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The effect of in vivo administration of molybdenum (as sodium molybdate) and tungsten (as sodium tungstate) was investigated in the skin of laboratory rats. It was proved that the amount of both bound molybdenum and tungsten in collagen is relatively small being 0.05 and 0.06 moles per mole respectively. Besides the fraction of firmly bound molybdenum and tungsten a much higher extractable pool of both these metals was found. It was also demonstrated that in vivo shadowing of collagen is caused by the fraction of loosely bound metals. On the other hand pronounced changes were shown in the mechanical properties of connective tissue after molybdate and tungstate administration. Surprisingly, the change in mechanical properties indicated a lower level of cross-linking after the administration of the investigated metals. It is therefore concluded that bitopical binding of molybdenum and tungsten in the collagen structure is unlikely. It also appears that the biological effect of these metals is due to the competition with copper and the interference with the physiological cross-linking reactions based on the partial blockade of lysyloxidase.
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PMID:The mechanism of action of molybdenum and tungsten upon collagen structures in vivo. 296 7

Chemical analysis of dimethyl sulfoxide reductase from Rhodobacter sphaeroides f. sp. denitrificans has shown that its molybdenum center contains two molybdopterin guanine dinucleotide molecules and a single atom of molybdenum. The enzyme, which exists as a monomer of 86 kDa, was shown to contain 1 mol of molybdenum, 4 mol of organic phosphate, and 2 mol of guanine per mole of protein. In addition, the relative yield of Form A, a fluorescent derivative of molybdopterin, was twice that obtained from sulfite oxidase, a protein which contains a single molybdopterin per molybdenum. These findings correlate with the recent report of the presence of two molybdopterin ligands in the tungsten cofactor of aldehyde ferredoxin oxidoreductase from Pyrococcus furiosus, providing the first example of a bis(pterin)molybdenum cofactor and extending this structural motif to the molybdopterin dinucleotide enzymes.
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PMID:Identification of the molybdenum cofactor of dimethyl sulfoxide reductase from Rhodobacter sphaeroides f. sp. denitrificans as bis(molybdopterin guanine dinucleotide)molybdenum. 855 38

The thermodynamic activities of SiO(2) in Al(2)O(3)-SiO(2) liquid slags were measured by the high-temperature Knudsen cell mass spectromeric method in the present work. The measurements were carried out in the temperature range 1863-2169 K. Tungsten crucibles were used to hold the slags. The system was calibrated using a CaF(2) standard. The mass spectra obtained for pure SiO(2) were in agreement with earlier data. The activities of silica, measured in the present work at 2150 K, show a slight negative deviation at very low alumina mole fractions which changed to a positive deviation at higher alumina contents. The activity values are in reasonable agreement with the assessment carried out by Hillert et al. The results were analysed on the basis of a slag model developed earlier at KTH, Stockholm. The present results are found to be compatible with the phase diagram proposed by Klug et al.
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PMID:A mass spectrometric study of Al(2)O(3)-SiO(2) melts using a Knudsen cell. 1134 45

Thermococcus celer cells contain a single hydrogenase located in the cytoplasm, which has been purified to apparent homogeneity using three chromatographic steps: Q-Sepharose, DEAE-Fast Flow, and Sephacryl S-200. In vitro assays demonstrated that this enzyme was able to catalyze the oxidation as well as the evolution of H2. T. celer hydrogenase had an apparent MW of 155,000+/-30,000 by gel filtration. When analyzed by SDS polyacrylamide gel electrophoresis a single band of 41,000+/-2,000 was detected. Hydrogenase activity was also detected in situ in a SDS polyacrylamide gel followed by an activity staining procedure revealing a single band corresponding to a protein of apparent Mr 84,000+/-3,000. Measurements of iron and acid-labile sulfide in different preparations of T. celer hydrogenase gave values ranging from 24 to 30 g-atoms Fe/mole of protein and 24 to 36 g-atoms of acid-labile sulfide per mole of protein. Nickel is present in 1.9-2.3 atoms per mole of protein. Copper, tungsten, and molybdenum were detected in amounts lower than 0.5 g-atoms per mole of protein. T. celer hydrogenase was inactive at ambient temperature, exhibited a dramatic increase in activity above 70 degrees C, and had an optimal activity above 90 degrees C. This enzyme showed no loss of activity after incubation at 80 degrees C for 28 h, but lost 50% of its initial activity after incubation at 96 degrees C for 20 h. Hydrogenase exhibited a half-life of approximately 25 min in air. However, after treating the air-exposed sample with sodium dithionite, more than 95% of the original activity was recovered. Copper sulfate, magnesium chloride and nitrite were also inactivators of this enzyme.
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PMID:Purification and characterization of an iron-nickel hydrogenase from Thermococcus celer. 1147 15

