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PubMed2000

Metallokinetic analysis of disposition of vanadyl complexes as insulin-mimetics in rats using BCM-ESR method.

Among vanadium's wide variety of biological functions, its insulin-mimetic effect is the most interesting and important. Recently, the vanadyl ion (+4 oxidation state of vanadium) and its complexes have been shown to normalize the blood glucose levels of streptozotocin-induced diabetic rats (STZ-rats). During our investigations to find more effective and less toxic vanadyl complexes, the vanadyl-methylpicolinate complex (VO-MPA) was found to exhibit higher insulin-mimetic activity and less toxicity than other complexes, as evaluated by both in vitro and in vivo experiments. Electron spin resonance (ESR) is capable of measuring the paramagnetic species in biological samples. We have developed the in vivo blood circulation monitoring-electron spin resonance (BCM-ESR) method to analyze the ESR signals due to stable organic radicals in real time. In the present investigation, we have applied this method to elucidate the relationship between the blood glucose normalizing effect of VO-MPA and the global disposition of paramagnetic vanadyl species. This paper describes the results of vanadyl species in the circulating blood of rats following intravenous administration of vanadyl compounds. ESR spectra due to the presence of vanadyl species were obtained in the circulating blood, and their pharmacokinetic parameters were estimated using compartment models. The results indicate that vanadyl species are distributed considerably to the peripheral tissues, as estimated by BCM-ESR, and eliminated from the body through the urine, as estimated by ESR at 77 K. The exposure of vanadyl species in the blood was found to be enhanced by VO-MPA treatment. Given these results, we concluded that the pharmacokinetic character of vanadyl species is closely related with the structure and antidiabetic activity of the vanadyl compounds.

Animals↗
PubMed1986

The influence of tunichrome and other reducing compounds on tunic and fin formation in embryonic Ascidia callosa Stimpson.

Tunic in 46-hr-old Ascidia callosa larvae reared from dechorionated neurulae is either markedly reduced in thickness or absent altogether. The epidermis is fragile and cuticular fins fail to develop. Dechorionated neurulae treated with tunichrome and other reducing compounds (e.g., glutathione, ascorbate) show an enhancement in tunic formation and rudimentary fin development. UV absorbance spectra of extracts from unfertilized eggs, late tail-bud embryos, and tadpole larvae indicate that tunichrome may be present in all developmental stages. Experiments with neurulae in which the chorion was punctured with tungsten needles but not removed signify that the test cells are the most likely source of tunichrome. Results are consistent with the hypothesis that tunichrome is involved in the natural processes of tunic morphogenesis in ascidian embryos.

Animals↗
PubMed1983

Ion-gated channel induced in planar bilayers by incorporation of (Na+,K+)-ATPase.

An ion-gated channel was conferred on a planar lipid bilayer membrane upon incorporation of (Na+,K+)-ATPase. The channel exhibited two conductance states. The high conductance state was only observed when an ion gradient was present across the planar membrane. This state corresponded to an enzyme conformation which was ouabain and vanadate sensitive (i.e. conductance was inhibited by these compounds), while the low conductance state showed no sensitivity to either inhibitor. Single channel conductance behavior was observed when minimal amounts of enzyme were incorporated into the planar bilayer. The observed single channel conductance was 270 +/- 14 picosiemens. Similar transport behavior was observed for enzyme purified from ovine kidney using sodium dodecyl sulfate (anionic), eel electroplax using Lubrol-WX (nonionic), and kidney microsomes. In addition, the data strongly suggest that enzyme from the kidney microsomes was asymmetrically incorporated into the planar bilayer.

Animals↗
PubMed1997

Vanadium Hydrotris(pyrazolyl)borate Complexes of Diphenyl Phosphate. Heterometallic Complexes of the [LV{(PhO)(2)PO(2)}(3)](-) Fragment.

