdL6 could cleave DNA via an oxidative pathway in the presence of an external agent. Data obtained from an in vitro anti‐proliferative study clearly established the anticancer potency of these compounds against the human colorectal carcinoma cell line HCT 116.  相似文献   

12.
The peptide linkage Schiff base (H2L) and its complexes have been synthesized and fully characterized by elemental analysis, UV–Vis, FTIR, 1H-NMR, 13C-NMR, EPR, and FAB-mass spectra. The stoichiometry of the complexes is [ML] (where M = Cu(II), Co(II), Ni(II), Zn(II), and VO(IV)). All the complexes exhibit square-planar geometry except the vanadyl complex which has square-pyramidal geometry. Interactions of the complexes and free ligand with double-stranded calf thymus DNA (CT-DNA) are studied by UV-spectrophotometric, electrochemical, and viscosity measurements. The data suggest that all the complexes form adducts with DNA and distort the double helix by changing the base stacking. Vanadyl complex forms a weaker adduct to CT-DNA than other complexes, probably due to the square-pyramidal geometry. CT-DNA induces extensive distortion in the planarity of vanadyl complex as EPR spectral calculations reveal. The intrinsic binding constants (K b) of [ZnL], [CuL], [CoL], and [NiL] are 1.1 × 105, 1.4 × 105, 0.8 × 105, and 0.6 × 105 M?1, respectively. Photo-induced DNA cleavage indicates that all complexes cleave DNA effectively. Control DNA cleavage experiments using pUC19 supercoiled (SC) DNA and minor groove binder distamycin suggest major groove binding for the synthesized complexes. The antimicrobial results indicate that the complexes inhibit the growth of bacteria and fungi more than the free ligand.  相似文献   

13.
Seven diorganotin complexes with the Schiff bases derived from salicylaldehyde and l-tyrosine, R2Sn[2-O-5-XC6H3CH?=?NCH(CH2C6 H4OH-4)COO] (X?=?H (1), Br (2); R?=?Me (a), Et (b), Bu (c), Cy (cyclohexyl) (d)), were synthesized and characterized by elemental analysis, IR, 1H and 13C NMR spectra, and the single-crystal X-ray diffraction. In methanol, the racemization of chiral center of l-tyrosinate fragment occurred and the racemic products were obtained. X-ray analyses of 1c, 1d, and 2a2c showed that the tin atoms of the complexes exhibit distorted trigonal-bipyramidal geometries. In 1c, 1d, and 2c, the intermolecular O–H???O hydrogen bonds connected the molecules into 1-D supramolecular chain or a R22(20) macrocyclic dimer, and 2a and 2b formed the 2-D supramolecular network by the intermolecular Sn???O and O–H???O interactions. Bioassay results indicated that 1a, 1c, and 1d had moderate antibacterial activity against Escherichia coli and 1c, 1d, and 2c belonged to the efficient cytostatic agents against two human tumor cell lines (A549 and HeLa) and the activity tends to follow the order Cy > Bu?>?Et?>?Me for the R group attached to tin.  相似文献   

14.
The reaction of the thiosemicarbazones (CH2)4C?NN(H)C(?S)NHR (R = H, Me) with zinc(II) acetate in methanolic solution proceeds readily under mild conditions to form stable mononuclear complexes Zn[(CH2)4C?NN?C(S)NHR]2. DNA interaction studies show that the zinc(II) complexes bind to DNA via groove mode and exhibit efficient DNA cleavage activity in the presence of hydrogen peroxide. Also, the complexes display a binding affinity to bovine serum albumin protein with KBSA values of ca 105 M?1. Topoisomerase catalytic inhibition studies suggest that both complexes are efficient topoisomerase‐I impeders. Furthermore, the anti‐proliferative effects of the two complexes on five human tumor cell lines (Caki‐2, MCF‐7, CaSki, NCI‐H322M and Co‐115) indicate that both complexes have the potential to act as effective anticancer drugs. Copyright © 2016 John Wiley & Sons, Ltd.  相似文献   

