Vanadyl Sulfate Research Articles

Physicochemical properties of vanadium impregnated Al-PILCs: Effect of vanadium source

Summary Clay from the Middle Anatolian previously pillared by Al13-Keggin ions and then calcined at 300 °C (Al-PILC) was impregnated with aqueous solutions of vanadium precursors by impregnation from solution (I), wet impregnation (WI) and washing after wet impregnation (WWI) methods. The crystal and textural properties were evaluated by X-ray powder diffraction (XRD), nitrogen sorption and transmission electron microscopy (TEM) images. Vanadium incorporation into the Al-PILC resulted decreases in the basal spacing from 1.75 nm to 1.35 nm with the preserved typical layered structure. The use of sodium metavanadate (NaVO3) as the source and the impregnation from solution as the incorporation method resulted in less structural deformation in the final solid. Loading of the vanadyl sulfate hydrate (VOSO4·H2O) resulted in a higher V/Si ratio in the solid since both settling and ion exchange mechanism occured. The vanadium was usually bonded in the +5 oxide form, and the particles were settled between these layers and onto the outer surface of the clay particles. The existence of V–O structural bonds and Bronsted and Lewis acid sites were observed in the Fourier transform infrared spectroscopy (FTIR) results. Up to 300 °C dehydration with high mass loss was observed, followed by the decreases in mass loss, and finally, at around 900 °C, hydroxylation reactions were observed in the TGA/DTA analyses.

Studies on the roles of vanadyl sulfate and sodium nitrite in catalytic oxidation of benzyl alcohol with molecular oxygen

An efficient catalytic system consisting of vanadyl sulfate/sodium nitrite was disclosed previously for the oxidation of benzylic alcohols into aldehydes with molecular oxygen. However, the roles of catalyst components were not investigated. In this paper, we examined catalytic oxidation of benzyl alcohol as a model reaction, especially by infrared spectroscopy. The role of each component is discussed including nitrite, vanadyl, sulphate, and water. Sodium nitrite could be converted into nitrate and nitric acid. The vanadium(IV) could be smoothly oxidized into vanadium(V) under mild and acidic conditions without any organic ligands. The transformation of sulfate and bisulfate, the cessation of an induction period, and the oxidation of benzyl alcohol were closely interrelated. The multiple roles of water are discussed, including reduction of the induction period, participation in redox cycles of nitric compounds, deactivation of vanadium, and as a byproduct of oxidation. This study contributes to further development of aerobic oxidation using vanadium based catalysts.

Trophic actions of oral vanadium and improved glycemia on the pancreatic beta-cell ultrastructure of streptozotocin-induced diabetic rats.

Oral vanadyl sulfate (vanadium) has potent hypoglycemic effects in diabetes animals, but data about its actions on pancreatic beta-cells (BC) ultrastructure is limited. Partial diabetic rats were treated with vanadium and insulin injection and their effects on BC ultrastructure are studied. Male rats were made diabetic with intravenous streptozotocin injection (STZ, 40 mg/kg). Animals were randomly divided to control (CD), vanadium-treated (1 mg/mL VOSO4 + 5H2O in base solution, VTD) and insulin-treated (80 U/kg/day NPH insulin injection, ITD) diabetic groups. Treatments started 10 days after STZ injection and terminated after 2 months. Intermittent tail blood samples were taken for measurements of blood glucose (BG) and plasma insulin (PI). Finally animals were sacrificed and pancreata prepared for assessments of BC ultrastructure, islets histology and insulin immunoreactivity (IIR). Vanadium decreased BG (P<0.0001), elevated the reduced PI (P<0.001), prevented islet atrophy and restored BC ultrastructure. Low BG seen during treatment in VTD and ITD only persisted in VTD after vanadium withdrawal. Hyperglycemia worsened in CD and repaired in ITD shortly after insulin withdrawal. CD islets were atrophied, had scattered IIR spots. BC had pyknotic nuclei, vacuolated cytoplasm and few tiny insulin secretory granules. VTD islets looked normal with compact centered IIR spots. BC had well-developed endoplasmic reticulum, many insulin secretory granules and mitochondria. ITD islet structure was slightly better than CD and BC had some immature insulin secretory granules. The trophic actions of vanadium in diabetic rats effectively renovated beta cell ultrastructure and prevented pancreatic islets atrophy, whereas the relief of glucotoxicity seen with insulin treatment could repair some beta cells and partially prevented islet atrophy.

