Phosphates, by oxidation

CFA is omnipresent in pelagic sediments, ferromanganese nodules, and seamount crusts, and marine phosphorites on continental margins and seamounts. Supply of phosphate by oxidation of organic matter and pre-concentration of phosphate by iron oxyhy dr oxides, supply of calcium by dissolution of carbonates or carbonates acting as substrates, and supply of fluorine from seawater are all important factors in the formation of marine phosphorites. 

Hexafluorophosphoric Acid. Hexafluorophosphoric acid (3) is present under ambient conditions only as an aqueous solution because the anhydrous acid dissociates rapidly to HF and PF at 25°C (56). The commercially available HPF is approximately 60% HPF based on PF analysis with HF, HPO2F2, HPO F, and H PO ia equiUbrium equivalent to about 11% additional HPF. The acid is a colorless Hquid which fumes considerably owiag to formation of an HF aerosol. Frequently, the commercially available acid has a dark honey color which is thought to be reduced phosphate species. This color can be removed by oxidation with a small amount of nitric acid. When the hexafluorophosphoric acid is diluted, it slowly hydrolyzes to the other fluorophosphoric acids and finally phosphoric acid. In concentrated solutions, the hexafluorophosphoric acid estabUshes equiUbrium with its hydrolysis products ia relatively low concentration. Hexafluorophosphoric acid hexahydrate [40209-76-5] 6 P 31.5°C, also forms (66). This... 

The acid process has three advantages over the alkaline process, ie, (/) higher yield of phosphine (60 vs 25%) (2) more pure gas for use in subsequent reactions (95 vs 40%) and (J) by-product phosphoric acid is relatively valuable and can be sold into a number of markets, eg, in the manufacture of fertilizers and flame retardants. There is no ready outlet for the mixture of phosphites produced via the alkaline route and additional processing by oxidative spray drying is needed to produce phosphates for sale (3). 

Coesite. Coesite, the second most dense (3.01 g/cm ) phase of silica, was first prepared ia the laboratory by heating a mixture of sodium metasibcate and diammonium hydrogen phosphate or another mineraliser at 500—800°C and 1.5—3.5 GPa (14,800—34,540 atm). Coesite has also been prepared by oxidation of silicon with silver carbonate under pressure (67). The stmcture is monoclinic = 717 pm, Cg = 1.238 pm, and 7 = 120°. 

Because the 2 NADH formed in glycolysis are transported by the glycerol phosphate shuttle in this case, they each yield only 1.5 ATP, as already described. On the other hand, if these 2 NADH take part in the malate-aspartate shuttle, each yields 2.5 ATP, giving a total (in this case) of 32 ATP formed per glucose oxidized. Most of the ATP—26 out of 30 or 28 out of 32—is produced by oxidative phosphorylation only 4 ATP molecules result from direct synthesis during glycolysis and the TCA cycle. 

One of the most widely used methods for the formation of phosphate esters involves the conversion of a P-N bond of a phosphorus(III) compound to a P-O bond by ROH, catalyzed by l//-tetrazole, followed by oxidation to the phosphorus(V) derivative ... 

Preparation of (Me0)2P-0-R ROH, (MeO)3P, CBr4, Pyr, 70-98% yield. The alkyl dimethyl phosphite may then be oxidized to the corresponding phosphate by aq. iodine, t-butyl hydroperoxide, or peracid. 

The SATE ester is formed from a phosphite using PvCl activation followed by oxidation to the phosphate with l2/H20. ... 

Production is still increasing steadily in many countries Thennar acid (made by oxidation of phosphorus in the presence of water vapour) is about 3 times as expensive as wet acid (made by treating rock phosphate with sulfuric acid). The present approximate pattern of production and uses is shown in the following scheme ... 

Step 4 With the coupling accomplished, the phosphite product is oxidized to a phosphate by treatment with iodine in aqueous tetrahydrofuran in the presence of 2,6-dimethylpyridine. The cycle (1) deprotection, (2) coupling, and (3) oxidation is then repeated until an oligonucleotide chain of the desired sequence has been built. 

Crucibles fitted with permanent porous plates are cleaned by shaking out as much of the solid as possible, and then dissolving out the remainder of the solid with a suitable solvent. A hot 0.1 M solution of the tetrasodium salt of the ethylenediaminetetra-acetic acid is an excellent solvent for many of the precipitates [except metallic sulphides and hexacyanoferrates(III)] encountered in analysis. These include barium sulphate, calcium oxalate, calcium phosphate, calcium oxide, lead carbonate, lead iodate, lead oxalate, and ammonium magnesium phosphate. The crucible may either be completely immersed in the hot reagent or the latter may be drawn by suction through the crucible. 

