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PubMed1991

EELS data acquisition, processing and display for the Zeiss CEM 902 based on LOTUS 1-2-3: application examples from a biological system and inorganic transition metal compounds.

A personal computer combined with LOTUS 1-2-3 software, including the RS232 module of LOTUS MEASURE and a 12-bit ADC, has been used for data acquisition of electron energy-loss spectroscopy (EELS) spectra with the Zeiss CEM 902. The internal macro language of LOTUS 1-2-3 allows a menu-driven procedure. Macro-programs partly combined with external FORTRAN programs can be chosen from the menu for background subtraction, removal of multiple scattering effects by deconvolution, elemental quantification and several utilities. For special applications or conditions the macro programs can easily be modified. Spectra from crystals of two inorganic transition metal compounds, ruthenium trichloride and vanadium disulphide, and from a biological sample are presented as examples of the application of this software.

Animals↗
PubMed1986

The mode of reduction of vanadate(+V) to oxovanadium(+IV) by glutathione and cysteine.

Vanadate(+V) is completely reduced to oxovanadium(+IV) in vitro by thiols. A high transient absorbance at 750 nm is observed (intense blue) in solutions of a pH below 5 immediately after starting the reduction. EPR-measurements and determinations of the consumption of free thiol groups prove that the transient absorbance is caused by an intermediate compound not containing vanadium in its reduced state (+IV). The way of reduction of vanadate(+V) by thiols is discussed. We propose the formation of an intermediate vanadate(+V)-thioester which is formed before reduction in a preequilibrium step.

Chemical Phenomena↗
PubMed1998

Dinuclear Oxovanadium(IV) N-(Phosphonomethyl)iminodiacetate Complexes: Na(4)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)].10H(2)O and Na(8)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)](2).16H(2)O(1).

The dioxovanadium(IV) complexes with pida(4)(-) ligands (H(4)pida) = N-(phosphonomethyl)iminodiacetic acid), Na(4)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)].10H(2)O (1) and Na(8)[V(2)O(2){(O)(2)P(O)CH(2)N(CH(2)COO)(2)}(2)](2).16H(2)O (2), were isolated from reactions of H(4)pida with either oxovanadium(V) (i.e., NaVO(3)) or oxovanadium(IV) precursors within the pH range of 2-8. The structures of complexes 1 and 2 were investigated by X-ray diffraction methods and in contrast to expectation were both found to be dinuclear. Complex 1 crystallized in the monoclinic system: P2(1)/n, a = 10.5632(1) Å, b = 11.1868(1) Å, c = 12.6921(1) Å, beta = 106.45 degrees, V = 1438.44(2) Å(3), Z = 4, and R (wR2) = 0.0781 (0.2017). Complex 2 crystallized in the monoclinic system P2(1)/c: a = 13.9822(2) Å, b = 11.1888(2) Å, c = 18.6519(3) Å, beta = 100.88 degrees, V = 2865.51(8) Å(3), Z = 4, and R (wR2) = 0.046 (0.125). Both complexes 1 and 2 have similar dimeric frameworks where two vanadium centers are linked by two phosphonate groups of two pida(4)(-) ligands (quadridentate binucleating), bridging through their four oxygen atoms to form a V(2)O(4)P(2) eight-membered ring which possesses a crystallographic inversion center. In contrast to their solid-state features, in aqueous solution both dinuclear crystalline compounds immediately dissociate to monomeric species, as observed by EPR and UV/vis spectroscopy. Both solution-state EPR and NMR spectroscopy confirmed that redox chemistry is involved in the reaction between vanadate and H(4)pida. Studies in mixed solvent systems showed that the dinuclear complex would remain intact in the presence of sufficient organic solvent. In the absence of oxygen the mononuclear and the dinuclear complexes will reversibly interconvert, whereas, in the presence of oxygen, the complexes will oxidize. These studies document the existence of higher oligomeric vanadium compounds and surprisingly, in general, lend credibility to several emerging mechanistic proposals involving oligomeric species of vanadium compounds in catalytic processes.

Journal Article↗
PubMed1990

An assessment of the genotoxicity of vanadium.

