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V2O5 nanorods on TiO2 nanofibers: a new class of hierarchical nanostructures enabled by electrospinning and calcination.

Electrospinning provides a simple approach to fabricating nanofibers and assemblies with controllable hierarchical structures. In this communication, we demonstrate that electrospinning can be combined with calcination to further maneuver the morphology and phase structure of nanofibers. More specifically, single-crystal V2O5 nanorods could be grown on rutile nanofibers by carefully calcining composite nanofibers consisting of amorphous V2O5, amorphous TiO2, and poly(vinylpyrrolidone). The size of the resulting V2O5 nanorods could be conveniently controlled by varying the composition of the nanofibers and/or the calcination temperature. In addition to the nanorod-on-nanofiber hierarchical structure, we believe this approach can also be extended to fabricate other more complex architectures.

Crystallization↗

Strain-induced self organization of metal-insulator domains in single-crystalline VO2 nanobeams.

We investigated the effect of substrate-induced strain on the metal-insulator transition (MIT) in single-crystalline VO(2) nanobeams. A simple nanobeam-substrate adhesion leads to uniaxial strain along the nanobeam length because of the nanobeam's unique morphology. The strain changes the relative stability of the metal (M) and insulator (I) phases and leads to spontaneous formation of periodic, alternating M-I domain patterns during the MIT. The spatial periodicity of the M-I domains can be modified by changing the nanobeam thickness and the Young's modulus of the substrate.

Crystallization↗

Site-selective DNA photocleavage involving unusual photoinitiated tautomerization of chiral tridentate vanadyl(V) complexes derived from N-salicylidene alpha-amino acids.

The titled vanadyl(V) complexes serve as efficient reagents for cleaving supercoiled plasmid DNA by photoinitiation. Complex 3d, derived from 2-hydroxy-1-naphthaldehyde and l-phenylalanine, exhibits a unique wedge feature, inducing a site-selective photocleavage at the C22-T23 of the bulge backbone for a HIV-27 DNA system at 0.1-5 muM. Transient absorption experiments for 3d indicate the involvement of LMCT with concomitant tautomerization, leading to an o-quinone-methide V-bound hydroxyl species responsible for the cleavage profiles. [structure: see text]

Base Sequence↗

Sodium selenate corrects glucose tolerance and heart function in STZ diabetic rats.

Sodium selenate, administered intraperitoneally (i.p.), resulted in an improvement in glucose tolerance in treated diabetic rats. Fed rat plasma glucose levels were reduced by selenate treatment in streptozotocin diabetic rats. The lowest values of blood glucose were reached within 3 weeks of beginning the treatment. Food and fluid consumption was reduced in treated compared to untreated diabetic rats. Diabetic treated rats did not release insulin in response to a glucose challenge and insulin release in response to a challenge was markedly reduced in control treated rats. Assessment of heart function using a working heart apparatus showed that treated diabetic rats with improved blood glucose levels had normal heart function at 8 weeks of diabetes in contrast to hearts from non-treated diabetics. This study extends previous observations on the in vivo insulin-like effects of sodium selenate.

Animals↗

A reversible copper extrusion-insertion electrode for rechargeable Li batteries.

Although widely used, the most promising Li-based technologies still suffer from a lack of suitable electrodes. There is therefore a need to seek new materials concepts to satisfy the increasing demands for energy storage worldwide. Here we report on a new layered electrode material, Cu(2.33)V(4)O(11), which shows a sustainable reversible capacity of 270 mA h g(-1) at a voltage of about 2.7 V, and electrochemically reacts with Li in an unusual and spectacular way. The reaction entails a reversible Li-driven displacement process leading to the growth and disappearance of Cu dendrites with a concomitant reversible decomposition and recrystallization of the initial electrode material. We show from structural considerations that the uniqueness of Cu(2.33)V(4)O(11) is rooted in the peculiar flexibility of the stacked [V(4)O(11)](n) layers, which is due to the presence of pivot oxygen atoms. Fully reversible displacement reactions could provide a new direction for developing an alternative class of higher energy density Li storage electrodes.

