Sensitive detection of estrogenic mycotoxin zearalenone by open sandwich immunoassay.

Zearalenone (ZEA) is an estrogenic mycotoxin produced by Fusarium sp., and its production on corn and small grains during storage has been of considerable concern. For sensitive ZEA detection, we applied an open sandwich (OS) immunoassay that can noncompetitively detect monovalent antigens utilizing an antigen-induced enhancement of the V(H)/V(L) interaction. We cloned the V(H) and V(L) cDNAs of anti-ZEA mAb to a split-Fv phagemid pKST2, and firstly both V(H) and V(L) fragments were displayed on M13 phage p9 and p7, respectively, using an amber suppressor, TG-1, as a host. The split-Fv phage showed specific binding to immobilized ZEA, which was well inhibited by free ZEA. Then, the V(H)/V(L) interaction and its antigen-dependency were analyzed using a non-suppressor HB2151 as a host to produce V(H)-displaying phage and his/myc-tagged soluble V(L) in the culture supernatant. By capturing V(L) with an anti-myc or -his antibody and probing bound V(H)-phage, ZEA was successfully detected with a superior detection limit as well as a wider working range than those of a competitive assay. Also, essentially the same results were reproduced with purified V(H)-alkaline phosphatase and MBP-V(L) fusion proteins.     

Determination of the valence distribution of vanadium in polyolefin catalysts prepared from vanadium trichloride

An electrochemical method has been developed for determining the relative amounts of V(II) and V(III) in polyolefin catalysts prepared using aluminum alkyls and vanadium trichloride. The catalyst, usually obtained as a slurry in n-heptane, is titrated potentiometrically with ceric sulfate using a platinum indicator electrode. Under proper experimental conditions, 2 breaks are obtained, corresponding to the reactions V(II) →V(III) + e and V(III) →V(IV) + e. Interferences from other components of the catalyst are negligible. The method is useful for the analysis of both laboratory catalysts and grab samples taken from pilot plant reactors.     

A visible light photocatalyst: effects of vanadium substitution on ETS-10

Hybrid density functional theory/molecular mechanics (DFT/MM) methods have been used to investigate the effects of vanadium substitution in ETS-10. Models have been developed to contain varying concentrations of V(IV) and V(V) within the O-M-O (M = Ti, V) chain. Most of the V-substituted models have a localized mid-gap state. The occupation of this localized state depends upon the dopant oxidation state, leading to the addition of multiple low energy transitions. A linear correlation has been identified between band gap energies estimated using ground state orbital energies and those calculated using the more accurate and computationally demanding time-dependent DFT (TDDFT) method for a variety of transition metal substituted models of ETS-10. Consistent with experimental data for V substitution, our models predict a decrease in the optical band gap with increasing [V], due to a lowering of the delocalized d-orbital states at the bottom of the conduction band with increasing V d-orbital character. This effect is more pronounced in the case of V(V) substitution than V(IV). Excitation energies for the V-doped models, calculated with TDDFT methods correlate well with experimental data, allowing for the assignment of specific optical transitions to experimental UV-Vis spectra. The electronic structure of V-substituted ETS-10 at high V concentration demonstrates band gap energies within the visible range of the spectrum. Additionally, at high [V] the band gap energy and presence of low energy electron traps can be controlled by the relative concentration of V(IV) and V(V) along the O-M-O chain, establishing V-substituted ETS-10 as a promising visible light photocatalyst.     

Determination of V(IV) and V(V) by electrothermal atomic absorption spectrometry following selective solid-phase extraction and the study on the change in the oxidation state of vanadium species in seawater during the sample storage.

The changes in the oxidation state of vanadium in artificial and natural seawater samples were studied by electrothermal atomic absorption spectrometry (ETAAS) with a direct injection of a resin suspension. V(IV) and V(V) were extracted as the complex with Chromazurol B and with N-cinnamoyl-N-2,3-xylylhydroxylamine, respectively, using a suspension of an anion-exchange resin and determined by ETAAS independently. The detection limits of both methods were 0.02 ng ml(-1) for 40 ml of a sample solution. The recovery tests for an artificial seawater sample spiked with V(IV) and/or V(V) were carried out carefully. The results showed that the recoveries of V(IV) or V(V) were 99.2-109% and the standard deviations were 1-6%. The total V was also determined after V(V) was reduced by ascorbic acid. In artificial seawater at pH 7.8, V(V) was stable but V(IV) was oxidized rapidly. In acidified artificial seawater (pH 2.0), V(IV) was oxidized slowly but only a small tendency of such reduction of V(V) was observed. In a natural seawater sample, V(IV) was not detected. The acidification of the natural seawater sample resulted in the reduction of V(V).     