A variable temperature study of the transport properties of aqueous solutions of VOSO4 and NH4VO3 in 2 M H2SO4

Variable temperature ionic conductivity, viscosity and 1H NMR spin-lattice relaxation times, linewidths and chemical shifts measurements were determined for various concentrations of aqueous ammonium metavanadate (NH4VO3) and vanadyl sulfate (VOSO4) over the temperature range of 20–100 °C. Concentration ranges of 0.05–2 M and 0.05–0.2 M were investigated for VOSO4 and NH4VO3 respectively in 2 M H2SO4. Results show ion and proton transport processes that are mediated strongly by increasing solution viscosity, especially in the case of VOSO4. Activation energies calculated from ionic conductivity and solution viscosity show greater energy being needed for translational ion dynamics with increasing concentration for both solutions. Additionally, data suggest that with greater metal ion concentration ion association is more prevalent for the vanadyl ion. The differences between the transport capabilities of the two solution are discussed in terms of the 1H NMR, ionic conductivity and viscosity data.

Speciation of Molybdates under Hydrothermal Conditions

AbstractIn situ Raman spectroscopy was applied to investigate the speciation of molybdates under hydrothermal conditions in 0.2 M aqueous solution in the temperature range between 20 °C and 200 °C and at pH values between 7 and 1. The nature and abundance of molecular and supra‐molecular species differs significantly compared to the distribution of species under ambient conditions at the same pH. Whereas heptamolybdate Mo7O246– dominates under ambient pressure at 25 °C in the pH range between 6 and 5, at 170–190 °C, chain‐like or molecular structures of dimolybdates Mo2O72– and trimolybdates Mo3O102– are preferentially formed. In acidic solutions (pH < 2), supramolecular species, like Mo36O1128–, which generally predominate at 25 °C, do not occur at T > 100 °C. Instead, β‐Mo8O264– is the final molecular precursor of precipitation reactions that was detectable by Raman spectroscopy. The structural type of the solid phase formed through addition of vanadyl sulfate under hydrothermal conditions is sensitively controlled by the nature of the molecular precursor, which is adjusted by the pH. In acidic medium, hexagonal MoO3 (ICSD 80290) is formed, while at pH = 5.8 nano‐crystalline M1 (ICSD 55096) was obtained.

Dynamic nuclear polarization enhancement of protons and vanadium-51 in the presence of pH-dependent vanadyl radicals.

We report applications of dynamic nuclear polarization to enhance proton and vanadium-51 polarization of vanadyl sulfate samples doped with TOTAPOL under magic angle spinning conditions. The electron paramagnetic resonance response stemming from the paramagnetic (51)V species was monitored as a function of pH, which can be adjusted to improve the enhancement of the proton polarization. By means of cross-polarization from the proton bath, (51)V spins could be hyperpolarized. Enhancement factors, build-up times, and longitudinal relaxation times T1((1)H) and T1((51)V) were investigated as a function of pH.

Determination of vanadyl sulfate ion-pair dissociation constant at 298.15 K by Fuoss method

Vanadium battery has fast and large capacity charge and discharge characteristics, and the concentration and stability of the battery electrolyte are the key to the electrolyte performance. In actual, with higher acidity and higher concentration of the vanadium battery electrolyte, the ion-pair is dominant. The ion-pair dissociation constant is one of the important thermodynamic data related to battery performance. The vanadyl sulfate conductivity in aqueous solution was determined using the conductance method at 298.15 K. Using the origin data fitting, the limiting molar conductance is obtained, and then by the improved Ostwald dilution law and the Davies equation, the activity coefficient is solved so as to obtain the ionic strength of the true solution. Using the Fuoss method, the dissociation constant of vanadyl sulfate ion-pair was calculated. At last, the vanadyl sulfate limiting molar conductance (Λ0) is 174.8251748 S·dm2·mol−1, and the vanadyl sulfate ion-pair dissociation constant Kd is 0.002636367, and then other thermodynamic properties can be studied.

