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PubMed2000

In vivo degradation of tungsten embolisation coils.

It has been suggested that tungsten embolisation coils in intracranial aneurysms may dissolve in situ. These coils are also used, in much larger quantities, for the occlusion of larger vessels outside the cranium. This study was performed to investigate whether tungsten embolisation coils may become degraded in vivo and to examine whether this is radiographically evident on medium-term follow-up. 10 patients who had undergone aortic stent-graft repair of an abdominal aortic aneurysm (8 male and 2 female, mean age 69.7 years) and 10 age- and sex-matched controls were studied. The study group had also received an average of 64 cm of tungsten coil either to prevent or to treat an endoleak. Whole blood, serum and urine tungsten levels were assayed. Immediate post-operative and follow-up abdominal radiographs were reviewed by two consultant vascular radiologists to detect visible changes in the coils. Whole blood, serum and urine levels of tungsten were highly and significantly elevated (p < 0.001) in the study group compared with the controls. No radiographic changes in the coils were seen at an average of 16.7 months. In conclusion, tungsten embolisation coils dissolve in humans but radiographic changes are not apparent on medium-term follow-up. The clinical significance of these findings is uncertain but long-term follow-up is needed.

Aged↗
PubMed2006

Interaction of CO with palladium supported on oxidized tungsten.

A model catalyst system, palladium on tungsten oxide, has been examined by temperature-programmed desorption and photoemission spectroscopy. The samples were prepared by evaporation of palladium onto an oxidized tungsten foil under ultrahigh vacuum conditions. Mostly three-dimensional (3-D) palladium (Pd) clusters were found to be present on oxidized tungsten (WOx) surfaces at room temperature. Upon annealing to 670 K, the palladium clusters are redispersed and decorated by the WOx surface layer. The nature of the WOx phase on top of the palladium clusters is dependent on the mode of oxidation of the tungsten foil prior to palladium deposition. Mainly W(2+) species decorate palladium deposits on tungsten oxidized at room temperature, while mainly W(4+) species are on top of palladium deposits on the surface oxidized at 1300 K. The appearance of a Pd(n+)-O-W(4+) mixed oxide phase with n < 2 was observed on the oxidized tungsten surface. The substantial reduction (relative to nonannealed samples) of molecular CO coverage induced by annealing is discussed in terms of the changes in chemical composition and morphology of the outermost surface.

Journal Article↗
PubMed1978

Cemented tungsten carbide pneumoconiosis.

An autopsy case of cemented tungsten carbide pneumoconiosis, the first lethal case in our country, is presented. A 28-year-old woman, who had been engaged in grinding presintered metallic matrix for four years, developed respiratory symptoms. X-ray examinations were indicative of interstitial pulmonary fibrosis. Corticosteroid therapy revealed only little effect. She expired five years after the onset of the symptoms. Postmortem examination showed nonspecific interstitial pneumonitis resulting in marked lung fibrosis. Ultrastructurally, crystals were observed in cytoplasm of presumable macrophages in the fibrotic lung tissue. Electron probe microanalysis of the lung tissue showed the presence of tungsten and other constituents of tungsten carbide except for cobalt. Metal analysis demonstrated a large amount of tungsten in the lung. Cobalt was detected tenfold of the normal value in the bone. In pathogenesis of the pneumoconiosis in the cemented tungsten carbide workers, toxicity of cobalt is most suspectable, and in addition, individual susceptibility may be also important.

Adult↗
PubMed2003

Composition and in vitro biocompatibility of corroding tungsten coils.

The purpose of the article is to evaluate composition and biocompatibility of corroding mechanically detachable spirals (MDS, Balt Extrusion, Montmorency, France). Analysis of the material composition of corroding MDS coils was assessed by inductively coupled plasma atomic emission spectroscopy, inductively coupled plasma mass spectroscopy, and wavelength-dispersive x-ray spectrometry. Toxicity assays were performed with human venous endothelial cells, venous smooth muscle cells and fibroblasts. The analyses of the MDS coils demonstrated a tungsten content of the dissolving MDS spirals of > 99.9 mas%. In vitro, human endothelial, vascular smooth muscle cells and fibroblasts were not adversely affected by markedly elevated tungsten concentrations (60,500 microg/l) after 12 days in the culture medium. The examined cells showed an extensive vital growth on the coil surface. Corrosion of tungsten coils leads to markedly elevated tungsten levels in the culture medium. However, growth and vitality of endothelial cells, fibroblasts, and vascular smooth muscle cells are not adversely affected by elevated tungsten concentrations.