The activities of vanadium oxide (V2O3), vanadyl sulfate (VOSO4) and ammonium metavanadate (NH4VO3) in inducing sister chromatid exchange (SCE) and chromosomal aberrations (CAb) were assayed in Chinese hamster ovary cells. The toxic concentrations (TC50) for these compounds were found to be 25, 23 and 16 micrograms elemental vanadium/ml, respectively. At does 1/50-1/4 TC50, vanadium compounds were able to induce significant increases (P less than 0.01) in the SCE frequency with or without the addition of rat hepatic S9 mix. These compounds also induced CAb in the cells at doses closely equivalent to the TC50.

Animals↗
PubMed2000

Redox reactions via vanadium-induced electron transfer.

One-electron reduction and oxidation induced by vanadium complexes are demonstrated to be useful in oxidative and reductive transformations of carbonyl compounds. The redox interaction between vanadium complexes and redox-active ligands is achieved with coenzyme PQQ and polyanilines that afford the corresponding redox systems.

Electron Transport↗
PubMed2000

Effect of peroxovanadate compound on phenylalanine hydroxylase gene expression.

Vanadium, a trace element in human cells and regarded as an essential nutrient, plays an active role in all tissues. It is known that peroxovanadate-nicotinic acid (POV), a complex compound of vanadium, can decrease hyperglycemia; however, its biochemical mechanism remains unclear. The object of the present study is to explore the hypoglycemia mechanism of POV at gene molecular levels. Rats rendered diabetic with streptozotocin were treated with POV. Total RNA was isolated from rat liver, and phenylalanine hydroxylase (PAH) mRNA abundance was determined by reverse transcriptase-polymerase chain reaction. PAH activity, blood glucose, and lipid levels were measured. Significantly increased hepatic PAH activity and corresponding mRNA with concomitant hyperglycemia and hyperlipemia were found in diabetic rats. These levels returned to normal after POV treatment and accompanied by negative glucosuria, normoglycemia, and normolipemia. The results from the current study indicates one of the mechanisms of POV action is to inhibit PAH gene expression and PAH activity, thus decreasing gluconeogenesis and hyperglycemia. At the same time, POV is able to promote diabetic recovery by lowering hyperlipemia.

Animals↗
PubMed1986

Organ toxicity of metallocene dichlorides. The effect of (C5H5)2TiCl2 and (C5H5)2VCl2 on renal structure.

The effect of a single application of toxicologically equivalent doses of the cytostatically active metal complexes titanocene dichloride (TDC), vanadocene dichloride (VDC) or cis-diamminedichloroplatinum(II) (DDP) upon the morphologic appearance and the functional behavior of the kidneys was analyzed in mice by use of light and electron microscopy, by determination of blood retention values and by urine analysis. Whereas DDP induced severe structural lesions of the epithelial cells of the proximal and distal tubules as well as profound functional disturbances of the kidneys, the dichlorides of titanium and vanadium caused only slight morphologic alterations such as increased vacuolation in the proximal tubular cells even after administration of LD50 doses; severe pathologic injuries within the kidneys were always lacking. In correspondence to these morphologic findings, no impairment of renal function was detectable after treatment with TDC either in effective or in toxic doses.

Animals↗
PubMed2004

Methods evaluating vanadium tolerance in bacteria isolated from crude oil contaminated land.

Investigations into bacterial responses to vanadium are rare, and in this study were initiated by isolating cultures from crude oil contaminated soil from Russia and Saudi Arabia. Addition of vanadyl sulphate and vanadium pentoxide created acid conditions in the media whilst sodium metavanadate and sodium orthovanadate produced neutral and alkaline effects, respectively. Buffers were introduced for wider comparison of the sample set treatments and to distinguish between the effects of pH and compound toxicity. This study has resulted in the creation of protocols for the pH stabilisation of media containing vanadium compounds and revealed that, although vanadium salts demonstrated some toxic effects, as revealed by MIC and bioluminescence decay tests, the effects were mainly due to pH rather than inherent toxicity of the metal. Capacity for sorption of vanadium to biomass was also investigated.

Bacteria↗
PubMed1990

Chelating agents in the treatment of acute vanadyl sulphate intoxication in mice.