The synthesis and characterization of nine trinuclear, mixed metal complexes of the type [LV{&mgr;-(PhO)(2)PO(2)}(3)](2)M, where the vanadium is in the 3+ oxidation state, L = hydrotris(pyrazolyl)borate, and M = Ba(II) (1), Ca(II) (2), Mg(II) (3), Mn(II) (4), Co(II) (5), Ni(II) (6), Fe(II) (7), 2 Na(I) (8), Al(III) (9), and La(III) (10), are described. X-ray crystal structural analysis of 1, 3, and 4 gave the following parameters: 1, C(92)H(84)B(2)N(12)O(24)P(6)Cl(4)BaV(2), C2/c, a = 26.730(5) Å, b = 15.521(3) Å, c = 27.648(6) Å, beta = 100.53(3) degrees, Z = 4; 3, C(94)H(80)B(2)N(14)O(24)P(6)MgV(2), P&onemacr;, a = 13.410(3) Å, b = 14.179(3) Å, c = 15.694(3) Å, alpha = 112.22(3) degrees, beta = 101.31(3) degrees, gamma = 106.15(3) degrees, Z = 1; 4, C(111)H(80)B(2)N(12)O(28)P(6)MnV(2), R&thremacr;c, a = 18.670(3) Å, b = 18.671(3) Å, c = 61.114(12) Å, Z = 6. Magnetic measurements indicate that compounds containing an integral spin central ion display moderate antiferromagnetic coupling while those with half-integral spins give more complex behavior.

Journal Article↗
PubMed1994

The effect of hemoglobin, hematin, and iron on neutrophil inactivation in superoxide generating systems.

When Escherichia coli was incubated with xanthine oxidase and acetaldehyde, the killing of E. coli was accelerated by iron-EDTA but inhibited by hematin or hemoglobin. On the other hand, when E. coli was incubated with human neutrophils in the presence of phorbol myristate acetate (PMA), all of these iron species at concentrations of a few micromolar accelerated the inactivation of neutrophils and in so doing protected the E. coli from being killed by the neutrophils. The inactivation of the neutrophils was accompanied by an increase in lipid peroxidation and by a decrease in viability measured with trypan blue. This inactivation was inhibited by scavengers such as deoxyribose, mannitol, or thiourea. Desferrioxamine B and 5,5-dimethyl-1-pyrroline-1-oxide (DMPO) both inhibited the inactivation mediated by iron-EDTA, but had no effect on the hematin- or hemoglobin-mediated inactivation. Vanadium (vanadyl ion), an effective Fenton reagent, behaved in the same way as iron-EDTA relative to the effects of DMPO on neutrophil inactivation. These results led us to conclude that neutrophils were inactivated during PMA stimulation by OH radicals in the presence of iron-EDTA and by some other oxidizing species when hematin or Hb is present. Ascorbate enhanced the inactivation of neutrophils mediated by these iron species. Catalase was very effective in inhibiting neutrophil inactivation. Superoxide dismutase was not as effective but the combination with catalase was most effective.

Adult↗
PubMed2004

Copper(III) and vanadium(IV)-oxo corrolazines.

As part of our efforts to develop the transition metal chemistry of corrolazines, which are ring-contracted porphyrinoid species most closely related to corroles, the vanadium and copper complexes (TBP)(8)Cz(H)V(IV)O (1) and (TBP)(8)CzCu(III) (2) of the ligand octakis(para-tert-butylphenyl)corrolazine [(TBP)(8)Cz] have been synthesized. The coordination behavior, preferred oxidation states, and general redox properties of metallocorrolazines are of particular interest. The corrolazine ligand in 1 was shown to contain a labile proton by acid/base titration and IR spectroscopy, serving as a -2 ligand rather than as the usual -3 donor. The oxidation state of the vanadium center in 1 was shown to be +4, in agreement with the overall neutral charge for this complex. The EPR spectrum of 1 reveals a rich signal consistent with a V(IV)(O) (d(1), S = 1/2) porphyrinoid species (g(xx) = 1.989, g(yy) = 1.972, g(zz) = 1.962). The electrochemical analysis of 1 shows behavior closer to that of a porphyrazine than a corrolazine, with a positively shifted, irreversible reduction at -0.65 V (vs Ag/AgCl). Resonance Raman and IR data for 1 confirm the presence of a triply bonded terminal oxo ligand with nu(V(16)O) = 975 cm(-1) and nu(V(18)O) = 939 cm(-1). The copper complex 2 exhibits a diamagnetic (1)H NMR spectrum, indicative of a bona fide square planar copper(III) (d(8), low-spin) complex. Previously reported copper corroles have been characterized as copper(III) complexes which exhibit a paramagnetic NMR spectrum at higher temperatures, indicative of a thermally accessible triplet excited state ([(corrole(*+))Cu(II)]). The NMR spectrum for 2 shows no paramagnetic behavior in the range 300-400 K, indicating that compound 2 does not have a thermally accessible triplet excited state. These data show that the corrolazine system is better able to stabilize the high oxidation state copper center than the corresponding corroles. Electrochemical studies of 2 reveal two reversible processes at +0.93 and -0.05 V, and bulk reduction of 2 with NaBH(4) generates the copper(II) species [(TBP)(8)CzCu(II)](-) (2a), which exhibits an EPR signal typical of a copper(II) porphyrinoid species.