Electrochemical codeposition of vanadium oxide and polypyrrole for high-performance supercapacitor with high working voltage.

Electrochemical codeposition of vanadium oxide (V2O5) and polypyrrole (PPy) is conducted from vanadyl sulfate (VOSO4) and pyrrole in their aqueous solution to get V2O5-PPy composite, during which one-dimensional growth of polypyrrole (PPy) is directed. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR) are used to characterize the composite, while scanning electron microscopy (SEM) is used to investigate their morphologies. Cyclic voltammetry (CV), chronopotentiometry (CP) for galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) are used to study electrochemical activities and pseudocapacitive properties of the composite. The influences of VOSO4 to pyrrole ratio in the electro-codeposition solution on morphologies and pseudocapacitive properties of the composite are discussed. Due to the organic-inorganic synergistic effect, V2O5-PPy composite exhibits good charge-storage properties in a large potential window from -1.4 to 0.6 V vs SCE, with a specific capacitance of 412 F/g at 4.5 mA/cm(2). A model supercapacitor assembled by using the V2O5-PPy composite as the electrode materials displays a high operating voltage of 2 V and so a high energy density of 82 Wh/kg (at the power density of 800 W/kg).

An efficient and reusable vanadium based catalytic system for room temperature oxidation of alcohols to aldehydes and ketones

A simple and efficient vanadium based catalyst system for the oxidation of primary and secondary alcohols to aldehydes or ketones is reported using tert-butyl hydroperoxide as oxidizing agent and vanadyl sulfate as catalyst at room temperature. The versatility of the catalytic protocol is studied with wide variety of substrates.

Carbon materials for the positive electrode in all-vanadium redox flow batteries

Abstract The electrode material in all-vanadium redox flow batteries often consists of fibrous carbon felts. It is believed that surface functional groups such as carboxyl and hydroxyl groups, e.g. introduced by heat-treatment, increase the activity of the carbon electrodes due to a facilitated electron transfer. However, other properties of the carbon material have not been investigated in detail. In this paper, the structure of morphologically different carbon materials, such as graphite flakes, two carbon blacks and a carbon fiber material, was correlated with the electrochemical activity obtained by cyclic voltammetry in a three-electrode configuration in vanadyl sulfate solution. Furthermore, the respective carbon materials were heat-treated in air at 400 °C and the corresponding structural changes in sp2 carbon content and amount and kind of surface functional groups determined by NEXAFS analysis were correlated with the activity. Our work shows that the sp2 carbon content on the surface is an important parameter significantly affecting the activity. The results can be utilized to choose a suitable carbon powder material to impregnate the felts in order to increase their reactive surface area.

Does the relief of glucose toxicity act as a mediator in proliferative actions of vanadium on pancreatic islet beta cells in streptozocin diabetic rats?

Background: Data shows vanadium protects pancreatic beta cells (BC) from diabetic animals. Whether this effect is direct or through the relief of glucose toxicity is not clear. This study evaluated the potential effect of oral vanadyl sulfate (vanadium) on glycemic status and pancreatic BC of normal and diabetic rats. Methods: Rats were divided into five groups of normal and diabetic. Diabetes was induced with streptozocin (40 mg/kg, i.v.). Normal rats used water (CN) or vanadium (1 mg/ml VOSO4, VTN). Diabetic rats used water (CD), water plus daily neutral protamine Hagedorn insulin injection (80 U/kg, ITD) or vanadium (VTD). Blood samples were taken for blood glucose (BG, mg/dL) and insulin (ng/dL) measurements. After two months, the pancreata of sacrificed rats were prepared for islet staining. Results: Pre-treated normal BG was 88 ± 2, and diabetic BG was 395 ± 9. The final BG in CD, VTD, and ITD was 509 ± 22, 138 ± 14, and 141 ± 14, respectively. Insulin in VTN (0.75 ± 0.01) and VTD (0.78 ± 0.01) was similar, higher than CD (0.51 ± 0.07) but lower than CN (2.51 ± 0.02). VTN islets compared to CN had larger size and denser central core insulin immunoreactivity with plentiful BC. CD and ITD islets were atrophied and had scattered insulin immunoreactivity spots and low BC mass. VTD islets were almost similar to CN. Conclusion: Besides insulin-like activity, vanadium protected pancreatic islet BC, and the relief of glucose toxicity happening with vanadium had a little role in this action.