Biocompatible Materials↗
PubMed1994

Tungstate can substitute for molybdate in sustaining growth of Methanobacterium thermoautotrophicum. Identification and characterization of a tungsten isoenzyme of formylmethanofuran dehydrogenase.

Methanobacterium thermoautotrophicum (strain Marburg) was found to grow on media supplemented with tungstate rather than with molybdate. The Archaeon then synthesized a tungsten iron-sulfur isoenzyme of formylmethanofuran dehydrogenase. The isoenzyme was purified to apparent homogeneity and shown to be composed of four different subunits of apparent molecular masses 65 kDa, 53 kDa, 31 kDa, and 15 kDa and to contain per mol 0.4 mol tungsten, < 0.05 mol molybdenum, 8 mol non-heme iron, 8 mol acid-labile sulfur and molybdopterin guanine dinucleotide. Its molecular and catalytic properties were significantly different from those of the molybdenum isoenzyme characterized previously. The two isoenzymes also differed in their metal specificity: the active molybdenum isoenzyme was only synthesized when molybdenum was available during growth whereas the active tungsten isoenzyme was also generated during growth of the cells on molybdate medium. Under the latter conditions the tungsten isoenzyme was synthesized containing molybdenum rather than tungsten.

Aldehyde Oxidoreductases↗
PubMed1995

A simple and comprehensive method for the construction, repair and recycling of single and double tungsten microelectrodes.

A method for the construction, repair and recycling of tungsten-in-glass micro-electrodes is described. Essentially, the method employs insulating tungsten electrodes by collapsing borosilicate-glass capillaries onto tungsten wires. Procedures are described for either (1) removing excess glass insulation from the microelectrode tip or (2) fine adjustment and reshaping of the exposed electrode tip. This approach enables the controlled shaping of the electrode tip during preparation and/or reshaping the electrode tip or glass insulation of damaged electrodes. The method may be applied in the preparation of bipolar tungsten-in-glass electrode and tungsten electrode/micropipette assemblies. Advantages of the method are discussed.

Electrophysiology↗
PubMed1985

Sputter shadowing improved by using a tungsten target.

This work builds upon a previous paper (W. Colquhoun, 1984, J. Ultrastruct. Res. 87, 97) in which a sputter shadowing device was briefly described. The device allowed TEM specimens to be shadowed in a conventional sputter coater. Images obtained by sputter shadowing with a standard Au/Pd target were of good quality but were slightly inferior to the best that could be obtained by e--beam evaporation of tungsten. Here we show that construction and use of a tungsten target greatly improves the quality of the sputter shadowed deposit. Images of DNA and ribosomal subunits contrasted by sputter shadowing with tungsten are shown. The DNA images indicate that sputter shadowing with tungsten is a gentle contrasting technique. The sputter shadowed images of the 30 S ribosomal subunits show the major features of the particle revealed by evaporation shadowing using the most sophisticated of methods in that technology. Advantages of sputter shadowing are discussed and a rationale for the improved grain obtained by sputtering tungsten is suggested.

Bacteriophage lambda↗
PubMed2006

Bio-availability of tungsten in the vicinity of an abandoned mine in the English Lake District and some potential health implications.

This research addresses the occurrence, detection and possible fate of tungsten in the vicinity of an abandoned mine in the English Lake District. Aqua regia extraction and subsequent analysis of spoil and vegetation confirmed the presence of tungsten and other heavy metals. Spoil samples examined were last worked almost 100 years ago and the concentrations of copper, zinc, tungsten and arsenic detected demonstrate the environmental persistence of these metals in an area of relatively high rainfall. The bioaccumulation of tungsten by two species of plants is indicated and partitioning within different tissues of Calluna vulgaris is demonstrated. Mechanisms relating to mobility and speciation of the metals present were explored using sequential and single stage extraction systems. Tungsten appears to be relatively immobile when subjected to sequential extraction but increased bioavailability is indicated when single stage extraction using EDTA is employed.

Arsenic↗
PubMedDate not supplied

Exposures from thorium contained in thoriated tungsten welding electrodes.

