Structural characterization and electrochemical behavior of oxovanadium(V) complexes with N-salicylidene hydrazides

The hydrazone ligands derived from salicylaldehyde and aliphatic carbonic acid hydrazides react with equimolecular amounts of ammonium metavanadate and 8-hydroxyquinoline in refluxing methanol to yield oxovanadium(V) complexes. The synthesis can alternatively be performed starting from [VO(acac)₂] followed by aerial oxidation to form the corresponding oxovanadium(V) complexes. The molecular structures determined by X-ray crystallography feature in all cases a oxovanadium(V) moiety in an distorted octahedral arrangement with an oxygen and nitrogen rich environment. The obtained compounds posses very good solubility in organic solvents, permitting electrochemical investigation. Square wave voltammetric measurements revealed two reversible one-electron reduction steps at 0.355 and −1.638 V. The reduction of the oxovanadium(V) complexes to the corresponding vanadium(IV) species occurs at relatively positive potential, which is independently verified by ESR spectroscopy. While the second reduction step appears to be accompanied by a pre-wave exhibiting an unusual frequency dependence which can be attributed to ligand addition/elimination equilibria related to the 8-hydroxyquinoline coligand. The oxovanadium(V) complexes can be converted into the corresponding cis-dioxovanadium(V) compounds by reaction with aqueous NaOH. ⁵¹V NMR monitoring of this reaction reveals that one equivalent of base results in a full conversion with the cis-dioxovanadium(V) complex being the only species present in solution.     

Vanadium (V) peroxocomplexes: structure, chemistry and biological implications

A short account on the identification in solution of diverse type of vanadium peroxocomplexes is offered. The methodology used is a combination of several techniques, i.e., multinuclear NMR spectroscopy, electrospray ionization mass spectrometry (ESI-MS) and theoretical calculation. The analysis has been carried out in aqueous alcoholic solutions, and in some case also in the presence of appropriate ligands, in order to model some of the natural conditions where vanadium-dependent haloperoxidase enzymes (VHPO) work. With the results obtained, it has been possible to shed light on important aspects of the catalytic cycle of VHPO. Furthermore, a number of synthetic aspects of the reactivity of the various vanadium peroxocomplexes is reviewed.     

Synthesis, spectroscopic and biological aspects of iron(II) complexes

Five novel coordinated complexes of iron(II) with ciprofloxacin and neutral bidentate ligands have been prepared and characterized using elemental analyses, magnetic measurements, IR spectra, UV-VIS spectral, thermogravimetric analyses, 1H-NMR and 13C-NMR. The antimicrobial activity of the individual ligands, metal salt and metal complexes with respect to Bacillus subtilis, Escherichia coli, Bacillus cereus, Staphylococcus aureus, Salmonella typhi, Serratia marcescens, Aspergillus niger, Aspergillus flavus and Lasiodiplodia theobromae were evaluated by the agar-plate technique in comparison to reference standard drugs (ofloxacin, levofloxacin and fluconozole). Binding of the complexes to DNA was studied and is discussed.     

Oxovanadium(IV) and oxovanadium(V) complexes relevant to biological systems

A novel method for the analysis of trace element chemical speciation at parts per billion (ppb) levels in wound fluid samples both contributes to the fundamental inorganic biochemistry of the healing process and permits improved treatments. Potentiometric Stripping Analysis in combination with acid digestion has been used to quantify the total copper and zinc levels in a series of 0.5 ml samples of fluid obtained from surgical wounds. Further, the degree of blood contamination has been investigated using visible spectroscopy. The prevailing chemical speciation (chemical forms) of these total concentrations of copper and zinc amongst low molecular mass ligands in wound fluid has been investigated by computer modelling using JESS, the Joint Expert Speciation System. The model, involving 38 components, generates in the region of 3500 individual low molecular mass complexes including copper, zinc, iron, calcium and manganese species, and predicts that the majority of low molecular mass (lmm) copper complexes are electrically net-neutral, whilst those of zinc are predominantly charged. Further studies indicate that supplementing the concentrations of histidine and tryptophan may increase the net-neutral zinc fraction, the optimum effect being achieved at pH=7.4. This may be important in transporting zinc into healing cells.     

