Spectral characterization, cyclic voltammetry, morphology, biological activities and DNA cleaving studies of amino acid Schiff base metal(II) complexes

Metal complexes are synthesized with Schiff bases derived from o-phthalaldehyde (opa) and amino acids viz., glycine (gly) l-alanine (ala), l-phenylalanine (pal). Metal ions coordinate in a tetradentate or hexadentate manner with these N(2)O(2) donor ligands, which are characterized by elemental analysis, molar conductance, magnetic moments, IR, electronic, (1)H NMR and EPR spectral studies. The elemental analysis suggests the stoichiometry to be 1:1 (metal:ligand). Based on EPR studies, spin-Hamiltonian and bonding parameters have been calculated. The g-values calculated for copper complexes at 300K and in frozen DMSO (77K) indicate the presence of the unpaired electron in the dx2-y2 orbital. The evaluated metal-ligand bonding parameters showed strong in-plane sigma- and pi-bonding. X-ray diffraction (XRD) and scanning electron micrography (SEM) analysis provide the crystalline nature and the morphology of the metal complexes. The cyclic voltammograms of the Cu(II)/Mn(II)/VO(II) complexes investigated in DMSO solution exhibit metal centered electroactivity in the potential range -1.5 to +1.5V. The electrochemical data obtained for Cu(II) complexes explains the change of structural arrangement of the ligand around Cu(II) ions. The biological activity of the complexes has been tested on eight bacteria and three fungi. Cu(II) and Ni(II) complexes show an increased activity in comparison to the controls. The metal complexes of opapal Schiff base were evaluated for their DNA cleaving activities with calf-thymus DNA (CT DNA) under aerobic conditions. Cu(II) and VO(II) complexes show more pronounced activity in presence of the oxidant.     

Synthesis, potentiometric and antimicrobial studies on metal complexes of isoxazole Schiff bases

The metal complexes of Cu(II), Ni(II) and Co(II) with Schiff bases of 3-(2-hydroxy-3-ethoxybenzylideneamino)-5-methyl isoxazole [HEBMI] and 3-(2-hydroxy-5-nitrobenzylidene amino)-5-methyl isoxazole [HNBMI] which were obtained by the condensation of 3-amino-5-methyl isoxazole with substituted salicylaldehydes have been synthesized. Schiff bases and their complexes have been characterized on the basis of elemental analysis, magnetic moments, molar conductivity, thermal analysis and spectral (IR, UV, NMR and Mass) studies. The spectral data show that these ligands act in a monovalent bidentate fashion, co-ordinating through phenolic oxygen and azomethine nitrogen atoms. Chelates of Co(II), Ni(II) appear to be octahedral and Cu(II) appears to be distorted octahedral. To investigate the relationship between formation constants of binary complexes and antimicrobial activity, the dissociation constants of Schiff bases and stability constants of their binary metal complexes have been determined potentiometrically in aqueous solution at 30+/-1 degrees C and at 0.1 M KNO3 ionic strength and discussed. Antimicrobial activities of the Schiff bases and their complexes were screened. The structure-activity correlation in Schiff bases and their metal(II) complexes are discussed, based on the effect of their stability constants. It is observed that the activity enhances upon complexation and the order of activity is in accordance with stability order of metal ions.     

Synthesis, potentiometric and antimicrobial activity studies on DL-amino acids-Schiff bases and their complexes

A relationship between antimicrobial activities and the formation constants of amino acid-Schiff bases and their Cu(II) and Ni(II) complexes was studied. For this purpose, a series of Schiff bases were prepared from DL-amino acids (DL-glycine, DL-alanine) and halo aldehydes (5-chloro-2-hydroxybenzaldehyde, 5-bromo-2-hydroxybenzaldehyde). Schiff bases and their Cu(II) and Ni(II) complexes were characterized by the elemental analysis, spectral analysis, magnetic moment (at ca. 25°C), molar conductivity, and thermal analysis data. The complexes were found to have general compositions [ML(H₂O)]. The protonation constants of the Schiff bases and stability constants of the complexes were determined potentiometrically in a dioxane-water (1: 1) solution at 25°C and 0.1 M KCl ionic strength. Antimicrobial activities of the Schiff bases and their complexes were estimated for six bacteria, such as Bacillus cereus RSKK 863, Staphylococcus aureus ATCC 259231, Micrococcus luteus NRLL B-4375, Escherichia coli ATCC 11230, Aeromonas hydrophila 106, Pseudomonas aeroginosa ATCC 29212, and the yeast Candida albicans ATCC 10239. The role of halogen substitution on the ligands, effect of the metal ion, and stabilities of the complexes are discussed on antimicrobial activities. The text was submitted by the authors in English.     