Information provided in this article can be used for estimating the radiation dose associated with the use of thoriated tungsten electrodes in tungsten inert gas welding. Area and breathing zone concentrations of 232Th generated by welding and electrode sharpening along with particle size information; isotopic composition of electrodes from two domestic manufacturers and one European manufacturer; and process variables and estimates on the number of thoriated tungsten electrodes manufactured are presented. Past literature is reviewed and compared with the results of this study. Isotopic analysis of a nominal 2% thoriated electrode found 0.6 ppm +/- 0.4 ppm 230Th and less than 0.1 ppm 228Th. Analysis of a ceriated tungsten electrode and a lanthanated tungsten electrode for 232Th found 124 ppm and 177 ppm, respectively. Electrode consumption during welding was primarily the result of tip sharpening. Less than 3% of the weight loss was attributable to the welding process. The in-mask concentration of respirable thorium particulate in the welder's breathing zone was 0.002 x 10(-12) microCi 232Th/mL. The concentration of respirable thorium particulate from electrode sharpening was 1.3 x 10(-12) microCi 232Th/mL. The measured sharpening time was 20 sec per electrode. Estimates of the activity median aerodynamic diameters for the respirable fraction of the welding and electrode sharpening aerosols were 3.5 and 5 microns, respectively, when measured in the breathing zone at 0.3 m (12 inches) from the point of operation. The respirable fraction of the total welding and sharpening aerosols was 45 and 60%.

Air Pollutants, Occupational↗
PubMed1992

A molybdenum and a tungsten isoenzyme of formylmethanofuran dehydrogenase in the thermophilic archaeon Methanobacterium wolfei.

We have recently reported that the thermophilic archaeon Methanobacterium wolfei contains two formylmethanofuran dehydrogenases, I and II. Formylmethanofuran dehydrogenase II, which is preferentially expressed in tungsten-grown cells, has been purified and shown to be a tungsten-iron-sulfur protein. We have now purified and characterized formylmethanofuran dehydrogenase I from molybdenum-grown cells and shown that it is a molybdenum-iron-sulfur protein. The purified enzyme, with a specific activity of 27 U/mg protein, was found to be composed of three subunits of apparent molecular mass 64 kDa, 51 kDa, and 31 kDa and to contain per mol 146-kDa molecule approximately 0.23 mol molybdenum, 0.46 mol molybdopterin guanine dinucleotide, and 6.6 mol non-heme iron but no tungsten (< 0.01 mol). The molybdenum enzyme differed from the tungsten enzyme (8 U/mg) in that it catalyzed the oxidation of N-furfurylformamide and formate and was inactivated by cyanide. The two enzymes also differed significantly in the pH optimum, in the apparent Km for the electron acceptor, and in the chromatographic behaviour. The molybdenum enzyme and the tungsten enzyme were similar, however, in that the N-terminal amino acid sequences determined for the alpha and beta subunits were identical up to residue 23, indicating that the two proteins are isoenzymes. The molybdenum enzyme, as isolated, was found to display an EPR signal derived from molybdenum as evidenced by isotope substitution.

Aldehyde Oxidoreductases↗
PubMedDate not supplied

Use of a tungsten filter to improve beam uniformity.

A general method for calculating the dose distribution in an irradiated volume is to evaluate the primary and scatter components separately according to the method described by Clarkson and Cunningham. It was found, however, that for a 6 MV Siemens accelerator the calculated dose overestimated the peripheral dose at depths beyond 10 cm by 3%-6%. The difference was attributed to the varying beam quality across the field. This beam quality variation was decreased by hardening the beam with a permanently installed 1/3 in. tungsten filter inserted between the beam flattening filter and the mirror base assembly. The tungsten filter had a more pronounced beam hardening effect at the beam edge than along the central ray. For example, the dose rate in air at the beam edge for a 30 x 30 cm2 field was 13% higher than along the central ray without the tungsten filter. The addition of the 1/8 in. filter decreased this horn to 6%. The beam quality along the central ray also increased. The tissue-air ratio for zero field size along the central ray increased by 2% with the addition of the tungsten filter. The scatter-air ratio, however, did not change with the added filter. Agreement within 1%-2% was achieved between the calculated and measured beam profiles at all depths in a phantom when the tungsten filter was added.

Filtration↗
PubMed1995

Maintenance of stellite and tungsten carbide saw tips: respiratory health and exposure-response evaluations.

OBJECTIVE: To study exposure to cobalt and chromium in saw maintenance rooms and test respiratory health among saw filers at lumber mills. Hard-metal lung disease is associated with cobalt in the manufacture of tungsten carbide tools; recently it has also been reported among tool maintenance workers. Lumber mills often use saws tipped with tungsten carbide or with a newer alloy, stellite (containing more cobalt, as well as chromium). METHODS: A cross sectional study of 118 saw filers at eight lumber mills was carried out that included a standardised questionnaire, spirometry, personal air sampling, and examination of tasks every 10 minutes (by observation). Comparison data were from a study of bus mechanics tested with similar methods. RESULTS AND CONCLUSION: Cobalt exposure was associated with tungsten carbide grinding but not with stellite grinding. Chromium exposure was associated mainly with stellite welding. Saw filers had a twofold increase in phlegm and wheeze (P < 0.01) and a threefold increase in cough, phlegm, and wheeze related to work (P < 0.001), but no increase in breathlessness. Stellite welding was associated with a significant increase in nasal symptoms and cough related to work and a small decrease in airflow (forced expiratory volume in one second/forced vital capacity (FEV1/FVC%), P < 0.05). Saw filers wet grinding with tungsten carbide had significant reductions in forced expiratory lung volumes (FEV1 and FVC, P < 0.05) and were significantly more likely to have FEV1 and FVC values in the abnormal range. Cobalt exposure (in wet grinding) and duration of work that involved tungsten carbide grinding were both associated with significant reductions in FEV1 and FVC. Average cobalt exposures in this study were about 5 micrograms/m3, well below the currently accepted permissible concentration, which suggests that the current workplace limit for cobalt may be too high.