Structure-dependent spectroscopic and redox properties of copper(I) complexes with bidentate iminopyridine ligands

A series of iminopyridine ligands; cyclopropylpyridin-2-ylmethyleneamine (A), cyclopentylpyridin-2-ylmethyleneamine (B), cyclohexylpyridin-2-ylmethyleneamine (C), and cycloheptylpyridin-2-ylmethyleneamine, (D) and their copper(I) complexes, [Cu(L)₂]⁺ (1a-1d) and [Cu(L)(PPh₃)₂]⁺ (2a-2d) have been synthesized and characterized by CHN analyses, ¹H NMR and IR and UV-Vis spectroscopy. Structures of 1a, 1b, 1c and 2a were determined by X-ray crystallography. The coordination polyhedron about the Cu^I center in the complexes is best described as a distorted tetrahedron. The dihedral angles between the least-squares planes of the chelate ligands show considerable variation from 86.1° in 1a to 68.3° in 1b, indicating the importance of packing forces in the crystalline environment. The UV-Vis spectra of the complexes are characterized by first metal to ligand charge transfer bands increasing in wavelength with increasing size of the ring substituents in the ligands, except for the cyclopropyl compounds (1a and 2a), in good agreement with the variation of the dihedral angles between the ligand planes. Cyclic voltammetry of the complexes indicates a quasireversible redox behavior for the complexes. The bulkier ligands (PPh₃) inhibit the geometric distortion within the oxidized form and the redox potentials of complexes 2a-2d are shifted to more positive values, therefore.     

Structural variations and spectroscopic properties of copper(I) complexes with bis(schiff base) ligands

Six copper(I) complexes {[Cu₂(L1)(PPh₃)₂I₂] · 2CH₂Cl₂}_n (1), {[Cu₂(L2)(PPh₃)₂]BF₄}_n (2), [Cu₂(L3)(PPh₃)₄I₂] · 2CH₂Cl₂ (3), [Cu₂(L4)(PPh₃)₄I₂] (4), [Cu₂(L5)(PPh₃)₂I₂] (5) and [Cu₂(L6)(PPh₃)₂I₂] (6) have been prepared by reactions of bis(schiff base) ligands: pyridine-4-carbaldehyde azine (L1), 1,2-bis(4′-pyridylmethyleneamino)ethane (L2), pyridine-3-carbaldehyde azine (L3), 1,2-bis(3′-pyridylmethyleneamino)ethane (L4), pyridine-2-carbaldehyde azine (L5), 1,2-bis(2′-pyridylmethyleneamino)ethane (L6) with PPh₃ and copper(I) salt, respectively. Ligand L1 or L2 links (PPh₃)₂Cu₂(μ-I)₂ units to form an infinite coordination polymer chain. Ligand 3 or 4 acts as a monodentate ligand to coordinate two copper(I) atoms yielding a dimer. Ligand 5 or 6 chelates two copper(I) atoms using pyridyl nitrogen and imine nitrogen to form a dimer. Complexes 1-4 exhibit photoluminescence in the solid state at room temperature. The emission has been attributed to be intraligand π-π* transition mixed with MLCT characters.     

Synthesis,spectroscopic, and biological characterization of the palladium(II) oxalato complexes with heterocyclic ligands

Palladium(II) oxalato complexes with heterocyclic ligands have been prepared and characterized by spectroscopic and biological studies. The compounds are of the general formula Pd(ox)(L)_n where ox = oxalato For n = 1, the ligand is isoxazole, 3,5-dimethylisoxazole, 2-methyl-benzoxazole, 2,5-dimethylbenzoxazole, and ethylenediamine, for n = 2, the ligand is N methylimidazole, N-ethylimidazole, N-propylimidazole, 3-amino, 5-methylisoxazole, and 5-amino 3,4 dimethylisoxazole. The Pd(ox)(L)₂ soluble in water are monomeric square-planar; the Pd(ox)(L) that are little soluble in water are dimeric square-planar with the ligand bridging bidentate except to the chelate ethylenediamine. All the compounds exhibit a certain inhibitorial effect with the exception of the Pd(ox)(en) derivative.     

