钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)的双-N(2-羟基乙基)水杨醛亚胺螯合物的合成及其抗癌活性的初步试验

合成了-N(2-羟基乙基)水杨醛亚胺合钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)和锌(Ⅱ)并为元素分析和红外光谱数据所表征。其中三种螯合物为新的席地夫碱金属配合物。用体外美兰法对Co(Ⅱ)、Ni(Ⅱ)和Cu(Ⅱ)配合物进行了抗癌活性试验。结果表明,这些螯合物对六种人体肿瘤具有抑瘤活性。     

Transition metal polymeric chelates: Spectral, magnetic, thermal behaviour of polymeric chelates of poly(resacetophenone diyl ethylene)s with Ni(II), Cu(II), Mn(II), Zn(II) and Co(II)

Polymeric chelates of the type [ML₂]_n where M = Ni(II), Cu(II), Zn(II) or Co(II), L = poly(resacetophenone diyl ethylene)s, andn= degree of polymerization, have been synthesized. Their structures have been elucidated on the basis of analytical, magnetic, electronic and IR spectral studies. Electronic spectra in conjunction with magnetic moments are in accord with an octahedral environment around the central metal ion in all polymeric chelates except Cu(II) and Zn(II) polymeric chelates which have been shown to possess square planar and tetrahedral geometries, respectively. IR spectral studies further suggest that the metal ions are coordinated through the oxygens of the carbonyl and the phenolic hydroxyl groups. All the chelates are paramagnetic except Zn(II), which is found to be diamagnetic.     

Fractional sublimation of some metal chelates of thenoyltrifluoroacetone

Studies on the fractional sublimation of various metal β-diketone chelates have been extended to include the chelates of thenoyltrifluoroacetone (TTA). Many of the common metal chelates were found to be stable, to sublime readily, and to form well-defined zones in the vacuum fractional sublimator. Of the 17 chelates reported only those of manganese (II) and iron(II) were not volatile. The chelates of UO₂(II), Zr(IV), Pb(II), and Cr(III) partially decomposed during sublimation and their recovery was incomplete. The recovery of the sublimed chelates of Ni(II), Mg(II), Al(III), Pd(II), Co(II), Cu(II). Fe(III), Tl(III), Zn(II) and Be(II) ranged from 87 to 100%, with most recoveries being quantitative. The sublimation recrystallization zone temperatures of the various chelates are compared to those of the metal acetylacetonates and the benzoyltrifluoroacetonates; in general, the metal chelates of TTA sublime more readily than those of benzoyltrifluoroacetone but are potentially less useful for fractional sublimation separations than the corresponding metal acetylacetonates. Even so, a quantitative separation of iron(III) from Ni(II), Al(III), Mn(II), and Fe(II) is proposed that depends upon the fractional sublimation of the TTA chelates.     

Studies on Polymeric Chelates

Chelates of Cu(II), Ni(II), Co(II), Mn(II), Fe(III), Zn(II), and dioxouranium(VI) have been prepared from p-hydroxybenzoic acid (P)-urea (U)-formaldehyde (F) copolymer (PUF). The metal-ligand ratios in the chelates were established by eiemental analysis. The probable structures were elucidated on the basis of reflectance and IR spectra in conjunction with magnetic moments. These indicated a distorted octahedral structure for all the chelates except for dioxouranium(VI) chelate. Thermogravimetric analysis has been carried out to ascertain the relative thermal stability of ligand and chelates.     

Magnetic,Spectral, Thermal,and Electrical Properties of Coordination Polymers Derived from Terpolymers

Coordination polymers of Cu(II), Ni(II), Co(II), zinc(II), chromium(IU), iron(IU), oxovanadium(N), and dioxouranium-(VI) with p-hydroxybenzoic acid (PHB)-thiourea (T)-trioxane (T) (PHBTT) polymer were prepared. The analytical data agree with 1:1 metal-ligand stoichiometry. Magnetic susceptibility, visible and IR spectra, and thermal and electrical conductivities of the chelates have been studied and probable structures assigned to the chelates.     