Journal Article↗
PubMed2004

Investigation of the microcharacteristics of PM2.5 in residual oil fly ash by analytical transmission electron microscopy.

Atmospheric emissions from combustion of residual oils often consist of carbonaceous material and metal compounds, both of which are of concern for health and environmental issues. In this study, particulate matter fractions with aerodynamic diameters nominally less than 2.5 microm (PM2.5) in two residual oil fly ash (ROFA) samples generated from combustion experiments were investigated by analytical transmission electron microscopy (TEM) techniques, including energy-dispersive X-ray spectroscopy, selected area electron diffraction (SAED), high-resolution TEM, and electron energy loss spectroscopy (EELS). Carbonaceous particles, which dominate both samples, exist in two distinctive forms: as soot aggregates with spherical primary particles of size 10-80 nm that exhibit a concentric arrangement of graphitic layers around the particle center and as larger spherical or irregular-shaped porous residual char particles of size 1-20 microm that usually have anisotropic microtextures and contain organic sulfur species. Such carbon-rich particles were often observed to be coated with inorganic species, notably transition metals (V, Ni, Fe, Zn) in the form of sulfates, oxides, vanadates, and phosphates. In this respect, they therefore differ from similar carbonaceous particles generated in combustion of diesel fuels that lack significant inorganic species. Crystalline phases of vanadium, nickel, and iron oxides and multi-element oxides were identified by the SAED technique. The valence state of V in some V-rich oxide particles probed by EELS was found to vary from +2 to +5. Individual transition metal sulfate, oxide, and phosphate particles are typically compositionally complex, containing multiple metallic elements. These microcharacteristics of individual PM2.5 particles revealed by electron microscopy techniques should be important parameters to include in future toxicological investigations of ROFA PM.

Air Pollutants↗
PubMed2003

Effect of chromium on apolipoprotein A-I expression in HepG2 cells.

OBJECTIVE: Chromium is a key micronutrient required for lipid and carbohydrate metabolism. Some but not all clinical trials have associated use of chromium supplements with improved insulin sensitivity and lipid profile including increased high-density lipoprotein cholesterol levels. METHODS: Because apolipoprotein A-I (apoA-I) is the principal protein of high-density lipoprotein, the molecular pathways underlying chromium-related changes in apoA-I expression were studied in a human hepatoma cell line (HepG2) transfected with full-length apoA-I promoter attached to the reporter chloramphenicol acetyl transferase gene. RESULTS: Exposure of these cells to different concentrations of chromium chloride (0, 0.5, 1.0, and 3.0 mM) resulted in a dose-dependent decrease in apoA-I promoter activity (chloramphenicol acetyl transferase activity expressed as a percentage of an internal control was 99.4 +/- 7.2% in control cells versus 87.6 +/- 5.0%, 73.4 +/- 2.3%, and 36.6 +/- 3.9%, respectively, P < 0.01). Chromium chloride at 10 mM concentration was toxic and caused death in a large number of cells. Treating HepG2 cells with other minerals known to have insulin-sensitizing effects such as magnesium (1 mM), zinc (0.2 mM), and vanadyl sulfate (0.1 mM) significantly reduced apoA-I promoter activity in the presence and absence of 100 microU/mL of insulin. Northern blot analyses showed that the apoA-I mRNA content of cells treated with 0.2 mM of chromium chloride relative to G3PDH mRNA was not significantly increased compared with controls (0.652 +/- 0.122 versus 0.745 +/- 0.143, the ratio of apoA-I to glyceraldehyde 3-phosphate dehydrogenase (G3PDH) mRNA in control and chromium-treated cells, respectively). Western blot analyses of proteins secreted in culture media indicated that neither chromium treatment of the HepG2 cells (858.0 +/- 151.4 arbitrary units) nor treatment with magnesium (1323.3 +/- 175.7) or vanadium (1102 +/- 78.7) significantly altered apoA-I concentrations compared with controls (1061.7 +/- 114.7). However treatment of HepG2 cells with 0.2 mM of zinc significantly reduced apoA-I concentrations (291.0 +/- 29.2 versus 1061.7 +/- 114.7; P < 0.001). CONCLUSIONS: Supraphysiologic concentrations of chromium and other minerals with known insulin-sensitizing activity may reduce apoA-I promoter activity in cultured cells. Whether similar changes may occur in vivo remains to be shown. However, these observations do not support the use of pharmacologic amounts of chromium supplementation to enhance the cardioprotective lipid profile.