Photoelectrochemical performance of W-doped BiVO4 thin films deposited by spray pyrolysis

The effects of tungsten doping and hydrogen annealing on the photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) photoanodes for solar water splitting were studied. Thin films of BiVO4 were deposited on indium tin oxide-coated glass slides by ultrasonic spray pyrolysis of an aqueous solution containing bismuth nitrate and vanadium oxysulfate. Tungsten doping was achieved by adding either silicotungstic acid (STA) or ammonium metatungstate (AMT) to the precursor. The 1.7- to 2.2-μm-thick films exhibited a highly porous microstructure. Undoped films that were reduced at 375°C in 3% H2 exhibited the largest photocurrent densities under 0.1 W cm−2 AM1.5 illumination, where photocurrent densities of up to 1.3 mA cm−2 at 0.5 V with respect to Ag/AgCl were achieved. Films doped with 1% or 5% (atomic percent) tungsten from either STA or AMT exhibited reduced PEC performance and greater sample-to-sample performance variations. Powder x-ray diffraction data indicated that the films continue to crystallize in the monoclinic polymorph at low doping levels but crystallize in the tetragonal scheelite structure at higher doping. It is surmised that the phase and morphology differences promoted by the addition of W during the deposition process reduced the PEC performance as measured by photovoltammetry.

A series of novel oxovanadium(IV) complexes: Synthesis, spectral characterization and antimicrobial study

Oxovanadium(IV) complexes have been synthesized by reacting vanadyl sulfate with Schiff bases derived from 4-amino-5-(substitutedphenoxyacetic acid)-1,2,4-triazole-3-thiol and benzil. All these complexes are soluble in DMF and DMSO; low molar conductance values indicate that they are non-electrolytes and characterized by elemental analysis, spectral techniques (UV–Vis, IR, EPR and XRD) and magnetic moment measurements. The EPR spectra indicate that the free electron is in dxy orbital. In vitro antifungal activity of ligands and synthesized compounds was determined against fungi Aspergillus niger, Colletotrichum falcatum and Colletotrichum pallescence and in vitro antibacterial activity was determined by screening the compounds against Gram-negative (Escherichia coli and Salmonella typhi) and Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacterial strains. The antimicrobial activities have shown that the activity increases upon complexation.

Ameliorative effect of vanadium on oxidative stress in stomach tissue of diabetic rats.

Between their broad spectrum of action, vanadium compounds are shown to have insulin mimetic/enhancing effects. Increasing evidence in experimental and clinical studies suggests that oxidative stress plays a major role in the pathogenesis of diabetes and on the onset of diabetic complications. Thus, preventive therapy can alleviate the possible side effects of the disease. The aim of the present study was to investigate the effect of vanadyl sulfate supplementation on the antioxidant system in the stomach tissue of diabetic rats. Male Swiss albino rats were randomly divided into 4 groups: control; control+vanadyl sulfate; diabetic; diabetic+vanadyl sulfate. Diabetes was induced by intraperitoneal injection of streptozotocin (STZ; 65 mg/kg body weight). Vanadyl sulfate (100 mg/kg body weight) was given daily by gavage for 60 days. At the last day of the experiment, stomach tissues were taken and homogenized to make a 10% (w/v) homogenate. Catalase (CAT), superoxide dismutase (SOD), glutathione reductase (GR), glutathione peroxidase (GPx), glutathione-S-transferase (GST), myeloperoxidase (MPO), carbonic anhydrase (CA), glucose-6-phosphate dehydrogenase (G6PD) and lactate dehydrogenase (LDH) activities were determined in the stomach tissue. CAT, SOD, GR, GPx, GST, CA, G6PD and LDH activities were increased in diabetic rats when compared to normal rats. Vanadium treatment significantly reduced the elevated activities of GR, GPx, GST compared with the diabetic group whereas the decreases in CAT, SOD, CA, G6PD and LDH activities were insignificant. No significant change was seen for MPO activity between the groups. It was concluded that vanadium could be used for its ameliorative effect against oxidative stress in diabetes.