Evaluation of 1-(2-thiazolylazo)-2-hydroxy-3-naphthoic acid as a metallochromic indicator

The acid dissociation constants of 1-(2-thiazolylazo)-2-hydroxy-3-naphthoic acid (TAHN) and the formation constants of Cu(II), Ni(II) and Zn(II) chelates of this dye have been determined spectrophotometrically at 25 degrees in a 5% v/v mixture of dioxan and water. The formation constants of the 1:2 chelates are smaller than those of other o-hydroxythiazolylazo compound chelates. TAHN is a satisfactory indicator for the titrations of Cu(II) and Ni(II) with EDTA.     

Studies on some antifungal transition metal chelates of N-(5-phenyl-1, 3, 4-thiadiazol-2-yl) dithiocarbamic acid

Mn(III), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) chelates of N - (5 - phenyl - 1, 3, 4 - thiadiazol - 2 - yl) dithiocarbamic acid have been prepared and authenticated by analytical, conductance, magnetic and spectroscopic techniques. The ligand and its metal chelates were compared with Dithane M-45, a commercial fungicide, for their fungicdal action against Aspergillus niger and Rhizopus nigracans. Of these, Mn(III), Fe(III) and Cu(II) chelates displayed fungitoxicity of the order of Dithane M-45 at 1000 ppm. It was also noted that there was a parallel relationship between fungicidal activity and stability constants of the metal chelates.     

Syntheses,Characterization and Anti-inflammatory Activity of a Benzamide Derivative and its Metal Chelates

N-Phenylbenzamide-2,2′-dicarboxylic acid (PBDA) and its copper(II), nickel(II), cobalt (II), zinc(II) and manganese(II) chelates have been synthesized and characterized by their physical measurements, infrared and electronic spectra and magnetic moment data. In an acute anti-inflammatory test, the cobalt chelate was most active (31.1% inhibition) followed by the zinc and copper chelates, whereas the copper chelate (22.3% inhibition) was most active in an adjuvant arthritis test. Again the cobalt chelate was most active in the cotton-wad granuloma test. Gastric irritancy was markedly reduced after chelation by copper, followed in order by zinc, cobalt, manganese and nickel chelates. © 1997 John Wiley & Sons, Ltd.     

Structure and behavior of organic analytical reagents : Dimethylglyoxime and its oxygen monomethyl ether

The titration procedure described in previous papers of this series has been applied to a study of some metallic chelates of dimethylglyoxime and of its O-monomethyl ether. Evidence is presented for the existence of dimethylglyoxime chelates with Zn (II), Pb (II), Cd (II), and La (III) in addition to the known Cu (II), Ni (II), and Co (II) complexes. Formation constants are calculated for these complexes, and for those of dimethylglyoxime O-monomethyl ether, on the basis of their most probable structures. The results indicate that the famed specificity of dimethylglyoxime fur nickel does not lie in any special stability of this chclate. but in some other factor, possibly solubility. A comparison of the chelates of dimethylglyoxime with those of its O-ether is discussed in terms of such structural factors as hydrogen bonding and steric hindrance. Heat content and entropy changes have been calculated for the chelation of dimethylglyoxime with Cu (II) and Ni (II) ions.     

Synthesis,characterization, coordination and antibacterial properties of novel asymmetric 1,1′‐disubstituted ferrocene‐derived Schiff‐base ligands and their Co(II), Cu(II) Ni(II) and Zn(II) complexes

Some new asymmetric 1,1 ′‐disubstituted ferrocene‐derived Schiff‐bases have been prepared and used as ligands in the preparation of their Co(II), Cu(II), Ni(II) and Zn(II) metal chelates. These synthesized ligands and their metal chelates have been characterized by their physical, analytical and spectral data. These have also been used for screening against pathogenic bacterial species, e.g. Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa and Klebsiella pneumonae and have been found to be a novel class of organometallic‐based antibacterials. Copyright © 2001 John Wiley & Sons, Ltd.     