15.
Zn (II), Cd (II), Hg (II) and U (VI)O22+ complexes of water‐soluble thiosemicarbazone ligand (NaH3PyTSC) have been prepared and characterized using various techniques. Fourier transform‐infrared (FT‐IR) demonstrated that NaH3PyTSC ligand behaves as a binegative NOS tridentate in [Hg(H2PyTSC)(H2O)]2 and [UO2(H2PyTSC)(H2O)]2 complexes via the deprotonated SH, (C=N)az groups from one molecule and SO3? group from another molecule, while it behaves as a binegative NNSO tetradentate in [Cd(H2PyTSC)(H2O)2]2 complex through the deprotonated SH group, the SO3? group and the nitrogen of both the (C=N)az and (C=N)py. Finally, it behaves as a binegative OO bidentate in [Zn(H2PyTSC)(H2O)2]2·2H2O complex by the deprotonated OH group from one molecule and SO3? group from another ligand molecule. The spectral data suggest a tetrahedral coordination around Hg (II) and Zn (II) ions, and an octahedral coordination around Cd (II) and U (VI)O22+ ions. The NaH3PyTSC ligand exhibited maximum luminescent intensity at 501 nm, while Zn (II), Cd (II) and Hg (II) chelates show emission bands at 459, 458 and 358 nm, respectively. Two comparable methods were used to estimate various thermodynamic parameters. Cyclic voltammetry has been studied for Cd (II) complex in solution. Different biological applications of the isolated complexes have been estimated. It was found that [Cd(H2PyTSC)(H2O)2]2 showed the most effective antioxidant and anticancer activity.  相似文献   

16.
Reaction of copper(I) chloride with thiophene-2-carbaldehyde thiosemicarbazone (Httsc) in acetonitrile in the presence of Ph3P yielded a sulfur-bridged dimer [Cu2Cl22-S-Httsc)2(PPh3)2] · 2CH3CN (1), while a similar reaction with isatin-3-thiosemicarbazone (H2itsc) formed a monomer, [CuCl(H2itsc)(Ph3P)2] · 2CH3CN (3). Furan-2-carbaldehyde thiosemicarbazone (Hftsc) also formed a compound of the composition [Cu2Cl2(Hftsc)2(PPh3)2] · 2H2O (2). Complexes 13 have been characterized using elemental analysis, IR, 1H and 31P NMR spectroscopy and single crystal X-ray crystallography (1 and 3). Acetonitrile is engaged in hydrogen bonding with the chlorine atom {NCCH2–H?Cl)}, which is necessary for the stabilization of the bridging sulfur in 1. In compound 3, however, acetonitrile is strongly hydrogen bonded to the NH hydrogen of the isatin ring {CH3CN?NH(isatin)} and not to the chlorine atom. The Cu?Cu contact of 2.7719(5) Å in dimer 1 is close to twice the van der Waals radius of the Cu atom (2.80 Å).  相似文献   

17.
The reaction of [RuHCl(CO)(B)(EPh3)2] (where E = As, B = AsPh3; E = P, B = PPh3, py, pip, or mor) and dehydroacetic acid thiosemicarbazone (abbreviated as H2dhatsc where H2 stands for the two dissociable protons) in benzene under reflux afford a series of new ruthenium(II) carbonyl complexes containing dehydroacetic acid thiosemicarbazone of general formula [Ru(dhatsc)(CO)(B)(EPh3)] (where E = As, B = AsPh3; E = P, B = PPh3, py, pip or mor; dhatsc = dibasic tridentate dehydroacetic acid thiosemicarbazone). All the complexes have been characterized by elemental analyses, FT-IR, UV-Vis, and 1H NMR spectral methods. The thiosemicarbazone of dehydroacetic acid behaves as dianionic tridentate O, N, S donor and coordinates to ruthenium via phenolic oxygen of dehydroacetic acid, the imine nitrogen of thiosemicarbazone and thiol sulfur. In chloroform solution, all the complexes exhibit metal-to-ligand charge transfer transitions (MLCT). The crystal structure of one of the complexes [Ru(dhatsc)(CO)(PPh3)2] (1) has been determined by single crystal X-ray diffraction which reveals the presence of a distorted octahedral geometry in the complexes. All the complexes exhibit an irreversible oxidation (RuIII/RuII) in the range 0.76-0.89 V and an irreversible reduction (RuII/RuI) in the range −0.87 to −0.97 V. Further, the free ligand and its ruthenium complexes have been screened for their antibacterial and antifungal activities. The complexes show better activity in inhibiting the growth of bacteria Staphylococcus aureus and Escherichia coli and fungus Candida albicans and Aspergillus niger. These results made it desirable to delineate a comparison between free ligand and its ruthenium complexes.  相似文献   