Synthesis,spectral characterization and biological studies of transition metal(II) complexes with triazole Schiff bases

New metal based triazoles (1–12) have been synthesized by the interaction of novel Schiff base ligands (L¹–L³) with the Co(II), Ni(II), Cu(II) and Zn(II) metal ions. The Schiff base ligands and their all metal(II) complexes have been thoroughly characterized using various physical, analytical and spectroscopic techniques. In vitro bacterial and fungal inhibition studies were carried out to examine the antibacterial and antifungal profile of the Schiff bases in comparison to their metal(II) complexes against two Gram‐positive, four Gram‐negative and six fungal strains. The bioactivity data showed the metal(II) complexes to have more potent antibacterial and antifungal activity than their uncomplexed parent Schiff bases against one or more bacterial and fungal species. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis, spectral, thermal and magnetic studies of Mn(II), Ni(II) and Cu(II) complexes with some benzopyran-4-one Schiff bases

The Schiff bases of N(2)O(2) dibasic ligands, H(2)La and H(2)Lb are prepared by the condensation of ethylenediamine (a) and trimethylenediamine (b) with 6-formyl-7-hydroxy-5-methoxy-2-methylbenzopyran-4-one. Also tetra basic ligands, H(4)La and H(4)Lb are prepared by the condensation of aliphatic amines (a) and (b) with 6-formyl-5,7-dihydroxy-2-methylbenzopyran-4-one. New complexes of H(4)La and H(4)Lb with metal ions Mn(II), Ni(II) and Cu(II) are synthesized, in addition Mn(II) complexes with ligands H(2)La and H(2)Lb are also synthesized. Elemental and thermal analyses, infrared, ultraviolet-visible as well as conductivity and magnetic susceptibility measurements are used to elucidate the structure of the newly prepared metal complexes. The structures of copper(II) complexes are also assigned based upon ESR spectra study. All the complexes separated with the stoichiometric ratio (1:1) (M:L) except Mn-H(4)La and Mn-H(4)Lb with (2:1) (M:L) molar ratio. In metal chelates of the type 1:1 (M:L), the Schiff bases behave as a dinegative N(2)O(2) tetradentate ligands. Moreover in 2:1 (M:L) complexes, the Schiff base molecules act as mono negative bidentate ligand and binuclear complex is then formed. The Schiff bases were assayed by the disc diffusion method for antibacterial activity against Staphylococcus aureus and Escherichia coli. The antifungal activity of the Schiff bases was also evaluated against the fungi Aspergillus flavus and Candida albicans.     

Polymer-anchoring Schiff base ligands and their metal complexes: Investigation of their electrochemical,photoluminescence, thermal and catalytic properties

In this study, we prepared three polymer-anchored Schiff base ligands and their Cu(II), Co(II) and Ni(II) transition metal complexes. For this purpose, we synthesized three Schiff base ligands from the reaction of 2,4-dihydroxybenzaldehyde with diamines in the ethanol solution and characterized by the analytical and spectroscopic methods. We investigated the electrochemical and photophysical properties of the free Schiff base ligands in different solvents and concentrations. In the electrochemical studies, we found that the ligands show the reversible and irreversible redox processes. In order to obtain the polymer-anchored ligands, we used Merrifield’s peptide resin (PS) as solid support. The surface morphologies of the polymer anchored Schiff base ligands were done with the scanning electron microscopy (SEM). We did alkene epoxidation and alkane oxidation reactions of the metal complexes and used the cyclohexene, styrene, cyclohexane and cyclooctane as the substrate and they show the low catalytic activity. The metal complexes have no selectivity in the oxidation reactions. The polymer anchored Schiff base ligands and their metal complexes have high thermal stability at the higher temperatures.     

Stoichiometric and catalytic methods of asymmetric synthesis of nonproteinogenic α-and β-amino acids via transition metal coordination compounds

The complexes of glycine, -alanine, and -alanine with (S)-[N-(N-benzylprolyl)amino] benzophenone formed by Ni(II) and Cu(II) ions and Schiff bases enter into different nucleophilic and electrophilic reactions with the formation of diastereoisomeric complexes which decompose into proteinogenic and nonproteinogenic L-amino acids with a high chemical yield and elevated optical purity (70–90%). Optically pure amino acids can be obtained from diastereoisomerically pure complexes after the complexes are separated by recrystallization of the mixture of diastereoisomeric complexes formed. A new type of interphase catalysts of C-alkylation of achiral Schiff bases was proposed. The catalysts are positively charged Ni(II) and Cu(II) complexes of Schiff bases of chiral diamines. In some cases, these complexes have a higher activity and capacity to execute asymmetric alkylation than traditional chiral interphase catalysts based on cinchonidine.Based on materials in the section report by Yu. N. Belokon' to the 7th European Symposium on Organic Chemistry, ESOC-7.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 5, pp. 1106–1127, May, 1992.     