Determination of Volume Properties of Aqueous Vanadyl Sulfate at 283.15 to 323.15 K

This paper reports the densities of aqueous VOSO4 that were measured by an Anton Paar DMA 4500 M from 0.0500 mol·kg–1 to 3.000 mol·kg–1 at 283.15 to 323.15 K. The apparent molar volume, ϕVB, the partial molar volume of VOSO4, V̅B, the apparent molar expansibility of the solute, ϕE, and coefficient of thermal expansion of the solution, α, were calculated. First, these properties described above have been discussed with the temperature and concentration variation. Then the values of the apparent molar volume, ϕVB, were fitted to Pitzer’s model for volumetric properties by the method of the least squares, which allowed the partial molar volume of the VOSO4 at infinite dilution, V̅B0, and Pitzer’s parameters, βMX(0)V, βMX(1)V, and CMXV, to be obtained. The small standard deviations of the fitting show that Pitzer’s model is also appropriate for representing the volumetric properties of aqueous solutions of VOSO4. Using the data from literature, the partial molar volume of the ion VO2+ at infinite dilution, V̅C0, was discussed and the result showed that the negative value of V̅C0 can be attributed to strong hydration of VO2+ as other divalent ions.

Polymeric heterometallic dicarboxylates [MIIx(VIVO)xL2x(H2O)y] (MII = Ba, Mn; L = Me2mal, Bumal) and their electrochemical study on solid and composite paste electrodes

The main goal of this work was to obtain VIV–BaII and VIV–MnII heterometallic dycarboxylates, to characterize their structures, magnetic properties and to investigate the possibility of using obtained compounds in composite paste electrodes. The reactions of vanadyl sulfate VOSO4·3H2O with barium salts of dimethylmalonic (H2Me2mal=C3H6(COOH)2) and butylmalonic (H2Bumal=C4H10(COOH)2) acids taken in a ratio of 1:2 in aqueous solution gave crystals of the coordination polymers {[Ba(VO)(Me2mal)2(H2O)]·H2O}n (1) and {[Ba3(VO)3(Bumal)6(H2O)13]·4H2O}n (2), respectively. The crystal structures of the compounds are built of mononuclear bis-chelate metal fragments containing vanadium(IV), which are bridged to barium ions by carboxylate groups. The reactions of the synthesized compounds with manganese(II) sulfate in aqueous solutions were found to give new heterometallic polymers 3 and 4 {[Mn(VO)(L)2(H2O)5]·H2O}n (L=Me2mal in 3 and L=Bumal in 4), which retain the bis-chelate vanadyl moiety formally acting as a vanadium-containing O-donor ligand. Compounds 1–4 were studied by cyclic voltammetry in solution and as composites in paste electrodes; the potential values as well as localization sites of oxidation and reduction processes were determined.

Effects of vanadium (III, IV, V)-chlorodipicolinate on glycolysis and antioxidant status in the liver of STZ-induced diabetic rats