Autocatalytic membrane-amplification on a pre-existing vesicular surface

In water, phosphoric membrane molecule (V(-)) self-assembled to form an anionic giant vesicle, the surface of which served as a catalyst for the autocatalytic formation of V(-) from its membrane precursor (V*), and the amplified V(-) produced a new vesicle using the original vesicle as a scaffold.     

Determination of V(V), Nb(V) and Ta(V) as their 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol chelates by reversed-phase HPLC

This paper reports the separation and determination of V(V), Nb(V) and Ta(V) by RP-HPLC using 5-Br-PADAP as a precolumn derivatizing reagent. On C(18) column, the three metal chelates can be separated on a baseline in 9 min with the mobile phase of methanol-water (59:41, v/v) containing tartaric acid (0.2%) and acetate buffer (pH 3.5, 10 mM). The detection limits of V(V), Nb(V) and Ta(V) are 0.13 ppb, 0.22 ppb and 1.79 ppb, respectively when S/N is 3. This method is simple and rapid, and has been used in mineral analysis with satisfactory results.     

Controlling transformations in the assembly of polyoxometalate clusters: {Mo11V7}, {Mo17V8} and {Mo72V30}

The reaction of molybdate with vanadium(V) in the presence of sulfite anions is explored showing how, via cation control, stepwise assembly through the {Mo(11)V(7)} cluster yields a {M(25)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(μ(9)-SO(3))(Mo(VI)(6)V(V)O(22))](10-) (1a), which was first discovered using cryospray mass spectrometry, whereas switching the cation away from ammonium allows the direct formation of the spherical 'Keplerate' {Mo(72)V(30)} cluster.     

Determination of niobium(V) and tantalum(V) as 4-(2-pyridylazo)resorcinol–citrate ternary complexes in geological materials by ion-interaction reversed-phase high-performance liquid chromatography

A method for the simultaneous separation and determination of Nb(V) and Ta(V) as ternary complexes formed with 4-(2-pyridylazo)resorcinol (PAR) and citrate was developed using ion-interaction reversed-phase high-performance liquid chromatography on a C₁₈ column. Method parameters, such as pre-column complex formation conditions and composition of the complexes were investigated using spectrophotometry and HPLC. Under the optimum conditions, the Nb(V) and Ta(V) complexes were eluted within 12 min with a mobile phase of methanol–water (32:68, v/v) containing 5 mM acetate, 5 mM TBABr and 5 mM citrate buffer at pH 6.5, with detection at 540 nm. A typical separation efficiency was 33 000 and 20 000 theoretical plates per metre for Nb(V) and Ta(V), respectively. The relative standard deviation of retention times for the Nb(V) and Ta(V) complexes were 0.16% and 0.17% and for peak areas were 0.28% and 1.36%, respectively. The detection limits (signal-to-noise ratio=3) for Nb(V) and Ta(V) were 0.4 ppb and 1.4 ppb, respectively. Results obtained for standard reference rock samples agreed well with certified values and results obtained by inductively coupled plasma MS.     

Solution identification and solid state characterisation of a heterometallic polyoxometalate {Mo(11)V(7)}: [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(mu(9)-SO(3))](7-)

A polyoxomolybdenum/vanadium-sulfite {M(18)} cluster-based compound, [Mo(VI)(11)V(V)(5)V(IV)(2)O(52)(mu(9)-SO(3))](7-), is reported that exhibits a unique structural motif, arising from the incorporation of five V(V) and two V(IV) ions into a {M(18)} cluster framework templated by SO(3)(2-); this cluster compostion was first identified using cryospray mass spectrometry.     

Separation of V(V)-4-(2-pyridylazo)resorcinolato complex from a large excess reagent using an ODS cartridge for high-performance liquid chromatography.

A selective off-line preconcentration technique for the V(V) complex with 4-(2-pyridylazo)resorcinol has been developed and successfully applied to the determination of V(V) in an air-borne sample. The target complex was separated from excess reagent using an ODS cartridge and water as the eluent. The complex was then concentrated on another ODS cartridge using tetrabutylammonium bromide and eluted with methanol; the eluate was applied to a one-drop concentration/HPLC. A detection limit as low as (6.05 +/- 0.82)x 10(-11) M (5 ppt) was achieved.     