Synthesis, characterization, biological and thermal behaviour of Co(II), Ni(II) and Cu(II) complexes with Schiff bases having coumarin moieties

A series of Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff bases derived from 5-amino-1,3,4-thiadiazole-2-thiol and 8-formyl-7-hydroxy-4-methylcoumarin/8-acetyl-7-hydroxy-4-methylcoumarin. The chelation of the complexes has been proposed in the light of analytical, spectral (IR, UV–Vis), ESI-mass, magnetic, ESR and thermal studies. The measured molar conductance values indicate that the complexes are non-electrolytes. TG and DTA provide the useful information about the coordination of water molecules to the metal ion and the stability of the complexes. TG and DTA curves show that the Co(II) complexes decomposition takes place in two stages corresponds to loss due to water molecules and Schiff base moiety. Whereas, Ni(II) and Cu(II) complexes decomposition took place in three steps corresponding to the loss of coordinated water molecules, 1,3,4-thiadiazole moiety and coumarin moiety, respectively. The Schiff bases and their complexes have been screened for their antibacterial and antifungal activities. The results of these studies show the metal complexes to be more antibacterial and antifungal as compared to the uncomplexed coumarins.     

SYNTHESIS, CHARACTERIZATION AND SELECTIVITY STUDIES OF POLY(ACRYLAMIDE) INCORPORATING SCHIFF BASES

Three novel polymers incorporating Schiff bases,derived from condensation reactions of poly(acrylamide) with 5- chloro-2-hydroxybenzaldehyde,5-bromo-2-hydroxybenzaldehyde and 5-methyl-2-hydroxybenzaldehyde,have been synthesized,and their Cu(Ⅱ) and Ni(Ⅱ) complexes have been prepared.The ~1H-NMR signals of the—CH=N—and—NH_2 groups have been utilized to determine the relative abundances of Schiff base and acrylamide groups in the polymers containing Schiff bases.Poly(acrylamide) incorporating Schiff bases a...     

Influence of the nature of the metal ion on the rate of reduction of coordinated azomethine group

The kinetics of reduction of the azomethine bond in various Schiff bases and their transition metal complexes with sodium borohydride in dimethylformamide and ethanol solutions was studied. The reduction rate depends on both the structure of the starting Schiff bases and the nature of the metal ion. In transition metal N-phenylsalicylaldiminates, the rate of reduction of the azomethine group increases in the order Zn(II) < Ni(II) < Cu(II) < Co(II) < VO(II) < Mn(II). Similar trend is observed in other series of metal complexes with Schiff bases. The revealed trends are opposite to the Irving-Williams series of stability of complexes. This fact suggests that the major factor affecting the rate of reduction of the coordinated azomethine bond is the strength of its bonding with the metal ion. Depending on particular metal ion, the complexation can either decelerate or accelerate the reduction.     

Studies on some salicylaldehyde Schiff base derivatives and their complexes with Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II)

The formation constants of some transition metal ions Cr(III), Mn(II), Fe(III), Ni(II) and Cu(II) binary complexes containing Schiff bases resulting from condensation of salicylaldehyde with aniline (I), 2-aminopyridine (II), 4-aminopyridine (III) and 2-aminopyrimidine (IV) were determined pH-metrically in ethanolic medium (80%, v/v). The formation constants were determined for all binary complexes. The important infrared (IR) spectral bands corresponding to the active groups in the four ligands and the solid complexes under investigation were studied. The solid complexes have been synthesized and studied by thermogravimetric analysis. The thermal dehydration and decomposition of these complexes were studied kinetically using the integral method applying the Coats-Redfern equation. It was found that the thermal decomposition of the complexes follow second order kinetics. The thermodynamic parameters of the decomposition are also reported. The electronic absorption spectra of the investigated ligands were carried out to determine the pK(a) values spectrophotometrically.     