Antimicrobial studies of N - N ′-dicarboxydiethyloxamide and its Co(II), Ni(II), Cu(II) and Zn(II) complexes

Neutral complexes of Cu(II), Ni(II), Co(II), and Zn(II) have been synthesized from the oxamide-based ligand derived from leucine and diethyloxalate. The structural features have been deduced from their microanalytical, IR, UV/Vis, mass, ¹H and ¹³C NMR spectral data. The Co(II) and Ni(II) chelates have octahedral geometries and the Cu(II) chelate is a square-pyramidal geometry. The non-electrolytic and monomeric nature of the complexes is shown by their magnetic susceptibility and low conductance data. The biological activities of the ligand and its metal chelates against gram-positive and negative bacteria and fungi are also reported. All the compounds are antimicrobially active and show higher activity than the free ligand.     

Physico-chemical studies on some metal chelates of 5,5 dimethylcyclohexane-2-(2-hydroxyphenyl)hydrazono 1,3 dione (DCPHD)

Cu(II), Ni(II), Co(II), Fe(II) and Mn(II) chelates of 5,5 dimethylcyclohexane-2-(2-hydroxyphenyl) hydrazono 1,3 dione (DCPHD) have been prepared and characterised on the basis of analytical, magnetic moment, conductance and electronic and IR spectral data. Two type of complexes, 1:1 and 1:2 (M:L) are formed. Electronic spectral data suggest high spin octahedral geometry for all the chelates except that of Cu(II) which shows square planar geometry. The ligand shows unusual behaviour with Cu(II) which is explained by IR studies.     

Solid-state chelates of ethylenediamine- tetraacetate with alkali earth metals

Solid-state M-EDTA chelates, where M represents the divalent ions Mg(II), Ca(II), Sr(II) or Ba(II) and EDTA is ethylenediaminetetraacetate anion, were synthesized. Thermogravimetry, derivative thermogravimetry (TG, DTG), differential scanning calorimetry (DSC) and X-ray diffraction powder patterns have been used to characterize and to study the thermal behaviour of these chelates. The results provided information concerning the stoichiometry, crystallinity, thermal stability and thermal decomposition. This revised version was published online in August 2006 with corrections to the Cover Date.     

Magnetic,Spectral, Thermal,and Electrical Properties of Coordination Polymers Derived from Terpolymers

Coordination polymers of Cu(II), Ni(II), Co(II), Zn(II), Cr(III), Fe(III), oxovanadium (IV), and dioxouranium(VI) with salicylic acid (S)-thiourea (T)-trioxane (T) (STT) polymer were prepared. The analytical data agree with 1:1 metal-ligand stoichiometry. Elemental analyses, magnetic, spectral, and thermal properties, and electrical conductivities of STT and its chelates have been studied and probable structures are assigned to the coordination polymers. All the chelates are amorphous powders, insoluble in common organic solvents, and showing slight solubility in DMF.     

Reversed-phase HPLC determination of Co(II), Ni(II) and Fe(III) as their 2-(2-thiazolylazo)-5-dimethylaminophenol chelates

The optimum chromatographic separation conditions for Co(II), Ni(II), and Fe(III) chelates with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM) were investigated. The compositions of chelates were also determined by the HPLC method and thus the possible structure of chelates was given. A precolumn derivatization method was used, followed by separation on an octyl-bonded silica stationary phase with a methanol-tetrahydrofuran-water (40:9:51, v/v/v) mobile phase containing pH 5.8 acetate buffer and 1 x 10(-4)M TAM. The detection limits of Co(II), Ni(II), and Fe(III) at 560 nm are 0.03, 0.02 and 0.1 ng (S N = 2 ), respectively. They can be determined by means of the proposed method without interference from other common metal ions and have been determined in five standard alloys with satisfactory results.     

Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Synthesis,characterization and antibacterial properties of symmetric 1,1′‐ferrocene derived Schiff‐base ligands and their Co(II), Cu(II), Ni(II) and Zn(II) chelates

Symmetric 1,1′‐dimethylferrocene derived Schiff‐base ligands have been prepared by the condensation reaction of 1,1′‐diacetylferrocene with 2‐aminopyrazine, 2‐aminopyridine and 2‐aminothiazole respectively. Their transition metal chelates, of the type [M(L)]Cl₂ [M = Cu(II)] and [M(L)(Cl₂)] [M = Co(II), Ni(II) and Zn(II)] have been prepared. The synthesized Schiff‐base ligands and their metal(II) chelates have been characterized by their physical, analytical and spectral data. Copyright © 2000 John Wiley & Sons, Ltd.     

Thermal analysis of some metal benzohydroxamates

The preparation and thermal analysis of metal chelates of benzohydroxarnic acid (BHA) with Al(III), Cd(II), Co(II), Cu(II) (two compounds), Fe(III), La(III), Pb(II), Mn(II), Ni(II), U(VI) and Zn(II) is discussed. The Al(III), La(III), Pb(II) and Mn(II) chelates are new compounds. DTA and TGA curves of the chelates and of BHA are presented, and the heats of decomposition of the chelates are estimated.     

Mononuclear and polynuclear chelates of picolinoyldithiocarbazate

Mononuclear and polynuclear chelates of potassium picolinoyldithiocarbazate (KHPcDC) with Mn(II), Fe(ll1), Fe(II), Co(Il), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II), Pd(II) and U(VI)O2 have been prepared and characterized by chemical and thermal (TG, DTG, DTA) analyses, molar conductivities, spectral (UV-Visible, IR, NMR, ESR) and magnetic moment measurements. The molar conductivities of the complexes lie in the non-electrolyte range whilst KHPcDC is a 1:1 electrolyte. Changes in selected vibrational absorption of the ligand upon coordination indicate that KHPcDC behaves as monoanionic and coordinates in a bidentate, tridentate and/or bridging tetradentate manner. Trans-form structure is proposed for [Pd(HPcDC)2] x 2H20 and [Cd(HPcDC)2] complexes on the basis of NMR data. An octahedral structure is proposed for Fe(III), Fe(II) and Ni(II) complexes, a square-planar structure for Co(II) and Pd(II) complexes and a tetragonally distorted octahedral structure for the Cu(II) chelate on the basis of spectroscopic and magnetic data. The ligand field parameters (B, Dq, beta) for the Fe(III) and Ni(II) chelates were calculated. TG, DTG and DTA studies support the different modes of chelation of KHPcDC. The solid metal acetate chelates have a unique decomposition exotherm profile which can be used as a rapid and sensitive tool for the detection of acetate-containing complexes.     

Synthesis,structural identification,DNA interaction and biological studies of divalent Mn,Co and Ni chelates of 3-amino-5-mercapto-1,2,4-triazole azo ligand

New Mn (II), Co (II) and Ni (II) azo chelates of 3-amino-5-mercapto-1,2,4-triazole have been designed and obtained. The structures of these newly isolated complexes were assigned according to elemental, thermal analyses, spectral measurements, conductivity and magnetic moment. The metal complexes were predicted to be not electrolytic from the measured molar conductance values. The magnetic moment and UV–Vis spectral data denoted the formation of octahedral geometries for Mn (II), Co (II) and Ni (II) complexes. Thermal properties and decomposition kinetics of the metal chelates are investigated using Coats-Redfern method. The kinetic parameters like activation energy (E^*), pre-exponential factor (A) and entropy of activation (ΔS^*) were quantified. The geometry of the metal complexes is optimized with the help of molecular modeling. The interaction of metal chelates with calf thymus DNA (CT-DNA) was evaluated via UV–Vis absorption and viscosity measurements. The obtained data elucidated that the Ni (II) chelate interact with DNA by groove binding while partial intercalative binding mode have been predicted for Mn (II) and Co (II) chelates. The estimated binding constants for the DNA-complexes are 3.85 ± 0.03 × 10⁴, 1.03 ± 0.2 × 10⁵ and 2.81 ± 0.02 × 10⁵ M⁻¹, for Mn (II), Co (II) and Ni (II) azo chelates, successively. Also, the synthesized complexes were tested for their in-vitro antimicrobial and anticancer efficacy.