Vanadium compounds exert various insulin-mimetic and anti-diabetic effects both in vitro and in vivo. Vanadium(III, IV, V)-chlorodipicolinate (Vdipic-Cl) compounds, including H[VIII(dipic-Cl)2]·5H2O (V3dipic-Cl), VIVO(dipic-Cl)(H2O)2 (V4dipic-Cl) and K[VVO2(dipic-Cl)] (V5dipic-Cl), were synthesized with the indicated oxidation states. The present study was conducted to investigate if chemical valence and anti-oxidation effects of vanadium compounds are involved in the anti-diabetic effects observed in streptozotocin (STZ)-induced diabetic rats treated with these vanadium compounds. V3dipic-Cl, V4dipic-Cl, V5dipic-Cl, inorganic vanadium salts vanadyl sulfate (VOSO4) or sodium metavanadate (NaVO3) were orally administered in drinking water (50μgV/ml) to STZ-induced diabetic rats for 28days. The results showed that Vdipic-Cl treatment significantly improved hyperglycemia and glucose intolerance, as well as increased hepatic glycogen synthesis in diabetic rats. The mRNA levels of key glycolytic enzymes in liver, phosphoenolpyruvate carboxykinase (PEPCK), glucokinase (GK), and L-pyruvate kinase (L-PK) altered in diabetic animals were significantly restored towards normal values by treatment with some of the vanadium compounds. Moreover, the diabetes elevated activities of aspartate aminotransferase (AST), alanine aminotransferase (ALT) and alkaline phosphatase (ALP) in serum were significantly decreased after treatment with Vdipic-Cl complexes. Furthermore, treatment of diabetic rats with V4dipic-Cl and V5dipic-Cl compounds significantly reduced malondialdehyde (MDA) production and increased glutathione peroxidase (GSH-Px) and catalase (CAT) activities. These data suggest that vanadium compounds with the indicated chemical valence promote glycogen synthesis and recover suppressed glycolysis in the liver of diabetic rats due to their capacity to reduce oxidative stress by stimulating antioxidant enzymes.

Vanadyl sulfate treatment stimulates proliferation and regeneration of beta cells in pancreatic islets.

We examined the effects of vanadium sulfate (VOSO4) treatment at 5 and 10 mg/kg for 30 days on endocrine pancreas activity and histology in nondiabetic and STZ-induced diabetic rats. In diabetic group, blood glucose levels significantly increased while insulinemia level markedly decreased. At the end of treatment, VOSO4 at a dose of 10 mg/Kg normalized blood glucose level in diabetic group, restored insulinemia, and significantly improved insulin sensitivity. VOSO4 also increased in a dose-dependent manner the number of insulin immunopositive beta cells in pancreatic islets of nondiabetic rats. Furthermore, in the STZ-diabetic group, the decrease in the number of insulin immunopositive beta cells was corrected to reach the control level mainly with the higher dose of vanadium. Therefore, VOSO4 treatment normalized plasma glucose and insulin levels and improved insulin sensitivity in STZ-experimental diabetes and induced beta cells proliferation and/or regeneration in normal or diabetic rats.

Protective effect of vanadyl sulfate on skin injury in streptozotocin-induced diabetic rats

The aim of the present study was to investigate the effect of vanadyl sulfate supplementation on the skin tissues of diabetic and control rats. In this study, 6-6.5 months old male Swiss albino rats were used. The animals were randomly divided into the following four groups: group I, control (nondiabetic intact animals); group II, vanadyl sulfate control; group III, streptozotocin (STZ)-diabetic animals and group IV, STZ-diabetic animals given vanadyl sulfate. The animals were made diabetic by intraperitoneal injection of a single dose of 65mg/kg STZ in 0.01M citrate buffer (pH=4.5). From day 1 to day 60, 100mg/kg vanadyl sulfate was given daily by gavage technique to one of the control and diabetic groups. Body weights and blood glucose levels were estimated on experimental days 0, 1 and 60. On the 60th day, skin tissue samples were taken, glutathione (GSH), lipid peroxidation (LPO), nonenzymatic glycosylation (NEG) and protein levels, catalase (CAT), superoxide dismutase (SOD) and glutathione-S-transferase (GST) activities were determined. Blood glucose, skin LPO and NEG levels increased, but skin GSH levels and CAT, SOD and GST activities decreased in the STZ group. Treatment with vanadyl sulfate reversed these effects. The present study showed that vanadyl sulfate exerted antioxidant properties and may prevent skin damage caused by diabetes.

Oxovanadium complexes with multidentate ligands

Vanadium has ability to coordinate with multidentate ligands in different geometries to produce variety of complexes. Usually the reactions are carried out by refluxing the methanolic solution of oxovanadium salt (VOSO4) with the ligands. Vanadyl sulphate can easily exchange its sulphate group with organic ligands. Sometimes solvent molecules are also attached with the complexes. Vanadyl oxygen usually occupies the axial position. The syntheses and geometries, and selective crystal structures of these complexes are discussed.