Antioxidants↗
PubMed1985

Inhibition by vanadyl of adenylate cyclase activation reactions in rat adrenal membranes.

In rat adrenal dispersed cells, both vanadyl and vanadate inhibited ACTH-stimulated steroidogenesis and the formation of cAMP, whereas these compounds did not inhibit the cAMP-dependent steroidogenesis. Then, the membrane fraction was prepared and activated by various secretagogues including ACTH, Gpp(NH)p, GTP gamma S, and forskolin. The cyclase activity was inhibited by vanadyl but not by vanadate in the presence of these stimulators. Based on these results, we conclude that cationic vanadyl acts against a metal-requiring step in the adenylate cyclase system containing G-protein and the catalytic subunit. In addition, we believe that vanadyl is a useful tool to investigate adenylate cyclase systems.

Adenylyl Cyclase Inhibitors↗
PubMed2000

Acute pulmonary effects of ultrafine particles in rats and mice.

Ambient fine particles consist of ultrafine particles (< 100 nm) and accumulation-mode particles (approximately 100 to 1,000 nm). Our hypothesis that ultrafine particles can have adverse effects in humans is based on results of our earlier studies with particles of both sizes and on the finding that urban ultrafine particles can reach mass concentrations of 40 to 50 micrograms/m3, equivalent to number concentrations of 3 to 4 x 10(5) particles/cm3. The objectives of the exploratory studies reported here were to (1) evaluate pulmonary effects induced in rats and mice by ultrafine particles of known high toxicity (although not occurring in the ambient atmosphere) in order to obtain information on principles of ultrafine particle toxicology; (2) characterize the generation and coagulation behavior of ultrafine particles that are relevant for urban air; (3) study the influence of animals' age and disease status; and (4) evaluate copollutants as modifying factors. We used ultrafine Teflon (polytetrafluoroethylene [PTFE]*) fumes (count median diameter [CMD] approximately 18 nm) generated by heating Teflon in a tube furnace to 486 degrees C to evaluate principles of ultrafine particle toxicity that might be helpful in understanding potential effects of ambient ultrafine particles. Teflon fumes at ultrafine particle concentrations of approximately 50 micrograms/m3 are extremely toxic to rats when inhaled for only 15 minutes. We found that neither the ultrafine Teflon particles alone when generated in argon nor the Teflon fume gas-phase constituents when generated in air were toxic after 25 minutes of exposure. Only the combination of both phases when generated in air caused high toxicity, suggesting the existence of either radicals on the particle surface or a carrier mechanism of the ultrafine particles for adsorbed gas-phase compounds. We also found rapid translocation of the ultrafine Teflon particles across the epithelium after their deposition, which appears to be an important difference from the behavior of larger particles. Furthermore, the pulmonary toxicity of the ultrafine Teflon fumes could be prevented by adapting the animals with short 5-minute exposures on 3 days prior to a 15-minute exposure. This shows the importance of preexposure history in susceptibility to acute effects of ultrafine particles. Aging of the fresh Teflon fumes for 3.5 minutes led to a predicted coagulation resulting in particles greater than 100 nm that no longer caused toxicity in exposed animals. This result is consistent with greater toxicity of ultrafine particles compared with accumulation-mode particles. When establishing dose-response relationships for intratracheally instilled titanium dioxide (TiO2) particles of the size of the urban ultrafine particles (20 nm) and of the urban accumulation-mode particles (250 nm), we observed significantly greater pulmonary inflammatory