In the presence of mixed surfactant cetyl trimethyl ammonium bromide(CTMAB) and Tween80, the photometric analysis properties of color reaction of 3,5-dibronosalicyl fluorone (DBSAF) with tungsten(VI) were studied. The experimental result showed that tungsten(VI) reacted with DBSAF to form a micelle complex with a maximum absorption at 527 nm in a 0.60 mol x L(-1) hydrochloric acid medium. The mixed surfactant remarkably improved the sensitivity of the method and the dissolubility of the complex. The apparent molar absorptivity of the complex is 2.64 x 10(5) L x mol(-1) x cm(-1) at 527 nm. Tungsten (VI) reacted with DBSAF to form a complex with a stoichiometric ratio of 1:2, which was determined by mole ratio method and continual method of transformation, respectively. Beer's law was obeyed in the range of 0-400 microg tungsten (VI) per L. The proposed method has been applied to the determination of trace amount of tungsten in alloy steel samples.
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PMID:[Spectrophotometric study on the color reaction of multicomponent complex of tungsten-3,5-dibromosalicyl fluorone-CTMAB-Tween80]. 1576 29

A series of structurally characterized new examples of pentacoordinated heteroleptic tungsten(VI)-guanidinates complexes are described. Starting out from [WCl(2)(Nt-Bu)(2)py(2)] (1) (py = pyridine) and the guanidinato transfer reagents (TMEDA)Li[(Ni-Pr)(2)CNi-Pr(2)] (2a) (TMEDA = N,N,N',N'-tetramethylethylendiamine) and [Li(NC(NMe(2))(2))](x) (2b), the title compounds [WCl(Nt-Bu)(2)[(Ni-Pr)(2)CNi-Pr(2)]] (3) and [W(Nt-Bu)(2)Cl{NC(NMe(2))(2)]](2) (6) were selectively formed by the elimination of one mole equivalent of lithium chloride. The isopropyl-substituted guanidinato ligand [(Ni-Pr)(2)CNi-Pr(2)} of monomeric 3 is N(1),N(3)-bonded to the tungsten center. The introduction of the sterically less-demanding tetramethyl guanidinato ligand [NC(NMe(2))(2)] expectedly leads to dimeric 6 exhibiting a planar W(2)N(2) ring with the guanidinato group bridging the two tungsten centers via the deprotonated imino N-atom. The remaining chloro ligand of 3 is labile and can be substituted by sterically less-crowded groups such as dimethylamido or azido that yield the presumably monomeric compounds 4 and 5, respectively. A similar treatment of 6 with sodium azide yields the dimeric azido derivative 7. Reacting [WCl(2)(Nt-Bu)(2)py(2)] directly with an excess of sodium azide leads to the dimeric bis-azide species [[W(Nt-Bu)(2)(N(3))(mu(2)-N(3))py](2)]. The new compounds were fully characterized by single-crystal X-ray diffractometry (except 2, 4, and 5), NMR, IR, and mass-spectroscopy as well as elemental analysis. Compound 5, [W(N(3))(Nt-Bu)(2)[(Ni-Pr)(2)CNi-Pr(2)]], can be sublimed at 80 degrees C, 1 Pa.
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PMID:Mixed guanidinato/alkylimido/azido tungsten(VI) complexes: synthesis and structural characterization. 1639 65