Oxovanadium(IV) complexes of hydrazides: potential antifungal agents

Oxovanadium(IV) -derived antifungals have been prepared by condensing equimolar amounts of vanadyl sulfate with hydrazides. All the synthesized ligands and their metal complexes were characterized by IR, UV-Visible and micro analytical data. These synthesized compounds were screened for their antifungal activity against Aspergillus flavus (A. flavus), Trichophyton longifusus (T. longifusus), Candida albicans (C. albicans), Microsporum canis (M. canis), Fusarium solani (F. solani) and Candida glaberata (C. glaberata) fungal strains. All complexes showed promising antifungal activity against different fungal strains with the exception of F. Solani and C. glaberata. Minimum Inhibitory Concentration (MIC) of different complexes and ligands are in the range of 250 to 400 microg/mL. Complex 7a and ligand 13 exhibit lowest MIC of 250 microg/mL whereas, complex 5a and ligands 2, 7 and 14 showed highest MIC of 400 microg/mL.     

Synthesis, characterization and biological properties of thienyl derived triazole Schiff bases and their oxovanadium(IV) complexes

A new series of biologically active thienyl derived triazole Schiff bases and their oxovanadium(IV) complexes have been synthesized and characterized on the basis of physical (m.p., magnetic susceptibility and conductivity), spectral (IR, 1H and 13C NMR, electronic and mass spectrometry) and microanalytical data. All the Schiff base ligands and their oxovanadium(IV) complexes have been subjected to in vitro antibacterial activity against four Gram-negative (Escherichia coli, Shigella flexneri, Pseudomonas aeruginosa, Salmonella enterica serover typhi) and two Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacterial strains and, for in vitro antifungal activity against Trichophyton longifucus, Candida albican, Aspergillus flavus, Microscopum canis, Fusarium solani and Candida glabrata. Brine shrimp bioassay was also carried out to check the cytotoxic nature of these compounds.     

Synthesis, structures and spectroscopic properties of palladium(II) complexes with tridentate piperidyl-containing pincer ligands

A new series of square planar palladium(II) complexes with pincer ligands, pip₂NCN⁻ (pip₂NCNH = 1,3-bis(piperidylmethyl)benzene) and pip₂NNN (2,6-bis(piperidylmethyl)pyridine), has been prepared: Pd(pip₂NCN)X (X = Cl, Br, I), [Pd(pip₂NCN)(L)](BF₄) (L = pyridine, 4-phenylpyridine), and [Pd(pip₂NNN)Cl]Cl. The X-ray crystal structures of Pd(pip₂NCN)Br, [Pd(pip₂NCN)(L)]BF₄, and [Pd(pip₂NNN)Cl]Cl confirm the tridentate coordination geometries of the pincer ligands. For the pip₂NCN⁻ complexes, each piperidyl ring adopts a chair conformation with the metal center at an equatorial position on the N(piperidyl) atom. However, one of the piperidyl groups of Pd(pip₂NNN)Cl⁺ adopts a previously unobserved coordination geometry, effectively placing the metal center at an axial position on the N(piperidyl) atom. ¹H NMR and UV-Vis absorption measurements provide additional insight into the electronic structures of these complexes. The ¹H NMR spectra of Pd(pip₂NCN)X (X = Cl, Br, I) are consistent with deshielding of the pip₂NCN⁻ ligand resonances along the Cl < Br < I series, in opposition to the relative halogen electronegativities. It is suggested that this trend is consistent with decreasing filled/filled repulsions between the dπ orbitals of the metal center and the lone pair orbitals of the halide ligands along this series. Electronic absorption spectra support the notion that ligand-to-metal charge-transfer states are stabilized in these palladium(II) complexes relative to their platinum(II) analogues.     

Syntheses of oligonucleotide derivatives with P(V) porphyrin and their properties.

Two types of oligonucleotide derivatives which are substituted by P(V) porphyrin at the phosphorus atom of an internucleotidic linkage and at the 5'-terminal internucleotidic linkage via a spacer were synthesized (Fig. 1), and hybridization capabilities of them with complementary oligonucleotides were evaluated. A novel method for a sensing of oligonucleotide by the fluorescence quenching via photo-induced electron transfer between the P(V) porphyrin labeled oligonucleotide and pyrene-labeled one on the oligonucleotide template is reported.     