Determination of Vanadium(IV) and Vanadium(V) in Benfield Samples by IEC with Conductivity Detection

In this study, the determination of vanadium valence state, V(IV) and V(V) has been achieved using ion-exchange chromatography with conductivity detector. In this method, V(IV) was determined as V(IV)-EDTA complex and V(V) as vanadate ion. Determination of V(IV) was successfully done using 3 mM carbonate/bicarbonate/EDTA at pH 8.6 as the eluent. The additive, EDTA in the mobile phase did not seem to interfere with the V(IV) analysis. The detection of V(V) was achieved with 5 mM disodium hydrogen phosphate buffer at pH 10.4. A linear calibration graph over VO₃ ^? and V(IV) with concentration ranges 5–15 mg L^?1 gave the detection limit at 0.09 and 0.1 mg L^?1, respectively. Both V(IV) and V(V) were successfully determined in Benfield sample, with concentrations of V(IV) and V(V) at 4 and 11,000 mg L^?1, respectively.     

Applications involving oxidation with KBrO3: III. Rapid potentiometric methods for vanadium alone or in mixtures

A rapid and reliable method is given for the determination of vanadium based on oxidation of the V(IV) with a known excess of bromate to V(V). The unreacted oxidant as well as V(V) are subsequently reduced with sulfurous acid to V(IV). The resulting Br^?1 was potentiometrically titrated with Hg(I) using silver amalgam as the indicator electrode. The method finds application to the analysis of some binary and ternary mixtures.     

Speciation of vanadium (IV) and vanadium (V) with Eriochrome Cyanine R in natural waters by solid phase spectrophotometry

The separation and preconcentration of vanadium (IV) and vanadium (V) using Sephadex DEAE A-25 with Eriochrome Cyanine R has been studied, based on the preconcentration of vanadium (IV) in the first step and V(V) after reduction with ascorbic acid in the second step. Factors affecting the optimum fixation of the complex were investigated. The absorbance of the solid phase is measured directly at 563 nm for V(IV), at 585 nm for V(V) and at 750 nm for both. The proposed method provides a simple and specific procedure for the separation of vanadium in natural waters. The calibration graph is linear up to 150 ng/mL, with RSD of 4.7% for V(IV) and 4.0% for V(V). The detection limits are 1.6 and 1.4 ng/mL for V(IV) and V(V), respectively.     

RP-HPLC study of redox equilibria in vanadium-PAR binary and ternary systems: Direct determination of vanadium in steel

The reversed-phase high-performance liquid Chromatographic (RP-HPLC) behaviour of the binary chelates of V(V) and V(IV) with 4-(2-pyridylazo) resorcinol (PAR) and ternary chelates of vanadium with PAR and auxiliary ligands: hydrogen peroxide, hydroxylamine, tartrate and citrate were studied using a C₁₈ column. The complex double-peak chromatograms of V(IV)/V(V)-PAR systems were studied and the origin of each peak was proved. Vanadium in ternary systems with PAR and hydrogen peroxide was found exclusively in V(V)-H₂O₂-PAR complex (single peak on the chromatogram) despite its initial oxidation state. The double role of hydroxylamine (complex agent and reductor) in vanadium systems with PAR was confirmed: in the V(V) system three species were identified (V(V)-PAR, V(V)-NH₂OH-PAR and V(IV)-PAR), but in the V(IV) system only two: V(IV)-PAR and V(V)-NH₂OH-PAR. Citrate and tartrate giving single peak were found as auxiliary ligands in ternary V(V) systems of analytical importance. Due to its masking potential towards iron (III) ions, citrate was chosen as the most suitable third component of a ternary vanadium system with PAR, to form the basis of an RP-HPLC method for direct determination of V in steel.     

Application of spectral beta-correction method and partial least squares for simultaneous determination of V(IV) and V(V) in surfactant media

Simultaneous determination of V(IV) and V(V) was performed by application of partial least squares when the calibration matrix was obtained using beta-correction spectra. Two reaction between V(IV) and V(V) and Pyrogallol Red as a ligand in presence of cethyltrimethylammoniumbromide (CTAB) media has been investigated and applied to the simultaneous spectrophotometric determination of these species. The parameters controlling behavior of the system were investigated and optimum conditions selected. Determinations were made over the concentration range 0.6-4.50 microg ml-1 of V(IV) and 0.3-5.50 microg ml-1 of V(V). Applying this method to simultaneous determination of these metal ions in several real samples with total relative standard error less than 5% validated the proposed method.     