response to ultrafine TiO2 in rats and mice. The greater toxicity of the ultrafine TiO2 particles correlated well with their greater surface area per mass. Ultrafine particles of carbon, platinum, iron, iron oxide, vanadium, and vanadium oxide were generated by electric spark discharge and characterized to obtain particles of environmental relevance for study. The CMD of the ultrafine carbon particles was approximately 26 nm, and that of the metal particles was 15 to 20 nm, with geometric standard deviations (GSDs) of 1.4 to 1.7. For ultrafine carbon particles, approximately 100 micrograms/m3 is equivalent to 12 x 10(6) particles/cm3. Homogeneous coagulation of these ultrafine particles in an animal exposure chamber occurred rapidly at 1 x 10(7) particles/cm3, so that particles quickly grew to sizes greater than 100 nm. Thus, controlled aging of ultrafine carbon particles allowed the generation of accumulation-mode carbon particles (due to coagulation growth) for use in comparative toxicity studies. We also developed a technique to generate ultrafine particles consisting of the stable isotope 13C by using 13C-graphite electrodes made in our laboratory from amorphous 13C powder. These particles are particularly useful tools for determining deposition efficiencies of ultrafine carbon particles in the respiratory tracts of laboratory animals and the translocation of particles to extrapulmonary sites. For compromised animals, we used acute and chronic pulmonary emphysema; a low-dose endotoxin inhalation aimed at priming target cells in the lung was also developed. Other modifying factors were age and copollutant (ozone) exposure. Exposure concentrations of the generated ultrafine particles for acute rodent inhalation studies were selected on the basis of lung doses predicted to occur in people inhaling approximately 50 micrograms/m3 urban ultrafine particles. Concentrations that achieved the same predicted lung burden per unit alveolar surface were used in rodents. (ABSTRACT TRUNCATED)

Administration, Inhalation↗
PubMed1984

Characterization of a Ca2+-stimulated Mg2+-dependent adenosine triphosphatase in Friend murine erythroleukemia cell plasma membranes.

Since agents which affect Ca2+ fluxes have been shown to affect the commitment to terminal differentiation of murine erythroleukemia cells treated with an inducer of differentiation (Bridges, K., Levenson, R., Housman, D., and Cantley, L. (1981) J. Cell Biol. 90, 542-544), we investigated the presence of Ca2+-transport systems in plasma membranes isolated from these cells. Plasma membranes from murine erythroleukemia cells exhibited a high affinity (Ca2+-Mg2+)-ATPase activity with a Vmax of 29 +/- 4 nmol/mg/min and an apparent K0.5 for free Ca2+ of 0.13 microM. This activity was strongly inhibited in a dose-dependent fashion by low concentrations of trifluoperazine, compound 48/80, lanthanum, and vanadate with I50 of 29 microM, 1.75 micrograms/ml, 1.5 microM, and 0.4 microM, respectively. The inhibitory effect of compound 48/80 was specifically reversed by exogenously added calmodulin. Phosphorylation of plasma membranes with [gamma-32P] ATP followed by sodium dodecyl sulfate electrophoretic analysis at low pH revealed a Ca2+-dependent phosphoprotein with an apparent molecular mass of 138,000 daltons which co-migrated with the Ca2+-dependent phosphoprotein from human erythrocytes and was separable from sarcoplasmic reticulum (Ca2+-Mg2+)-ATPase. The 32P incorporated into the phosphoprotein could be chased with unlabeled ATP and the protein-phosphate bond was unstable at alkaline pH suggesting an acylphosphate ATPase intermediate like that previously characterized in other (Ca2+-Mg2+)-ATPases.

Animals↗
PubMed2001

Effects of flue gas composition on the catalytic destruction of chlorinated aromatic compounds with a V-oxide catalyst.