Copper↗

Vanadium nitride functionalization and denitrogenation by carbon disulfide and dioxide.

A dramatic difference in behavior is observed for the dithiocarbamate and carbamate complexes [Ar(But)N]3V(NCE2)Na(THF)2(E = S or O, respectively), prepared from the corresponding nitride species ([Ar(But)N]3V identical to NNa)2 by way of a nucleophilic addition reaction involving carbon disulfide or dioxide, and is rationalized with the aid of DFT calculations.

Carbon Dioxide↗

Speciation in the aqueous H+/H2VO4-/H2O2/picolinate system relevant to diabetes research.

A detailed study of the quaternary aqueous H+/H2VO4-/H2O2/picolinate (Pi-) system has been performed at 25 degrees C in 0.150 M Na(Cl) medium using quantitative 51 V NMR (500 MHz) and potentiometric data (glass electrode). In the ternary H+/H2VO4-/Pi- system, six complexes have been found in the pH region 1-10. In the quaternary H+/H2VO4-/H2O2/Pi- system, eight additional complexes have been found. Generally, equilibria are fast in both systems. The rate of peroxide decomposition depends on the species in solution. Chemical shifts, compositions and formation constants for the species are given. Equilibrium conditions and the fit of the model to the experimental data are illustrated in distribution diagrams. Possible formation of mixed ligand species with imidazole, lactic acid and citric acid have been investigated and ruled out under the same experimental conditions. Structural proposals are given, based on 1)C NMR data and available crystal structures.

Carbon Isotopes↗

Synthesis, characterisation and catalytic potential of hydrazonato-vanadium(V) model complexes with [VO]3+ and [VO2]+ cores.

Reaction between [VO(acac)2] and H2L (H2L are the hydrazones H2sal-nah I or H2sal-fah II; sal = salicylaldehyde, nah = nicotinic acid hydrazide and fah = 2-furoic acid hydrazide) in methanol leads to the formation of oxovanadium(IV) complexes [VOL.H2O](H2L = I: 1, H2L = II: 4). Aerial oxidation of the methanolic solutions of 1 and 4 yields the dinuclear oxo-bridged monooxovanadium(V) complexes [{VOL}2mu-O](H2L = I: 2, H2L = II: 5). These dinuclear complexes slowly convert, in excess methanol, to [VO(OMe)(MeOH)L](H(2)L = I: 9, H(2)L = II: 10), the crystal and molecular structures of which have been determined, confirming the ONO binding mode of the dianionic ligands in their enolate form. Reaction of aqueous K[VO3] with the ligands at pH ca. 7.5 results in the formation of [K(H2O)][VO2L](H2L = I: 3, H2L = II: 6). Treatment of 3 and 6 with H2O2 yields (unstable) oxoperoxovanadium(v) complexes K[VO(O2)L], the formation of which has been monitored spectrophotometrically. Acidification of methanolic solutions of 3 and 6 with HCl affords oxohydroxo complexes, while the neutral complexes [VO2(Hsal-nah)] 7 and [VO2(Hsal-fah)] 8 were isolated on treatment of aqueous solutions of 3 and 6 with HClO4. These complexes slowly transform into 9 and 10 in methanol, as confirmed by 1H, 13C and 51V NMR. The anionic complexes 3 and 6 catalyse the oxidative bromination of salicylaldehyde in water in the presence of H2O2/KBr to 5-bromosalicylaldehyde and 3,5-dibromosalicylaldehyde, a reaction similar to that exhibited by vanadate-dependent haloperoxidases. They are also catalytically active for the oxidation of benzene to phenol and phenol to catechol and p-hydroquinone.

Aldehydes↗

Speciation in the aqueous H+/H2VO4-/H2O2/phosphate system.