Structural and Antimicrobial Studies of Some Divalent Transition Metal Complexes with Some New Symmetrical Bis (7-Formylanil Substituted-Sulfoxine) Schiff Base Ligands

Symmetrical bis (7-formyanil substituted-8-hydroxyquinoline-5-sulfonic acid), Schiff bases, react with Co(II), Ni(II) and Cu(II) ions to give M_nL (n=1, 2) complexes as established by conductometric titration in 1 : 1 DMF: H₂O. The complexes were identified by elemental analyses, molecular weight determination, thermal analysis, infrared, magnetic moments, electronic absorption, and electron spin resonance spectra. The suggested general geometry for these complexes may have a tetrahedral crystal structure and the general formula is [M₂L(OH₂4], where M(II) = Co, Ni and Cu and L = 7―X―H₂ L(―X―= dimethyl, p-phenyl, o-phenyl), while for the, trimethyl, ligand and the tetrahedral crystal structure has the general formula [M₂L(OH₂)₂].Antimicrobial activity of these ligands and their transition metal complexes has been investigated on some common fungi and bacteria. A considerable increase in the biocide acticity of these ligands has been observed on coordination with transition metal ions, therefore, these complexes can be used in the chemotherapy of candidiaces and other fungal skin diseases.     

Synthesis and characterization of some pyrimidine, purine, amino acid and mixed ligand complexes

Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) complexes of barbital, thiouracil, adenine, amino acids (methionine, lysine and alanine) and some mixed ligands were prepared and characterized by elemental analyses, IR, electronic spectra, magnetic susceptibility and ESR spectra. Coordination of the metallic centre to the oxygen and nitrogen atoms of barbital, thiouracil, amino acids and coordinate to amino group and nitrogen atom of adenine occurred. Electronic spectra and magnetic susceptibility measurements were utilized to infer the structure of the complexes which are octahedral for Mn(II), Fe(III), Co(II), Ni(II) and Cd(II) and tetrahedral for Mn(II), Cu(II), Zn(II) complexes. ESR spectra were observed for copper complexes with a d(x2)-(y2) ground state with small g(||) values indicating strong interaction between the ligands and their metal ions.     

Synthesis,structural characterization,and anti-ulcerogenic activity of schiff base ligands derived from tryptamine and 5-chloro, 5-nitro, 3,5-ditertiarybutyl salicylaldehyde and their nickel(II), copper(II), and zinc(II) complexes

Ni(II), Cu(II), and Zn(II) complexes with bidentate Schiff bases derived from the condensation reaction of 5-chlorosalicylaldehyde, 5-nitrosalicylaldehyde, and 3,5 ditertiarybutyl-2-hydroxy benzaldehyde with tryptamine, have been reported. The ligands and complexes were characterized by elemental analysis, IR, ¹H NMR and UV–Vis spectroscopy as well as single crystal X-ray structure analysis whenever possible. The complexes were found to have the general formula [M(L)₂]. Spectral studies reveal that these Schiff bases were acting as bidentate ligands and co-ordinating to the metal center through deprotonated phenolate oxygen and azomethine nitrogen atoms. The Zn(II) complexes establish a tetrahedral geometry in a 1:2 metal to ligand stoichiometry, whereas a square planar geometry was proposed for the nickel and copper complexes, slightly distorted in the case of the latter.The antiulcer activity of 5-chlorosalicylaldehyde derivative and its nickel and copper complexes were evaluated in ethanol-induced gastric mucosal injury in rats. This Schiff base and its complexes promote ulcer protection as ascertained by the comparative decrease in ulcer areas, and inhibition of edema and leucocyte infiltration of the submucosal layer.     

Synthetic,spectroscopic, fluorescence,and biological investigation of Co(II), Ni(II), Cu(II), and Zn(II) complexes of Schiff bases derived from 3-formyl-2-mercaptoquinolines (Quinol-2-thiones)

Co(II), Ni(II), Cu(II), and Zn(II) complexes have been prepared with Schiff bases derived from 3-formyl-2-mercaptoquinoline and substituted anilines. The prepared Schiff bases and chelates have been characterized by elemental analysis, molar conductance, magnetic susceptibilities, electronic, IR, ¹H-NMR, ESR, cyclic voltammetry, FAB-mass, and thermal studies. The complexes have stoichiometry of the type ML₂ · 2H₂O coordinating through azomethine nitrogen and thiolate sulfur of 2-mercapto quinoline. An enhancement in fluorescence has been noticed in the Zn(II) complexes whereas quenching occurred in the other complexes. The ligands and their metal complexes have been screened in vitro for antibacterial and antifungal activities by MIC methods with biological activity increasing on complexation. Cu(II) complexes show greater bacterial than fungicidal activities. The brine shrimp bioassay was also carried out to study the in vitro cytotoxicity properties of the ligands and their corresponding complexes. Only four compounds have exhibited potent cytotoxic activity against Artemia salina; the other compounds were almost inactive for this assay.     