Synthesis, spectroscopic characterization and radiosensitizing properties of acetato-bridged copper(II) complexes with 5-nitroimidazole drugs

Three novel acetato-bridged dinuclear copper(II) complexes with 5-nitroimidazoles (CuAcNtrim) and the known copper-acetato-metronidazole have been prepared by an environment-friendly route and spectroscopically characterized. The CuAcNtrim compounds of formula [Cu₂(μ-O₂CCH₃)₄Ntrim₂], where Ntrim = metronidazole (1), secnidazole (2), tinidazole (3) or nimorazole (4), exhibit dimeric copper-acetato paddle-wheel structures with Ntrim axial ligands coordinated to copper(II) ions through the N₃ atoms of the imidazole rings. EPR data indicate antiferromagnetic behavior for this novel series of copper complexes. The constant coupling has been found to decrease along with the increasing of basicity of the Ntrim axial ligand. The CuAcNtrim complexes and the correspondent Ntrim parent drugs have shown radiosensitizer properties for Hep2 (human larynx cancer) cell line in vitro. The best enhancement of radiosensitizer activity upon coordination of the Ntrim drug to copper(II) has been found for the nimorazole compound which has the strongest Cu-Ntrim bond and exhibits the highest lipophilicity within the series of CuAcNtrim complexes.     

Synthesis and biological studies of neutral technetium (V) complexes containing NNOS donor sets

Complexation of ligands containing an N₃S donor set has been affected with [^99mTc]. These are part of a ligand series of analogous structures which exhibit similar chemistry and potentially interesting biology. The complexes which have been characterized with [^33mTc]as [TcOL] are neutral and lipophilic and their biological behaviour has been assessed in rats. After HPLC purification of the no-carrier added preparation, brain uptake of the tracers was > 1% at 15 min p.i. Muscle activity was significant with slow blood clearance.     

Molecular complexes of ivy and licorice saponins with sildenafil citrate (Viagra) and their biological activity

The molecular complexation of triterpene glycosides α-hederin (hederagenin 3-O-α-L-rhamnopyranosyl-(l → 2)-O-α-L-arabinopyranoside), hederasaponin C (hederagenin 3-O-α-L-rhamnopyranosyl-(l → 2)-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(l → 4)-O-β-D-glucopyranosyl-(l → 6)-O-β-D-glucopyranoside), and glycyram (monoammonium glycyrrhizinate) with sildenafil citrate was investigated for the first time using electrospray ionization mass spectroscopy. The glycosides form a complex in a 1: 1 molar ratio. The influence of the complex on Avena sativa seeds germination and its ichthyotoxicity against Poecilia reticulata were studied.     

Synthesis, structure, spectroscopic properties and biological activity of mixed diorganotin(IV) complexes containing pyridine-2-carbaldehyde thiosemicarbazonato and diphenyldithiophosphinato ligands

Reaction of the title ligands (HPyTSC and HS(S)PPh2, respectively) with R2SnO (R = Me, Et, Bu) in ethanol (EtOH) afforded the complexes [SnMe2(PyTSC) (S2PPh2)].EtOH (1) and [SnR2(PyTSC) (S2PPh2)] (R = Et (2), Bu (3)). The structures of 1 and 2 were determined by single-crystal X-ray diffractometry. In both these complexes the tin atom is coordinated to an N,N,S-dentate thiosemicarbazonate ligand, an anisobidentate dithiophosphinato ligand and the two R groups. The coordination polyhedrons can be described as distorted pentagonal bipyramids. A comparative study of the IR spectra of 1, 2 and 3 indicates that the butyl complex has a similar structure. Multinuclear (1H, 13C, 31P and 119Sn) NMR data suggest that the structures of 1 and 2 probably remain in CDCl3 (or DMSO-d6) solution but compound 3 partially decomposes in these media. Preliminary results on the effects of the complexes on the proliferation and differentiation of FLC, CEM, U937, K562 and TOM-1 leukaemia cells, and on the clonogenic activity of K562 cells are also described.     

Antigenic complexes of Pseudomonas aeruginosa slime: their isolation and biological properties

The possibility of using antigenic complexes contained in the extracellular slime of P. aeruginosa clinical strains belonging to different serological groups as the components of a chemical vaccine has been revealed. Animal experiments have demonstrated a high immunogenicity of these preparations, as well as their low toxicity. The use of slime antigens stimulates the production of specific antibodies exerting a protective action against infection with homologous P. aeruginosa strains.     