Eighteen chelating or reducing agents were tested to determine their relative efficacy as antagonists in acute intramuscular vanadyl sulphate intoxication in mice. The chelating or reducing agents were administered intraperitoneally to male Swiss mice at doses equal to one-fourth of their respective LD50. Therapeutic effectiveness (TEF) was calculated. In a subsequent experiment, the effect of EDTA, glutathione, DFOA, ascorbic acid, succinic acid, monosodium phosphate, Tiron, DTPA, and 2-mercaptosuccinic acid on the excretion, and distribution of vanadium was determined. Of the compounds examined, Tiron followed by ascorbic acid, and 2-mercaptosuccinic acid were effective in increasing the urinary excretion of vanadium. Tiron, and 2-mercaptosuccinic acid were also effective in reducing the concentration of vanadium found in kidney, the main target organ of vanadium accumulation. Tiron appears to be the most effective agent of those tested in the prevention of acute vanadium (IV) intoxication in mice.

Animals↗
PubMed1999

Synthesis and Structure of Bis(pi-cyclopentadienyl)vanadium(IV) 1,10-Phenanthroline and 2,2'-Bipyridine Compounds and Their Interactions with Artificial Membranes.

The reaction of in situ generated Cp(2)V(OTf)(2) (Cp = cyclopentadienyl; OTf = O(3)SCF(3)) with excess 1,10-phenanthroline and 2,2'-bipyridine yields the d(1) vanadocene coordination compounds [Cp(2)V(phen)][OTf](2) (1) and [Cp(2)V(bpy)][OTf](2) (2), respectively. The compounds have been characterized by UV-vis and EPR spectroscopy and by cyclic voltammetry. The complexes have relatively low vanadium(IV)-vanadium(III) reduction potentials (-0.62 V vs Cp(2)Fe(+/0) in acetonitrile). Structures of 1 and 2 have been determined by X-ray crystallography. Compound 1 crystallized in a monoclinic system, space group P2(1)/n, with a = 10.2763(5) Å, b = 18.1646(9) Å, c = 13.5741(7) Å, beta = 99.4150(10) degrees, and Z = 4. Refinement of its structure by full-matrix least-squares techniques gave final residuals R = 0.040 and R(w) = 0.096. Compound 2 crystallized in a monoclinic system, space group P2(1)/c, with a = 10.6451(6) Å, b = 18.3863(10) Å, c = 12.6993(7) Å, beta = 98.6220(10) degrees, and Z = 4. Refinement of its structure by full-matrix least-squares techniques gave final residuals R = 0.046 and R(w) = 0.101. The two nitrogen atoms and centroids of the two cyclopentadienyl rings for both compounds occupy a distorted tetrahedral geometry around the vanadium(IV) center. The chelated ring plane is inclined closer to one of the neighboring Cp rings with the tilt more evident in 1 ( approximately 8 degrees ) than 2 ( approximately 4 degrees ). The membrane interactions of these compounds and the titanium analogues, [Cp(2)Ti(phen)][OTf](2) (3) and [Cp(2)Ti(bpy)][OTf](2) (4), have been studied with zwitterionic unilamellar liposomes as artificial membranes. We show that the ability of metallocenes to enhance the permeability of a liposomal membrane depends on the hydrophobicity, as well as the size and planarity of the ancillary chelated ligands, but not the nature of the central metal ion. Also provided is evidence that metallocene-induced permeability changes in artificial membranes are not caused by lipid peroxidation.

Journal Article↗
PubMed2001

Tetrakis(dimethylamido)vanadium(IV).

The title compound, [V(C(2)H(6)N)(4)], (I), has non-crystallographic D(2d) molecular symmetry and contains an approximately tetrahedrally coordinated V atom with dimethylamido ligands. Each N atom features a nearly trigonal planar geometry. There are two independent molecules of (I) in the asymmetric unit. The results are compared with those previously reported for gas-phase electron-diffraction studies [Haaland, Rypdal, Volden & Andersen (1992). J. Chem. Soc. Dalton Trans. pp. 891-895].

Journal Article↗
PubMed2006

Hydrogen-bonded sheets in racemic cis-(2,2'-bipyridyl-kappa2N,N')oxo(pentane-2,4-dionato-kappa2O,O')(thiocyanato-kappaN)vanadium(IV).

The title compound, [V(C5H7O2)(NCS)O(C10H8N2)], crystallizes with Z' = 2 in the space group Pbca. The molecules are linked into sheets by a combination of four C-H...O hydrogen bonds and one C-H...N hydrogen bond. The four C-H...O hydrogen bonds generate chains of rings, where each chain contains just a single enantiomer of each of the two independent molecules, while the C-H...N hydrogen bond generates a chain containing both enantiomers of just one of the independent molecules.