Chromium(V) peptide complexes: synthesis and spectroscopic characterization

A series of stable Cr(V) model complexes that mimic the binding of Cr(V) to peptide backbones at the C-terminus of proteins have been prepared for N,N-dimethylurea derivatives of the tripeptides Aib3-DMF, AibLAlaAib-DMF, and AibDAlaAib-DMF (Aib = 2-amino-2-methylpropanoic acid, DMF = N,N-dimethylformamide). The Cr(ll) precursor complexes were synthesized by the initial deprotonation of the amide and acid groups of the peptide ligands in DMF with potassium tert-butoxide in the presence of CrCl2. The Cr(II) intermediates thus formed were then immediately oxidized to Cr(V) using tert-butyl hydroperoxide. Spectroscopic and mass-spectrometric analyses of the Cr(V) complexes showed that a new metal-directed organic transformation of the ligand had occurred. This involved a DMF solvent molecule becoming covalently bound to the amine group of the peptide ligand, yielding a urea group, and a third coordinated deprotonated urea nitrogen donor. A metal-directed oxidative coupling has been proposed as a possible mechanism for the organic transformation. The Cr(V/IV) reduction potential was determined for the three Cr(V) complexes using cyclic voltammetry, and in all cases it was quasi-reversible. These are the first isolated and fully characterized Cr(V) complexes with non-sulfur-containing peptide ligands.     

Tetrabutylammonium tetra (tert-butyl alcohol) coordinated fluoride-an efficient reagent for the synthesis of fluorine derivatives of phosphorus(V) compounds

Direct conversion of phosphorus(V) chlorides to the corresponding phosphorus(V) fluorides was achieved using a solid reagent, tetrabutylammonium tetra (tert-butyl alcohol) coordinated fluoride. The phosphorus(V) fluorides were directly synthesized and efficiently isolated in very good yields.     

A theoretical study of the inner-sphere disproportionation reaction mechanism of the pentavalent actinyl ions

The inner-sphere mechanisms of the disproportionation reactions of U(V), Np(V), and Pu(V) ions have been studied using a quantum mechanical approach. The U(V) disproportionation proceeds via the formation of a dimer (a cation-cation complex) followed by two successive protonations at the axial oxygens of the donor uranyl ion. Bond lengths and spin multiplicities indicate that electron transfer occurs after the first protonation. A solvent water molecule then breaks the complex into solvated U(OH)2(2+) and UO2(2+) ions. Pu(V) behaves similarly, but Np(V) appears not to follow this path. The observations from quantum modeling are consistent with existing experimental data on actinyl(V) disproportionation reactions.     

Binding patterns of vanadium to transferrin in healthy human serum studied with HPLC/high resolution ICP-MS

Vanadium (V) is an essential metal for mammals. It has different valence states. In blood, V is bound to transferrin (Tf), a glycoprotein that has two metal-binding sites (C-lobe site and N-lobe site). In the present study, the binding patterns of V to serum Tf were analyzed by combined on-line HPLC and high-resolution ICP-MS (HPLC/HR-ICP-MS). The levels of (51)V, (56)Fe and (32)S, which are interfered with polyatomic ions such as (35)Cl(16)O(+), (38)Ar(13)C(+) and (37)Cl(14)N(+), (40)Ar(16)O(+) and (40)Ca(16)O(+), and (16)O(2)(+), respectively, when using quadrupole ICP-MS, could be monitored simultaneously by HR-ICP-MS at a resolution of m/[capital Delta]m= 4000. Sample (a 1 ml portion of serum from a healthy person or 2 mg of human serum Tf (hTf)) was directly subjected to HPLC equipped with an anion-exchange column. V in human serum without any in vitro V spike was detected as V(C)-Tf (V bound to C-lobe site of Tf) and metal(2)-Tf. Since V(iii) was most favorable in terms of the binding to hTf in the presence of bicarbonate and V bound to the C-lobe site of hTf was detected only in the case of V(iii) among the three valence states of V, it was suggested that a part, at least, of V in the V(C)-Tf in healthy human serum may be present as V(iii), in addition to the generally accepted V(iv).     

Optical fibre chemical sensor for trace vanadium(V) determination based on newly synthesized palm based fatty hydroxamic acid immobilized in polyvinyl chloride membrane

Fatty hydroxamic acid (FHA) immobilized in polyvinyl chloride (PVC) has been studied as a sensor element of an optical fibre chemical sensor for V(V). By using this instrument, V(V) in solution has been determined in the log concentration range of 0-2.5 (i.e. 1.0-300 mg/L). The detection limit was 1.0 mg/L. The relative standard deviation (R.S.D.) of the method for the reproducibility study at V(V) concentration of 200 mg/L and 300 mg/L were calculated to be 2.9% and 2.0%, respectively. Interference from foreign ions was also studied at 1:1 mole ratio of V(V):foreign ions. It was found that, Fe(III) ion interfered most in the determination of vanadium(V). Excellent agreement with ICP-AES method was achieved when the proposed method was applied towards determination of V(V).