When using catalytic flue gas cleaning, several flue gas compounds may influence oxidation reactions of hazardous volatile organic compounds, possibly leading to lower reaction rates and, thus, to an incomplete destruction. Experimental investigations were performed with regard to the influence of selected flue gas compounds, like hydrogen chloride, sulfur dioxide, oxygen, and water vapour, on the catalytic destruction behavior of chlorobenzenes under flue gas cleaning conditions of an incineration plant. For this purpose, a metal oxide catalyst was operated at different temperatures at a space velocity of 3600 h-1 in a laboratory-scale fixed bed reactor with model flue gases, and with real flue gases generated from the TAMARA waste incineration plant. The results obtained from the studies with model flue gas were analyzed with respect to reaction kinetics. These kinetics were applied for comparison with the experimental data gained in the real flue gas.

Catalysis↗
PubMed1995

[In vitro measurement of digitalis-like compounds by inhibition of Na+ K+-ATPase: determination of the inhibitory effect].

The linked optical test for the analysis of digital-like substances with the enzyme Na+/K(+)-ATPase was investigated with regard to inhibition by components of the reaction medium. Most of the tested inorganic salts influenced the activity of the enzyme. However, the concentrations of the salts in human tissues and fluids are too small to cause measurable effects. Higher concentration of salts, which may be obtained by the preparative treatment of clinical material can influence the test. The determination of a reference value is recommended in these cases. The organic solvents DMSO and Methanol influenced the activity of the Na+/K(+)-ATPase, too. While the influence of DMSO in concentrations below 50% (v/v) was negligible, the measurement of a reference sample at higher DMSO concentrations and for methanolic samples is necessary.

Ammonium Sulfate↗
PubMed2002

Factors affecting metal-metal bonding in the face-shared d(3)d(3) bioctahedral dimer systems, MM'Cl(9)(5-) (M, M' = V, Nb, Ta).

Density functional theory (DFT) calculations have been used to investigate the d(3)d(3) bioctahedral complexes, MM'Cl(9)(5-), of the vanadium triad. Broken-symmetry calculations upon these species indicate that the V-containing complexes have optimized metal-metal separations of 3.4-3.5 A, corresponding to essentially localized magnetic electrons. The metal-metal separations in these weakly coupled dimers are elongated as a consequence of Coulombic repulsion, which profoundly influences (and destabilizes) the gas-phase structures for such dimers; nevertheless, the intermetallic interactions in the V-containing dimers involve significantly greater metal-metal bonding character than in the analogous Cr-containing dimers. These observations all show good agreement with existing experimental (solid state) results for the chloride-bridged, face-shared dimers V(2)Cl(9)(5-) and V(2)Cl(3)(thf)(6)(+). In contrast to the V-containing dimers, complexes featuring only Nb and Ta have much shorter intermetallic distances (approximately 2.4 A) consistent with d-electron delocalization and formal metal-metal triple bond formation; again, good agreement is found with available experimental data. Calculations on the complexes V(2)(mu-Cl)(3)(dme)(6)(+), Nb(2)(mu-dms)(3)Cl(6)(2-), and Ta(2)(mu-dms)(3)Cl(6)(2-), which are closely related to compounds for which crystallographic structural data exist, have been pursued and provide an insight into the intermetallic interactions in the experimentally characterized complexes. Analysis of the contributions from d-orbital overlap (E(ovlp)) stabilization, as well as spin polarization (exchange) stabilization of localized d electrons (E(spe)), has also been attempted for the MM'Cl(9)(5-) dimers. While E(ovlp) clearly dominates over E(spe) as a stabilizing factor in those dimers containing only Nb and Ta metal atoms, detailed assessment of the competition between E(ovlp) and E(spe) for V-containing dimers is obstructed by the instability of triply bonded V-containing dimers against Coulombic explosion. On the basis of the periodic trends in E(ovlp) versus E(spe), the V-triad dimers have a greater propensity for metal-metal bonding than do their Cr-triad or Mn-triad counterparts.

Journal Article↗
PubMed1997

Synthesis, Magnetism, and X-ray Molecular Structure of the Mixed-Valence Vanadium(IV/V)-Oxygen Cluster [VO(4) subset(V(18)O(45))](9-).