Journal Article↗
PubMed1982

Effect of vanadium in the +5, +4 and +3 oxidation states on cardiac force of contraction, adenylate cyclase and (Na+ + K+)-ATPase activity.

The influence of vanadium in the nominally +5 (NH4VO3; referred to as V5+), +4 (C10H14O5V and VOSO4; V4+) and +3 oxidation states (VCl3; V3+) on cardiac force of contraction, adenylate cyclase and (Na+ + K+)-ATPase activity was investigated in order to determine which form of vanadium mediates the cardiac effects. V5+, V4+ and V3+ (300 microM each) increased the force of contraction of isolated electrically driven cat papillary muscles by about 100%. In the presence of the reducing agent ascorbic acid (5 mM) none of the three compounds led to any distinct increase in force of contraction. On the particulate adenylate cyclase preparation from feline right ventricles only V5+ stimulated the enzyme activity by about 100%, whereas V4+ and V3+ were ineffective. In the presence of 5 mM ascorbic acid all three compounds were ineffective. In contrast, in the presence of the oxidizing agent diamide (azodicarboxylic acid-bis-dimethylamide; 1 mM) all three compounds became stimulatory. On the isolated (Na+ + K+)-ATPase V5+ (500 microM) alone reduced the basal activity by about 95%. In the presence of ascorbic acid the inhibitory effect of V5+ was greatly diminished. Similar results were obtained with V4+, V3+ (100 microM) alone inhibited (Na+ + K+)-ATPase activity only by about 40%. In the presence of ascorbic acid V3+ was ineffective. From the results it is concluded that positive inotropism, stimulation of adenylate cyclase and inhibition of (Na+ + K+)-ATPase by vanadium compounds likewise result from an action of vanadium in the +5 oxidation state.

Adenylyl Cyclases↗
PubMed1985

Biodistribution and pharmacokinetics of vanadium following intraperitoneal administration of vanadocene dichloride to mice.

The biodistribution and pharmacokinetics of vanadium following i.p. administration of vanadocene dichloride (VDC), a representative of a new class of organometallic anticancer agents, is reported for Strain A mice. A convenient flameless atomic absorption spectroscopic assay is described and is used to determine kinetic profiles for vanadium in blood, kidney, liver, small intestine and brain tissue for times up to 24 h after administration. For a VDC dose of 80 mg/kg, vanadium concentration decreases rapidly from both the blood and small intestine, and the data can be fit to a phenomenological exponential function (blood: t1/2 = 118 +/- 43 min; small intestine: t1/2(alpha) = 18.10 +/- 0.14 min, t1/2(beta) = 341 +/- 45 min). In contrast, vanadium accumulates in both the kidney and liver up to a maximal concentration (1.12 +/- 0.06 mM and 0.56 +/- 0.06 mM after 12 and 8 h, respectively), and is then excreted with estimated half-lives of 7.9 +/- 0.7 and 12.1 +/- 0.1 h, respectively. No detectable levels of vanadium are found in the brain tissue over the temporal course of the experiment. These results are compared to previous mammalian studies with cis-dichlorodiammineplatinum(II) (CDDP) and related 'second generation' platinum derivatives; there are both qualitative similarities between the vanadium and platinum systems as well as important quantitative differences.

Animals↗
PubMed1986

Trace element interactions affecting pulmonary macrophage cytotoxicity.

Effluents from the smokestacks of powerplants contain respirable particles that are enriched with a variety of biologically active trace elements. To determine the relative toxicity of trace elements in coal fly ash, the effects of selected compounds, alone and in combination, were evaluated in cultures of pulmonary alveolar macrophages. The inorganic compounds studied were ZnO, Na2SeO3, V2O5, NaAsO2, Mn3O4, and Ni3S2. Vanadium pentoxide was the most cytotoxic compound while selenium was the least toxic (approximately 100-fold less toxic than vanadium). After dose-response curves for each element were established, interactions between various compounds were studied by coexposure to trace elements at different concentrations. Selenium was completely antagonistic to the toxic effects of vanadium and slightly antagonistic to arsenic. In contrast to selenite, sulfite, a moiety with a similar redox potential, was not antagonistic to vanadium toxicity. Zinc was weakly antagonistic to the in vitro effects of nickel. No other chemical combinations displayed antagonistic, synergistic or additive effects on the function of the cultured macrophages.

Air Pollutants↗