The speciation in the aqueous H(+)/H(2)VO(4)(-)/phosphate (dihydrogen phosphate, P(-)) and H(+)/H(2)VO(4)(-)/H(2)O(2)/P(-) systems has been determined in the physiological medium of 0.150 M Na(Cl) at 25 degrees C. A combination of multinuclear NMR integral and chemical shift (Bruker AMX500) as well as potentiometric data (glass electrode) have been collected and treated simultaneously by the computer program LAKE. The pK(a)-values for phosphoric acid have been determined by potentiometric and (31)P NMR chemical shift data, and have been found to be 1.85 +/- 0.02, 6.69 +/- 0.02 and 11.58 +/- 0.07. The errors given are 3sigma. Altogether nine vanadate-phosphate species have been found in the ternary H(+)/H(2)VO(4)(-)/P(-) system in the pH region 1-11, with the following compositions: VP, VP(2) and V(14)P. Equilibrium is very slow in acidic solutions, requiring more than 3 months for the formation of V(14)P species. On the other hand, less than 15 min are needed for equilibration at neutral and alkaline pH. In the quaternary H(+)/H(2)VO(4)(-)/H(2)O(2)/P(-) system, four new species have been found in addition to all binary and ternary complexes. They are of VXP and VX(2)P compositions, where X denotes the peroxo ligand. (51)V and (31)P NMR chemical shifts, compositions and formation constants are given, and equilibrium conditions are illustrated in distribution diagrams as well as the fit of the model to the experimental data. Biological and medical relevance of the species is also discussed and physiological conditions are modelled.

Anions↗

Elucidation of the molecular structure of hydrated vanadium oxide species by X-ray absorption spectroscopy: correlation between the V...V coordination number and distance and the point of zero charge of the support oxide.

The effect of the point of zero charge (PZC) of the support oxide (Al(2)O(3), Nb(2)O(5), SiO(2) and ZrO(2)) on the molecular structure of hydrated vanadium oxide species has been investigated with EXAFS spectroscopy for low-loaded vanadium oxide catalysts. It was found that the degree of clustering (i.e., the V[dot dot dot]V coordination number) and the V...V distance increase with decreasing PZC of the support oxide; i.e., Al(2)O(3) (8.7) < ZrO(2) (7) < Nb(2)O(5) (3.3) < SiO(2) (2). Upon hydration the silica-supported vanadium oxide exhibited a clear alteration in the position of the oxygen atoms surrounding the central vanadium atom and the number of oxygen atoms around vanadium increased to five. In contrast, only minor changes in the molecular structure were detected for the alumina-, niobia- and zirconia-supported vanadium oxide catalysts. Based on a detailed analysis of the EXAFS data a semi-quantitative distribution of vanadium oxide species present on the surface of the different support oxides can be obtained, which is in good agreement with earlier characterization studies primarily making use of Raman spectroscopy.

Absorption↗

Vanadium pharmacokinetics and oral bioavailability upon single-dose administration of vanadyl sulfate to rats.

Vanadium pharmacokinetic parameters and oral bioavailability were determined after administration of vanadyl sulfate, an antidiabetic agent, to male Wistar rats. An optimal sampling design was used over a 21-day period; vanadium was measured in blood by atomic absorption spectrophotometry (AAS). After i.v. bolus injection (3.025 mg V/kg body weight), a three-compartment model was fitted to the data. Mean (+/- SD) half-lives were 0.90 +/- 0.56 hours, 24.8 +/- 14.5 h and 201 +/- 74 h, respectively, for the three phases observed. Vanadium clearance averaged 37.6 +/- 15.8 mL/h. Initial volume of distribution was 2.43 +/- 1.22 L/kg whereas total volume of distribution was 25.4 +/- 3.9 L/kg; these values largely exceeded body weight (i.e. 300 g), in agreement with a great uptake and retention of vanadium in tissues. After oral gavage administration (15.12 and 7.56 mg V/kg body weight), vanadium disposition was best described by a three-compartment model, with absorption appearing to occur by a zero-order rate. This process lasted 10.3 +/- 1.3 h and 10.9 +/- 1.1 h for the two dosage levels, respectively. Half-lives corresponding to the terminal log-linear part of the curve were 173.5 +/- 1.6 h and 172 +/- 6 h (Bayesian estimates). No dose-dependency was observed for any of the parameters determined. Absolute bioavailabilities, with reference to the i.v. administration, were 12.5% and 16.8% when determined from AUCmod. Bioavailability appeared to be higher than generally stated in the literature.