Metal complex derivatives of bis(pyrazol-1-yl)methane ligands: synthesis,characterization and anti-Trypanosoma cruzi activity

Transition Metal Chemistry - In this work, the synthesis and characterization of seven complexes (1–7) was performed with Zn(II), Cu(II), Co(II) and Ni(II) transition metals and ligands...     

Exchange interactions in copper(II) complexes with tridentate Schiff bases: EPR and magnetic studies

The influence of the nature of ligands upon the magnetic and EPR properties was investigated for the series of polynuclear Cu(II) complexes with tridentate Schiff bases. A similar tendency of changes in the |J| and D parameters was found for binuclear Cu(II) complexes with ligands derived from condensation of 3-amino-1-propanol with 2-hydroxyaldehydes and acetylacetone as well as for Cu(II) complexes with condensation products of o-aminophenol and β-diketones. The Cu(II) complex with Schiff base of 1-amino-2-propanol and acetylacetone exhibits ferromagnetic behaviour suggesting tetrameric structure.     

Syntheses, characterization, antimicrobial and genotoxic activities of new Schiff bases and their complexes

Two new Schiff base ligands (L¹, L²) have been prepared from the reaction of 2,6-diacetylpyridine and 2-pyridinecarboxyaldehyde with 4-amino-2,3-dimethyl-1-phenyl-3-pyrozolin-5-on, and their Co(II), Cu(II), Ni(II), Mn(II), and Cr(III) metal complexes have also been prepared. The complexes are formed by coordination of N and O atoms of the ligands. Their structures were characterized by physico-chemical and spectroscopic methods. The analytical data shows that the metal to ligand ratio in the Schiff base complexes is 1:2. The Schiff base ligands and all complexes were evaluated for their in vitro antibacterial and antifungal activities by the disc diffusion method. In addition, the genotoxic properties of the ligands were studied.     

Mixed ligand complexes of bis(phenylimine) Schiff base ligands incorporating pyridinium moiety Synthesis, characterization and antibacterial activity

The synthesis and structural characterization of mixed ligand complexes derived from 2,6-pyridinedicarboxaldehydebis(o-hydroxyphenylimine), 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine) (1(ry) ligands) and 2-aminopyridne (2(ry) ligand) are reported. The ligands and their transition metal complexes were characterized on the bases of their elemental analyses, IR, solid reflectance, magnetic moment, molar conductance and thermal analysis (TGA). The mixed ligand complexes are formed in the 1:1:1 (M:L(1) or L(2):L') ratio as found from the elemental analyses and found to have the formulae [MX(2)(L(1) or L(2))(L')].nH(2)O where M = Co(II), Ni(II), Cu(II) and Zn(II), L(1) = 2,6-pyridinedicarboxaldehydebis(p-hydroxyphenylimine), L(2) = 2,6-pyridine dicarboxaldehydebis(o-hydroxyphenylimine), L' = 2-aminopyridine, X = Cl(-) in case of Cu(II) complex and Br(-) in case of Co(II), Ni(II) and Zn(II) complexes and y = 0-3. The molar conductance data reveal that the chelates are non-electrolytes. IR spectra show that the Schiff bases are coordinated to the metal ions in a terdentate manner with NNN donor sites of the pyridine-N and two azomethine-N. While 2-aminopyridine coordinated to the metal ions via its pyridine-N. Magnetic and solid reflectance spectra are used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes are found to be octahedral. The thermal behaviour of these chelates shows that the hydrated water molecules and the anions are removed in a successive two steps followed immediately by decomposition of the ligands (L(1), L(2) and L') in the subsequent steps. The activation thermodynamic parameters, such as, E*, DeltaH*, DeltaS* and DeltaG* are calculated from the TG curves and discussed. The ligands and their metal chelates have been screened for their antimicrobial activities and the findings have been reported, explained and compared with some known antibiotics.     

Synthesis,spectroscopic, DNA cleavage and antibacterial activity of binuclear schiff base complexes

The binuclear Schiff base complexes are formed newly using different transition metals at their stable oxidation state as Cu(II), Ni(II), and VO(II). 3,3′,4,4′-tetraminobiphenyl and 2-aminobenzaldehyde were condensed to form a new Schiff base ligand having an two N₄ group responsible for better chelating to the metal centers. The ligand and their complexes have been established by analytical, spectral and electrochemical data. The interaction studies of the complexes with CT-DNA were carried out using cyclic voltammetry, viscosity measurements and fluorescence spectroscopy. The free ligand and their metal complexes were screened for their antimicrobial activities against the following species: Klebsiella pneumoniae, Escherichia coli and Staphylococcus aureus. A comparative study of minimum inhibitory concentration (MIC) values of the Schiff base and its complexes indicate that the metal complexes exhibit higher antibacterial activity than the free ligand.