Selenium reductions

Although in humans only MsrBl is a selenoprotein, the depletion of selenium from the diet of mice led to increases in both R and S stereoisomers. This was not initially explained, yet a subsequent study has shown that small molecule selenols (organic selenocysteine homologues) could act as efficient electron donors in vitro for MsrA enzymes. ° This effect has only been shown in vitro, but the possibility that small molecular selenium reductants, or more likely that some selenoproteins that contain reduced selenols (in redox-active motifs) is quite intriguing. Several small selenoproteins do not have real roles and reside in nearly all subcompartments of the cell (mitochondria, ER) where electron donors for Msr enzymes are probably critical to maintain protein stability. Low selenium nutritional status would then have a significant impact on all methionine oxidation, as Future studies to address selenium nutrition and methionine oxidation could prove to be... 

Soil microorganisms may also oxidize elementary Se (Sarathchandra and Watkinson, 1981 Dowdle and Oremland, 1998) to selenite and selenate. However, microbial reduction of selenite and selenate to elementary selenium is thought to be more important and is certainly investigated more than is microbial oxidation. Both bacteria and fungi (Bautista and Alexander, 1972) play roles in selenium reduction, but the former have been studied more extensively (White et al., 1995). Bacteria may reduce Se under both aerobic (Lortie et al., 1992 Garbisu et al., 1995 Dungan et al., 2003) and anaerobic conditions (Oremland... 

To meet the needs of the advanced students, preparations have now been included to illustrate, for example, reduction by lithium aluminium hydride and by the Meerwein-Ponndorf-Verley method, oxidation by selenium dioxide and by periodate, the Michael, Hoesch, Leuckart and Doebner-Miller Reactions, the Knorr pyrrole and the Hantzsch collidine syntheses, various Free Radical reactions, the Pinacol-Pinacolone, Beckmann and Arbusov Rearrangements, and the Bart and the Meyer Reactions, together with many others. 

Phytoremediation is also being developed for dealing with soils contaminated with high levels of selenium in California again B.juncea seems to be particularly effective in accumulating the contaminant from soil, and all plants tested were more effective at removing selenate than selenite (92). This is an interesting contrast to bacterial systems, where selenite reduction is more commonly found than selenate reduction. 

Attempts have been made to develop methods for the production of aromatic isocyanates without the use of phosgene. None of these processes is currently in commercial use. Processes based on the reaction of carbon monoxide with aromatic nitro compounds have been examined extensively (23,27,76). The reductive carbonylation of 2,4-dinitrotoluene [121 -14-2] to toluene 2,4-diaLkylcarbamates is reported to occur in high yield at reaction temperatures of 140—180°C under 6900 kPa (1000 psi) of carbon monoxide. The resultant carbamate product distribution is noted to be a strong function of the alcohol used. Mitsui-Toatsu and Arco have disclosed a two-step reductive carbonylation process based on a cost effective selenium catalyst (22,23). 

In many reactions, selenium is an oxidant as well as a reductant. Strong oxidants convert selenium dioxide and its derivatives to the hexavalent state. Although hexavalent selenium compounds are oxidants, these are less active and difficult to reduce. Selenium salts resemble the corresponding sulfur and tellurium salts in behavior. 

Chlorine may initially convert the selenium in solution to the hexavalent state, but as the hydrochloric acidity increases, reduction to the tetravalent state occurs spontaneously. 

Selenium and precious metals can be removed selectively from the chlorination Hquor by reduction with sulfur dioxide. However, conditions of acidity, temperature, and a rate of reduction must be carefliUy controlled to avoid the formation of selenium monochloride, which reacts with elemental selenium already generated to form a tar-like substance. This tar gradually hardens to form an intractable mass which must be chipped from the reactor. Under proper conditions of precipitation, a selenium/precious metals product substantially free of other impurities can be obtained. Selenium can be recovered in a pure state by vacuum distillation, leaving behind a precious metals residue. 