Administration, Oral↗

Inhibition of vagally mediated immune-to-brain signaling by vanadyl sulfate speeds recovery from sickness.

To the ill patient with diabetes, the behavioral symptoms of sickness such as fatigue and apathy are debilitating and can prevent recuperation. Here we report that peripherally administered insulin-like growth factor 1 (IGF-1) attenuates LPS-dependent depression of social exploration (sickness) in nondiabetic (db/+) but not in diabetic (db/db) mice. We show that the insulin/IGF-1 mimetic vanadyl sulfate (VS) is effective at augmenting recovery from sickness in both db/+ and db/db mice. Specifically, peak illness was reached at 2 h for both VS and control animals injected with LPS, and VS mice recovered 50% faster than non-VS-treated animals. Examination of the mechanism of VS action in db/+ mice showed that VS paradoxically augmented peritoneal macrophage responsivity to LPS, increasing both peritoneal and ex vivo macrophage production of IL-1beta and IL-6 but not TNF-alpha. The effects of VS in promoting recovery from sickness were not restricted to LPS, because they were also observed after direct administration of IL-1beta. To explore the possibility that VS impairs immune-to-brain communication via vagal afferents, the vagally mediated satiety-inducing effects of cholecystokinin 8 were tested in db/+ mice. Cholecystokinin decreased food intake in saline-injected mice but not in VS-treated mice. VS also inhibited LPS-dependent up-regulation of IL-1beta and IL-6 mRNA in the brain, while increasing by 50% the cerebral expression of transcripts of the specific antagonist of IL-1 receptors IL-1RA and IL-1R2. Taken together, these data indicate that VS improves recovery from LPS-induced sickness by blocking vagally mediated immune-to-brain signaling and by up-regulating brain expression of IL-1beta antagonists.

Animals↗

Four-dimensional ultrafast electron microscopy of phase transitions.

Reported here is direct imaging (and diffraction) by using 4D ultrafast electron microscopy (UEM) with combined spatial and temporal resolutions. In the first phase of UEM, it was possible to obtain snapshot images by using timed, single-electron packets; each packet is free of space-charge effects. Here, we demonstrate the ability to obtain sequences of snapshots ("movies") with atomic-scale spatial resolution and ultrashort temporal resolution. Specifically, it is shown that ultrafast metal-insulator phase transitions can be studied with these achieved spatial and temporal resolutions. The diffraction (atomic scale) and images (nanometer scale) we obtained manifest the structural phase transition with its characteristic hysteresis, and the time scale involved (100 fs) is now studied by directly monitoring coordinates of the atoms themselves.

Crystallization↗

Role of oxidative stress in the action of vanadium phosphotyrosine phosphatase inhibitors. Redox independent activation of NF-kappaB.

The role of intracellular oxidative stress in the mechanism of action of phosphotyrosine phosphatase (PTP) inhibitors was studied using three vanadium-based compounds. Sodium orthovanadate (Na3VO4), sodium oxodiperoxo(1,10-phenanthroline)vanadate(V) (pV(phen), and bis(maltolato)-oxovanadium(IV) (BMOV) differentially induced oxidative stress in lymphocytes. Treatment with pV(phen), which caused intracellular oxidation, induced strong protein tyrosine phosphorylation compared with Na3VO4 and BMOV. Syk family kinases and the mitogen-activated protein kinase erk2 were rapidly activated by pV(phen) but not by BMOV or Na3VO4. In contrast, both BMOV and pV(phen) strongly activated NF-kappaB. The antioxidant pyrrolidine dithiocarbamate (PDTC) greatly diminished the intracellular oxidation and protein phosphotyrosine accumulation induced by pV(phen). Pretreatment of cells with PDTC reduced and delayed the activation of Syk kinases and erk2. However, NF-kappaB activation by pV(phen) was markedly enhanced in lymphocytes pretreated with PDTC, and another antioxidant, N-acetylcysteine, did not prevent the activation of NF-kappaB by BMOV. These results indicate a role for oxidative stress in the biological effects of some PTP inhibitors, whereas NF-kappaB activation by PTP inhibitors is mediated by mechanisms independent of intracellular redox status.