Within the transition metal oxide systems, vanadium presents a unique chemistry due to its capacity to form a great number of mixed-valence oxo clusters which often have the peculiarity to incorporate species that function, for size, shape, and charge, as templates. Prismatic, lustrous dark brown crystals of [(n-C(4)H(9))NH(3)](9)[V(19)O(49)].7H(2)O are obtained by reacting (n-C(4)H(9)NH(3))VO(3), VOSO(4), and (n-C(4)H(9))NH(2) in H(2)O. The X-ray crystal structure shows an ellipsoidal metal-oxo cluster formed by 15 VO(5) and 3 VO(4) polyhedra surrounding an almost regular VO(4) tetrahedron located on the 3-fold axis of a trigonal cell of dimensions a = 19.113(5) Å and c = 13.743(5) Å with space group P&thremacr; and Z = 2. Exponentially weighted bond valence sum calculations, manganometric titration of the V(IV) centers, and magnetic measurements are consistent with the presence of three localized and three delocalized electrons. Variable-temperature solid-state susceptibility studies indicate antiferromagnetic coupling between V(IV) centers. Cyclic voltammetry in acetonitrile shows a irreversible reduction at -1.24 V and a reversible oxidation at +0.17 V (vs Ag/AgCl). The title compound converts quantitatively to the metal oxide K(2)V(3)O(8) with an extended layered structure as soon as a potassium salt is added to a neutral aqueous solution of the polyoxoanion.

Journal Article↗
PubMed1986

The acylphosphate present in chromaffin granule membrane preparations is not associated with the proton-pump.

Chromaffin granule membranes were incubated in the presence of low ATP concentrations, at low temperature. A phosphorylated compound was rapidly formed which was stable in 10% trichloroacetic acid at 0 degree C. The lability of this compound in the presence of hydroxylamine or hot trichloroacetic acid indicated an acylphosphate, i.e., an ATPase phosphointermediate. Vanadate but not N-ethylmaleimide inhibited the formation of this derivative. Since the ATP-dependent generation of a transmembrane potential in chromaffin granule vesicles by the H+-pump was inhibited by N-ethylmaleimide but not by vanadate, the acylphosphate should not be associated with the H+-pump, i.e. ATPase I. We suggest that it is associated with ATPase II, an ATPase of unknown function present in chromaffin granule membrane preparations. This hypothesis is supported by the fact that ATPase II is vanadate sensitive and has a molecular mass of 140 kDa, properties similar to those of the phosphorylated intermediate.

Adenosine Triphosphate↗
PubMed2004

Urinary 8-hydroxy-2'-deoxyguanosine as a biomarker of oxidative DNA damage in workers exposed to fine particulates.

Residual oil fly ash (ROFA) is a chemically complex mixture of compounds, including metals that are potentially carcinogenic because of their ability to cause oxidative injury. In this study, we investigated the association between exposure to particulate matter with an aerodynamic mass median diameter <or= 2.5 micro m (PM2.5) and oxidative DNA damage and repair, as indicated by urinary 8-hydroxy-2'-deoxyguanosine (8-OHdG) concentrations, in a group of boilermakers exposed to ROFA and metal fumes. Twenty workers (50% smokers) were monitored for 5 days during an overhaul of oil-fired boilers. The median occupational PM2.5 8-hr time-weighted average was 0.44 mg/m3 (25th-75th percentile, 0.29-0.76). The mean +/- SE creatinine-adjusted 8-OHdG levels were 13.26 +/- 1.04 micro g/g in urine samples collected pre-workshift and 15.22 +/- 0.99 micro g/g in the post-workshift samples. The urinary 8-OHdG levels were significantly greater in the post-workshift samples than in the pre-workshift samples (p = 0.02), after adjusting for urinary cotinine levels, chronic bronchitis status, and age. Linear mixed models indicated a significant exposure-response association between PM2.5 exposure and urinary 8-OHdG levels (p = 0.03). Each 1-mg/m3 incremental increase in PM2.5 exposure was associated with an increase of 1.67 micro g/g (95% confidence interval, 0.21-3.14) in 8-OHdG levels. PM2.5 vanadium, manganese, nickel, and lead exposures also were positively associated with 8-OHdG levels (p <or= 0.05). This study suggests that a relatively young and healthy cohort of boilermakers may experience an increased risk of developing oxidative DNA injury after exposure to high levels of metal-containing particulate matter.