18.
Quinoline‐2‐caboxyaldehyde thiosemicarbazone (HL1) and quinoline ‐2‐caboxyaldehyde N‐dimethyl thiosemicarbazone (HL2) metal complexes were prepared and characterized using analytical and spectroscopic techniques. The measurements showed that ligands behave as monovalent or neutral tridentate ligands bonding via azomethine, quinoline ring nitrogen atoms and sulfur atoms in thiol or thion forms. The anti‐neurotoxic effect of ligands and their complexes showed that, exposure to aluminum increase oxidative stress in the brain, an effect that could be offset by concomitant thiosemicarbazone complexes. Complexes could be having an effect on absorption or excretion of aluminum, due to their chelating activity. These findings may shed light on the potential clinical importance of thiosemicarbazone complexes in Alzheimer's disease.  相似文献   

19.
A novel series of copper polymer complexes ( 1 – 4 ) were synthesized and characterized using various spectroscopic techniques. Spectra of all polymer complexes a tetragonal distorted geometry for the Cu(II) ion. The electronic spectra, magnetic moments and electron spin resonance results indicate tetragonal distortion geometry for the Cu(II) polymer complexes. The effects of various solvents on absorption spectra of the ligand are discussed. A prediction of the interaction of the ligand against anti‐cancer receptors was carried out using AutoDock server. The affinity of the compounds to calf thymus DNA was determined through UV–visible DNA binding titration, and intrinsic binding constant (Kb) was found to be 4.16 × 103, 3.10 × 105, 3.18 × 104 and 2.91 × 105 for polymer complexes 1 – 4 , respectively. The antimicrobial activity of the polymer complexes against bacterial species (Bacillus cereus, Staphylococcus aureus, Escherichia coli, Klebsiella pneumonia, Enterococcus faecalis and Pseudomonas aeruginosa) and fungal species (Aspergillus niger, Fusarium oxysporum and Candida albicans) was investigated.  相似文献   

20.
Six new nickel(II) complexes of thiosemicarbazone Schiff base with isatin moiety [Ni(L1)2–Ni(L6)2] were synthesized through reaction of Ni(II) with (Z)-2-(2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L1H), (Z)-2-(5-methyl-2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L2H), (Z)-2-(5-fluoro-2-oxoindolin-3-ylidene)-N-phenylhydrazinecarbothioamide (L3H), (Z)-N-methyl-2-(5-nitro-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L4H), (Z)-N-methyl-2-(5-methyl-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L5H), and (Z)-N-ethyl-2-(5-methyl-2-oxoindolin-3-ylidene)hydrazinecarbothioamide (L6H). The structures of the Ni complexes were characterized through elemental analysis, infrared, and mass spectral data. The structure of the NiL2 complex was further characterized through single-crystal X-ray diffraction. The interaction of these complexes with calf thymus (CT-DNA) exhibited high intrinsic binding constants (Kb = 1.4 × 105–2.4 × 106 M?1), which reflected their intercalative activity toward CT-DNA. This result was also confirmed by viscosity data. Electrophoresis studies revealed that these complexes could cleave the DNA through the oxidative pathway. The in vitro anti-proliferative study establishes the anticancer potency of these compounds against human colorectal carcinoma cell line.  相似文献   

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