Antioxidants↗

Vanadium K-edge x-ray absorption spectroscopy reveals species differences within the same ascidian genera. A comparison of whole blood from Ascidia nigra and Ascidia ceratodes.

Vanadium K-edge x-ray absorption spectroscopy (XAS) was used to examine whole blood preparations from the tunicates Ascidia nigra and Ascidia ceratodes. Each XAS spectrum exhibits a rising edge inflection near 5480 eV characteristic of vanadium(III) and an intensity maximum at 5484.0 eV. In A. ceratodes blood cells, intrinsic aquo-VSO4+ complex ion is indicated by an inflection feature at 5476 eV in the first derivative of the vanadium K-edge XAS spectrum, but this feature is notably absent from the first derivative of the vanadium K-edge spectrum of blood cells from A. nigra. A strong pre-edge feature at 5468.6 eV also uniquely distinguishes the vanadium K-edge XAS spectrum of A. nigra blood cells, implying that vanadyl ion represents approximately 25% of the endogenous vanadium. However, the energy position of the rising edge inflection of the vanadium K-edge XAS spectrum of A. nigra (5479.5 eV) is 1 eV lower than that of A. ceratodes (5480.5 eV), the reverse of any expected shift arising from the endogenous vanadyl ion. Thus, in contrast to A. ceratodes, a significant fraction of the blood cell vanadium(III) in A. nigra is apparently in a ligation environment substantially different from that provided by water. These novel species-related differences may have taxonomic significance.

Absorptiometry, Photon↗

Treatment of human T cells with bisperoxovanadium phosphotyrosyl phosphatase inhibitors leads to activation of cyclooxygenase-2 gene.

Protein-tyrosine phosphatase (PTP) inhibitors are potent activators of T lymphocytes, most likely by affecting the early steps of T cell receptor (TCR) signaling. We have analyzed the effect of the PTP inhibitor bisperoxovanadium (bpV) on expression of the human cyclooxygenase 2 (COX-2) gene, which is induced following TCR triggering. Here we show that COX-2 promoter activity is markedly up-regulated following exposure of Jurkat T cells to bpV(pic). Interestingly enough, treatment of Jurkat cells with cyclic AMP-elevating agents such as forskolin, in combination with bpV, resulted in a more important COX-2 transcriptional activation. Such activation is inhibited by the immunosuppressive drugs FK506 and cyclosporin A. The two nuclear factor of activated T cells (NFAT) binding sites located within the COX-2 promoter region are involved in bpV-mediated positive effect on COX-2 promoter. Electromobility shift assays showed that NFAT1 and activator protein-1 are both translocated to the nucleus following bpV treatment. The active participation of p56(lck), ZAP-70, p36(LAT), and calcium in the bpV-dependent signaling cascade leading to COX-2 transcriptional activation was demonstrated using deficient cell lines and specific inhibitors. Although several PTPs are most likely targeted by bpV, our data suggest that the bpV-mediated signaling cascade is initiated by inhibition of SHP-1, which leads to phosphorylation of p56(lck) and ZAP-70 and, ultimately, to NFAT and activator protein-1 nuclear translocation. These results suggest that PTP inhibitors can activate COX-2 gene expression in a manner very similar to the stimulation induced by TCR triggering.

Active Transport, Cell Nucleus↗