8-Hydroxy-2'-Deoxyguanosine↗
PubMed2006

Evolution of the structural chemistry of vanadium organodiphosphonate networks and frameworks: structural consequences of fluoride incorporation in the development of stable phases with void channels.

Hydrothermal reactions of solutions containing a vanadate source, an organodiphosphonate, an organonitrogen component, and HF (V/P/O/F) yield a series of oxyfluorovanadium-diphosphonates with charge-compensation provided by organoammonium cations or hydronium cations. While V/P/O/F networks provide the recurrent structural motif, the linkage between the layers and the details of the polyhedral connectivities within the layers are quite distinct for the five structures of this study. [H2pip][V4F4O2(H2O)2{O3P(CH2)3PO3}2] (1) (pip = piperazine) is a conventional three-dimensional (3D) "pillared" layer structure, whose V/P/O/F networks are buttressed by the propylene chains of the diphosphonate ligands. In contrast, [H2en][V2O2F2(H2O)2{O3P(CH2)4PO3}] (2) and [H2en]2[V6F12(H2O)2{O3P(CH2)5PO3}2 {HO3P(CH2)5PO3H}] (3) are two-dimensional (2D) slablike structures constructed of pairs of V/P/O/F networks sandwiching the pillaring organic tethers of the diphosphonate ligands. Despite the common overall topology, the layer substructures are quite different: isolated {VO5F} octahedra in 2 and chains of corner-sharing {VO(3)F(3)} octahedra in 3. The 3D structure of [H2en]2[V7O6F4(H2O)2{O3P(CH2)2PO3}4].7H2O (4.7H2O) exhibits a layer substructure that contains the ethylene bridges of the diphosphonate ligands and are linked through corner-sharing octahedral {VO6} sites. The connectivity requirements provide large channels that enclose readily removed water of crystallization. The structure of [H3O][V3F2(H2O)2{O3P(CH2)2PO3}2].3.5H2O (5.3.5H2O) is also 3D. Because of the similiarity with 4.7H2O, it exhibits V/P/O/F layers that include the organic tethers of the diphosphonates and are linked through corner-sharing {VO6} octahedra. In contrast to the network substructure of 4.7H2O, which contains binuclear and trinuclear vanadium clusters, the layers of 5.3.5 H2O are constructed from chains of corner-sharing {VO4F2} octahedra. Thermal studies of the open framework materials 4 and 5 reveal that incorporation of fluoride into the inorganic substructures provides robust scaffoldings that retain their crystallinity to 450 degrees C and above. In the case of 4, dehydration does not change the powder X-ray diffraction pattern of the material, which remains substantially unchanged to 450 degrees C. In the case of 5, there are two dehydration steps, that is, the higher temperature process associated with loss of coordinated water. This second dehydration results in structural changes as monitored by powder X-ray diffraction, but this new phase is retained to ca. 450 degrees C. The materials of this study exhibit a range of reduced oxidation states: 1 is mixed valence V(IV)/V(III) while 2 and 4.7H(2)O are exclusively V(IV) and 3 and 5.3.5H2O are exclusively V(III). These oxidation states are reflected in the magnetic properties of the materials. The paramagnetism of 1 arises from the presence of V(III) and V(IV) sites and conforms to the Curie-Weiss law with C = 2.38 em K/(Oe mol) and = -66 K with mu(eff) (300 K) = 4.33 mu(B). Compounds 3-5 exhibit Curie-Weiss law dependence of magnetism on temperature with mu(eff) (300 K) = 5.45 mu(B) for 3 (six V(III) sites), mu(eff) = 4.60 mu(B) for 4 (seven V(IV) sites) and mu(eff) = 4.13 mu(B) for 5 (two V(III) sites). Compound 2 exhibits antiferromagnetic interactions, and the magnetism may be described in terms of the Heisenberg linear antiferromagnetic chain model for V(IV). The effective magnetic moment at 300 K is 2.77 mu(B) (two V(IV) sites).

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