Bina Selenides. Most biaary selenides are formed by beating selenium ia the presence of the element, reduction of selenites or selenates with carbon or hydrogen, and double decomposition of heavy-metal salts ia aqueous solution or suspension with a soluble selenide salt, eg, Na2Se or (NH 2S [66455-76-3]. Atmospheric oxygen oxidizes the selenides more rapidly than the corresponding sulfides and more slowly than the teUurides. Selenides of the alkah, alkaline-earth metals, and lanthanum elements are water soluble and readily hydrolyzed. Heavy-metal selenides are iasoluble ia water. Polyselenides form when selenium reacts with alkah metals dissolved ia hquid ammonia. Metal (M) hydrogen selenides of the M HSe type are known. Some heavy-metal selenides show important and useful electric, photoelectric, photo-optical, and semiconductor properties. Ferroselenium and nickel selenide are made by sintering a mixture of selenium and metal powder. 

Comprehensive accounts of the various gravimetric, polarographic, spectrophotometric, and neutron activation analytical methods have been pubHshed (1,2,5,17,19,65—67). Sampling and analysis of biological materials and organic compounds is treated in References 60 and 68. Many analytical methods depend on the conversion of selenium in the sample to selenous acid, H2Se02, and reduction to elemental selenium when a gravimetric deterrnination is desired. 

A number of substances, such as the most commonly used sulfur dioxide, can reduce selenous acid solution to an elemental selenium precipitate. This precipitation separates the selenium from most elements and serves as a basis for gravimetry. In a solution containing both selenous and teUurous acids, the selenium may be quantitatively separated from the latter by performing the reduction in a solution which is 8 to 9.5 W with respect to hydrochloric acid. When selenic acid may also be present, the addition of hydroxylamine hydrochloride is recommended along with the sulfur dioxide. A simple method for the separation and deterrnination of selenium(IV) and molybdenum(VI) in mixtures, based on selective precipitation with potassium thiocarbonate, has been developed (69). 

A widely used procedure for determining trace amounts of selenium involves separating selenium from solution by reduction to elemental selenium using tellurium (as a carrier) and hypophosphorous acid as reductant. The precipitated selenium, together with the carrier, are collected by filtration and the filtered soflds examined directly in the wavelength-dispersive x-ray fluorescence spectrometer (70). Numerous spectrophotometric and other methods have been pubHshed for the deterruination of trace amounts of selenium (71—88). 

Selenium. Selenium is determined by atomic absorption after the organoselenides are broken down with acidic persulfate and all forms of selenium have been converted to H2Se. The reduction is brought about in acidic solution of KI—SnCl2 or borohydride, and H2Se is generated by addition... 

Although it is only slowly oxidized in moist air at ambient temperature, cadmium forms a fume of brown-colored cadmium oxide [1306-19-0] CdO, when heated in air. Other elements which react readily with cadmium metal upon heating include the halogens, phosphoms, selenium, sulfur, and tellurium. The standard reduction potential for the reaction... 

These are known as chemically pure (CP) cadmiums. With the development of other uses for cadmium and selenium, costs have risen substantially in recent years. Some cost reduction may be obtained by use of the cadmium Hthopones. These have the same relative shades but have been coprecipitated onto about 60% barium sulfate. The resulting extensions give better money value, if the higher pigment loading can be tolerated, with no loss in properties. 

It is known that Selenium catalyzes reaction of some dye reduction by Sulphide. On this basis spectrophotometric and test-techniques for Selenium determination are developed. Inefficient reproducibility and low sensitivity are their deficiencies. In the present work, solid-phase reagent on silica gel modified first with quaternary ammonium salt and then by Indigocarmine was proposed for Selenium(IV) test-determination. Optimal conditions for the Selenium determination by method of fixed concentration were found. The detection limit of Se(IV) is 10 ftg/L = 2 ng/sample). Calibration curve is linear in the range 50-400 ftg/L of Se(IV). The proposed method is successfully applied to the Selenium determination in multivitamins and bioadditions. 

Selenium, ionization energy, 410 Self oxidation-reduction, 361 Separation of charge, 312 Separations by crystallization, 413 by distillation, 70 by precipitation, 176 Seventh column of periodic table, 352... 

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