Vanadium(V) complexes in enzyme systems: aqueous chemistry, inhibition and molecular modeling in inhibitor design

Vanadate in aqueous solution is known to influence a number of enzyme-catalyzed reactions. Such effects are well known to carry over to living systems where numerous responses to the influence of vanadium have been well-documented; perhaps the most studied being the insulin-mimetic effect. Studies of the aqueous chemistry of vanadate provide an insight into the mechanisms by which vanadate affects enzyme systems and suggests methods for the elucidation of specific types of responses. Studies of the corresponding enzymes provide complementary information that suggests model vanadate systems be studied and provides clues as to functional groups that might be utilized in the development of selective enzyme inhibition. The insulin-mimetic effect is thought by many workers to originate in the effectiveness of vanadium as an inhibitor of protein tyrosine phosphatase (PTPase) activity. One, or more PTPases regulate the phosphotyrosine levels of the insulin receptor kinase domain. Appropriate ligands allow modification of the reactivity and function of vanadate. For instance, although the complex, ((CH(3))(2)NO)(2)V(O)OH, is not quite as good an inhibitor of PTPase activity as is vanadate, it is much more effective in cell cultures for increasing glucose transport and glycogen synthesis. Studies of the chemistry of this complex provide an explanation of the efficacy of this compound as a PTPase inhibitor that is supported by computer modeling studies. Computer calculations using X-ray data of known PTPases as a basis for homology modeling then suggests functionality that needs to be addressed in developing selective PTPase inhibitors.     

Synthesis and spectroscopic properties of some new seven-coordinate thioacetamide complexes of molybdenum(II) and tungsten(II)

The compounds [MI₂(CO)₃(NCMe)₂] (M = Mo or W) react with one equivalent of SC(NH₂)Me in CH₂Cl₂ at room temperature to initially give the acetonitrile substituted products [MI₂(CO)₃(NCMe)- {SC(NH₂)Me}] which was isolated for M = W. However, the molybdenum complex rapidly dimerizes with loss of acetonitrile to give the iodide-bridged compound [Mo(σ-I)I(CO)₃ {SC(NH₂)Me}]₂. The tungsten complex does not appear to dimerize, even after stirring at room temperature for 72 h in CH₂Cl₂. Two equivalents of thioacetamide react with [MI₂- (CO)₃(NCMe)₂] in CH₂Cl₂ at room temperature to give the new bisthioacetamide compounds [MI₂- (CO)₃{SC(NH₂)Me}₂] via displacement of the labile acetonitrile ligands. The low temperature (−70 °C) ¹³C NMR spectrum of [WI₂(CO)₃{SC(NH₂)Me}₂] indicates that the geometry of the complex is capped octahedral with a carbonyl ligand in the unique capping position.     

Spectroscopic and biological properties of palladium(II) complexes of ethyl 2-quinolylmethylphosphonate

Spectroscopic (1H NMR, UV-visible) and biological (cytostatic, antiviral activity) studies of palladium(II) complexes of monoethyl 2-quinolymethylphosphonate (2-Hmqmp): dihalide adducts trans-Pd(2-Hmqmp)2X2, chelate Pd(2-mqmp)2.2H2O and ion-pair salt complexes [2-H2mqmp]+[Pd(2-Hmqmp)X3]- (X = Cl, Br), have been carried out in order to determine structural and biological properties of these biologically interesting complex compounds. The complexes were evaluated in vitro for their cytostatic activity against murine L1210 and human KB and T-lymphoblast Molt4/C8 and CEM/0 cell lines, and the results obtained were compared with those obtained for the complexes of diethyl 2-quinolylmethylphosphonate (2-dqmp). The L1210 cell was the most responsive line and complexes of diester 2-dqmp were more active than complexes of monoester 2-Hmqmp. A good relationship was observed between the cytostatic activity of the complexes and their lypophilicity or solubility. Some complexes exhibited significant cell growth inhibitory effects, but none of the them was more cytostatic than cisplatin. Both 2-dqmp and 2-Hmqmp complexes were also evaluated in vitro for their antiviral activity in different assay systems, comprising a broad spectrum of DNA and RNA viruses, but no specific antiviral effects were noted. In addition, the complexes did not show any specific anti-HIV activity.