A method for determining up to 0.15% of vanadium in high-purity niobium and tantalum metals, cast iron, steel, non-ferrous alloys and silicates is described. The proposed method is based on the extraction of a red vanadium(V)-N-benzoyl-N-phenylhydroxylamine complex into chloroform from a sulphuric-hydrofluoric acid medium containing excess of ammonium persulphate as oxidant. The molar absorptivity of the complex is 428 l.mole(-1).mm(-5) at 475 nm, the wavelength of maximum absorption. Interference from chromium(VI) and cerium(IV) is eliminated by reduction with iron(II). Common ions, including large amounts of titanium, zirconium, molybdenum and tungsten, do not interfere.
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PMID:Determination of vanadium in refractory metals, steel, cast iron, alloys and silicates by extraction of an NBPHA complex from a sulphuric-hydrofluoric acid medium. 1896 Jul 75

Hydrogen peroxide, m a mixture that is 0.1M in manganese(II) sulphate and sulphuric add and exposed to light from a tungsten lamp, decomposes slowly at room temperature in a nitrogen atmosphere. At 75 degrees the reaction is fairly rapid in the dark (about 20-25% in 4 hr) and about 60% faster in light. Presence of oxalic add has little effect on the rate of disappearance of peroxide, the overall reaction corresponding to H(2)C(2)O(4) + H(2)O(2) --> 2CO(2) + 2H(2)O. In the presence of oxygen [and manganese(II)] this reaction does not take place; instead, hydrogen peroxide is formed and oxalic add disappears in equimolar amounts. The extent of all reactions greatly increases with increasing concentration of manganese. Acrylonitrilc acts as a retarder. Conditions m the presence of mangancse(II) are described, under which oxalic add can be oxidized quantitatively by oxygen to carbon dioxide with formation of an amount of hydrogen peroxide equimolar to the oxalic add oxidized. Reaction mechanisms are proposed to account for the fact that in the absence of oxygen 1 mole of peroxide disappears and in the presence of oxygen 1 mote of peroxide is formed for each mole of oxalic add reacted.
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PMID:Formation of hydrogen peroxide upon oxidation of oxalic acid in presence and absence of oxygen-II Oxygen as oxidant. 1896 Nov 68

A simple and sensitive spectrophotometric method for the determination of vanadium based upon the reaction of vanadate with 1,10-phenanthroline in the presence of sodium dithionite in ammoniacal solution is described. The absorbance of the complex measured at 645 nm follows Beer's law for solutions containing 30-400 microg of vanadium in 100 ml of solution. A 10-fold excess of molybdenum, tungsten, phosphorus or chromium does not interfere. The molar absorptivity is 8.0 x 10(3) 1 mole(-1) cm(-1). The complex is shown to be tris-1,10-phenanthroline vanadium(II). The method has been applied successfully to the determination of vanadium in bauxite.
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PMID:Spectrophotometric determination of vanadium with 1,10-phenanthroline. 1896 Dec 34

A method for determining up to about 6% of tungsten in ores and mill products is described. It is based on the extraction of the yellow tungsten(V)-thiocyanate-diantipyrylmethane ion-association complex into chloroform from a 2.4M sulphuric acid-7.8M hydrochloric acid medium containing ammonium hydrogen fluoride as masking agent for niobium. The molar absorptivity of the complex is 1510 1. mole(-1).mm(-1) at 404 nm, the wavelength of maximum absorption. Moderate amounts of molybdenum and selenium may be present in the sample solution without causing appreciable error in the result. Interference from large amounts is avoided by separating these elements from tungsten by chloroform extraction of their xanthate complexes. Large amounts of copper interfere during the extraction of tungsten because of the precipitation of cuprous thiocyanate. Common ions, including uranium, vanadium, cobalt, titanium, arsenic and tellurium, do not interfere. The proposed method is also applicable to steel.
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PMID:Spectrophotometric determination of tungsten in ores and steel by chloroform extraction of the tungsten-thiocyanate-diantipyrylmethane complex. 1896 41


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