Adult↗
PubMed1983

Tungsten anode tubes with K-edge filters for mammography.

A number of authors have calculated the optimum X-ray energies for mammography using, as a criterion, the maximum signal to noise ratio (SNR) per unit dose to the breast, or conversely the minimum exposure for constant SNR. Filters having absorption edges at appropriate energy positions have been used to modify the shape of tungsten anode spectra to bring them close to the calculated optimum. The suitability of such spectra for practical use has been assessed by comparing both the film image quality and the incident breast dose obtained using a K-edge filtered tungsten anode tube with that obtained using a molybdenum anode tube. Image quality has been assessed both by using a "random" phantom and by comparing mammograms of women attending a screening clinic where one breast was radiographed using a filtered tungsten anode tube and the other using a standard molybdenum anode unit. Relative breast doses were estimated from both ionisation chamber measurements with a phantom and thermoluminescent dosimetry measurements on the breast. The film image quality assessment indicated that the filtered tungsten anode tube gave results which were not significantly different from those obtained with a molybdenum anode tube for a tissue thickness of about 4 cm and which were better for larger breast thicknesses. The dose could be reduced to between one-half and one-third with the filtered tungsten anode tube.

Female↗
PubMed1998

Influences of supplementary dietary tungsten on methionine metabolism in rabbits fed a low-cholesterol plus methionine diet.

Hyperhomocysteinemia results from an impaired methionine metabolism. Sulfite oxidase, which is an important enzyme in methionine metabolism, contains molybdenum. In contrast, tungsten has a molybdenum-antagonistic effect. Thus, we hypothesized that dietary tungsten may decrease plasma homocysteine levels and influence methionine metabolism. Male New Zealand White rabbits (n=15) were fed a low-cholesterol basal diet and then placed on three different diets: 0.1% cholesterol (Chol), Chol plus 1% methionine (Met), and Chol plus Met plus 0.1% tungsten (W). The animals received these diets for 20 weeks. Biochemical tests of blood and urine were performed. Plasma homocysteine levels were significantly lower in the Chol+Met+W group than in the Chol+Met group. Plasma levels of total cholesterol, triglyceride, lipid peroxide, and urinary 24-h taurine concentrations were higher in the Chol + Met + W group than in the Chol + Met group. In comparison, concentrations of 2, 3-diphosphoglycerate (2, 3-DPG), reduced glutathione (GSH) in erythrocytes, and urinary 24-h SO4(2) were lower in the Chol+Met+W group than in the Chol+Met group. From these results, tungsten could be expected to exhibit an antiatherogenic effect. Conversely, it may have effects on atherogenic factors. Thus, tungsten may play a number of roles in the methionine metabolism.

2,3-Diphosphoglycerate↗
PubMed1976

Electron paramagnetic resonance of the tungsten derivative of rat liver sulfite oxidase.

Sulfite oxidase purified from livers of tungsten-treated rats has been used for EPR studies of tungsten substituted at the molybdenum site of the enzyme in a fraction of the molecules. The EPR signal of W(V) in sulfite oxidase is quite similar to that of Mo(V) in its line shape and in its sensitivity to the presence of anions such as phosphate and fluoride. Hyperfine interaction with a dissociable proton is also observed in both signals. The pH-dependent alteration in line shape exhibited by the Mo(V) EPR signal of the rat liver enzyme. Incomplete reduction of the tungsten center at pH 9 is indicated by attenuated signal intensity at this pH. The W(V) signal has g values lower than those of the Mo(V) signal, has a much broader resonance envelope, and is much less readily saturated by increasing microwave power. Kinetic studies on the reduction of the heme and tungsten centers of sulfite oxidase have shown that reduction of de-molybdo forms of sulfite oxidase by sulfite is catalyzed by the residual traces of native molybdenum-containing molecules. Reduction is accomplished by electron transfer involving intermolecular heme-heme interaction. The W(V) signal is generated only after all the heme centers are reduced. The rate and extent of heme reduction at pH 9 are the same as at pH 7. Studies on the reoxidation of W(V) and reduced heme by O2 and by cytochrome c suggest that the cytochrome b5 of sulfite oxidase is the site of electron transfer to cytochrome c, whereas oxidase activity is the property of the molybdenum center. It appears that the tungsten center in sulfite oxidase is incapable of oxidizing sulfite.

Anaerobiosis↗
PubMed2003

Tuning the redox potentials of dinuclear tungsten oxo complexes [(Cp*W(4,4'-R,R-2,2'-bpy)(mu-O))2][PF6]2 toward photochemical water splitting.

A series of novel dinuclear tungsten(IV) oxo complexes with disubstituted 4,4'-R,R-2,2'-bipyridyl (R(2)bpy) ligands of the type [(Cp*W(R(2)bpy)(mu-O))(2)][PF(6)](2) (R=NMe(2), tBu, Me, H, Cl) was prepared by hydrolysis of the tungsten(IV) trichloro complexes [Cp*W(R(2)bpy)Cl(3)]. Cyclic voltammetry measurements for the tungsten(IV) oxo compounds provided evidence for one reversible oxidation and two reversible reductions leading to the oxidation states W(V)W(IV), W(IV)W(III) and W(III)W(III). The corresponding complexes [(Cp*W(R(2)bpy)(mu-O))(2)](n+) [PF(6)](n) (n=0 for R=Me, tBu, and 1, 3 for both R=Me) could be isolated after chemical oxidation/reduction of the tungsten(IV) oxo complexes. The crystal structures of the complexes [(Cp*W(R(2)bpy)(mu-O))(2)][BPh(4)](2) (R=NMe(2), tBu) and [(Cp*W(Me(2)bpy)(mu-O))(2)](n+)[PF(6)](n) (n=0, 1, 2, 3) show a cis geometry with a puckered W(2)O(2) four-membered ring for all compounds except [(Cp*W(Me(2)bpy)(mu-O))(2)] which displays a trans geometry with a planar W(2)O(2) ring. Examining the interaction of these novel tungsten oxo complexes with protons, we were able to show that the W(IV)W(IV) complexes [(Cp*W(R(2)bpy)(mu-O))(2)][PF(6) (-)](2) (R=NMe(2), tBu) undergo reversible protonation, while the W(III)W(III) complexes [(Cp*W(R(2)bpy)(mu-O))(2)] transfer two electrons forming the W(IV)W(IV) complex and molecular hydrogen.

Journal Article↗
PubMed2003

Stereocontrolled synthesis of bicyclic lactone derivatives via tungsten-mediated [3 + 2] cycloaddition of epoxides with a tethered alkynyl group.

In the presence of BF3*Et2O, alkynyltungsten complexes underwent [3 + 2] cycloaddition with tethered epoxides to give bicyclic -lactones efficiently. Only one diastereomeric product was formed despite the presence of three stereogenic centers. A mechanism is proposed that involves formation of a tungsten-vinylidenium species via an SN2 attack of the epoxide carbon by an alkynyltungsten group to give a tungsten-enol ether species via counterattack at the central tungsten-vinylidenium carbon by the OBF3- terminus. Most of the tungsten enol ether species were too unstable for isolation and underwent hydrolysis to give only cis-fused -bicyclic lactones. This cyclization works for both cis- and trans-epoxides and tolerates various functional groups. In the case of trans-phenyl epoxide, the reaction led to an addition product via a 6-endo attack of epoxide by the tungsten fragment. This method provides a simple enantiospecific synthesis of complex bicyclic lactones if a chiral epoxide is used in the cyclization. It is also applicable to the one-pot synthesis of bicyclic unsaturated gamma-lactones if a suitable alkynyltungsten functionality is used.

Journal Article↗
PubMed2005

Atomic tungsten for ultrafast hard X-ray generation.

High-resolution X-ray absorption measurements (with an accuracy of +/-0.3 eV) of ZnSO(4) (aq) were performed with ultrafast selected energy X-ray absorption spectroscopy (USEXAS) using a laser-driven tungsten target X-ray source. The results were used to determine the absolute spectral positions of characteristic emission lines. By comparing these positions to those predicted for the line emission from tungsten of different oxidation states using the Dirac-Fock formula, the tungsten species responsible for ultrafast hard X-ray generation were found to be tungsten atoms. This finding provides the first direct evidence to support the mechanism of X-ray generation via high-energy electrons interacting with tungsten atoms in the solid target.

Journal Article↗