Fig. 3. Cation-exchange chromatography of protein standards. Column poly(aspartic acid) Vydac (10 pm), 20 x 0.46 cm. Sample 25 pi containing 12.5 pg of ovalbumin and 25 pg each of the other proteins in the weak buffer. Flow rate 1 ml/min. Weak buffer 0.05 mol/1 potassium phosphate, pH 6.0. Strong buffer same +0.6 mol/1 sodium chloride Elution 80-min linear gradient, 0-100% strong buffer. Peaks a = ovalbumin, b = bacitracin, c = myoglobin, d = chymotrypsinogen A, e = cytochrom C (reduced), / = ribonuclease A, g = cytochrome C (oxidised), h = lysozyme. The cytochrome C peaks were identified by oxidation with potassium ferricyanide and reduction with sodium dithionite [47]...

Oxidation of phenyl hexyl sulphide with sodium metaperiodate gave also only a trace amount of the corresponding sulphoxide72. On the other hand, Hall and coworkers73 prepared benzylpenicillin and phenoxymethyl penicillin sulphoxides from the corresponding benzyl esters by oxidation with sodium metaperiodate in dioxane solution with a phosphate buffer. A general procedure for the synthesis of penicillin sulphoxides was reported later by Essery and coworkers74 which consists in the direct oxidation of penicillins or their salts with sodium metaperiodate in aqueous solution at pH 6.5-7.0. 1-Butadienyl phenyl sulphoxide 4475 and a-phosphoryl sulphoxides 4576 were also prepared by the same procedure. 

The analysis of phosphates and phosphonates is a considerably complex task due to the great variety of possible molecular structures. Phosphorus-containing anionics are nearly always available as mixtures dependent on the kind of synthesis carried out. For analytical separation the total amount of phosphorus in the molecule has to be ascertained. Thus, the organic and inorganic phosphorus is transformed to orthophosphoric acid by oxidation. The fusion of the substance is performed by the addition of 2 ml of concentrated sulfuric acid to — 100 mg of the substance. The black residue is then oxidized by a mixture of nitric acid and perchloric acid. The resulting orthophosphate can be determined at 8000 K by atom emission spectroscopy. The thermally excited phosphorus atoms emit a characteristic line at a wavelength of 178.23 nm. The extensity of the radiation is used for quantitative determination of the phosphorus content. 

This process of aging is believed to be critical in the development of delayed neuropathy, after NTE has been phosphorylated by an OP (see Chapter 10, Section 10.2.4). It is believed that most, if not all, of the B-esterases are sensitive to inhibition by OPs because they, too, have reactive serine at their active sites. It is important to emphasize that the interaction shown in Fignre 2.11 occurs with OPs that contain an oxon group. Phosphorothionates, which contain instead a thion group, do not readily interact in this way. Many OP insecticides are phosphorothionates, but these need to be converted to phosphate (oxon) forms by oxidative desulfuration before inhibition of acetylcholinesterase can proceed to any significant extent (see Section 2.3.2.2). 

Figure 7-10. Coupled enzyme assay for hexokinase activity. The production of glucose 6-phosphate by hexokinase is coupled to the oxidation of this product by glucose-6-phosphate dehydrogenase in the presence of added enzyme and NADP". When an excess of glucose-6-phosphate dehydrogenase is present, the rate of formation of NADPH, which can be measured at 340 nm, is governed by the rate of formation of glucose 6-phosphate by hexokinase.

Figure 34-2 illustrates the intermediates and reactions for conversion of a-D-ribose 5-phosphate to inosine monophosphate (IMP). Separate branches then lead to AMP and GMP (Figure 34-3). Subsequent phosphoryl transfer from ATP converts AMP and GMP to ADP and GDP. Conversion of GDP to GTP involves a second phosphoryl transfer from ATP, whereas conversion of ADP to ATP is achieved primarily by oxidative phosphorylation (see Chapter 12).

Free-radical intermediates in the oxidation of a series of quinol phosphates by permanganate at pH 11.7 have been characterised by an esr rapid-mixing technique . Clearly a one-equivalent oxidation step to give a semiquinone phosphate radical operates in this case. 

Citraconic anhydride (Methyl maleic anhydride) was found to be produced from pyruvic acid by an oxidative decarboxy-condensation. The best catalyst is iron phosphate with a P/Fe atomic ratio of 1.2. The presence of oxygen is required to promote the reaction. The main side-reaction is formation of acetic acid and CO2 by oxidative C-C bond fission. The best results are obtained at a temperature of 200°C. The yield of citraconic anhydride reaches 71 mol% at a pyruvic acid conversion of 98%. 

The zinc oxide used in ZOE cements differs entirely from that used in zinc phosphate cements. Whereas the latter has to be ignited to a very high temperature to deactivate it, the opposite is true of the zinc oxides used in the ZOE cement, which are of an activated variety. They are normally prepared by the thermal decomposition of zinc salts at 350 °C to 450 °C such oxides are yellow. Zinc oxides prepared by oxidizing zinc in oxygen may also be used these are white. 

Baker, M.S., Feigan, J. and Lowther, D.A. (1989). The mechanisms of chondrocyte hydrogen peroxide damage. Depletion of intracellular ATP due to suppression of glycolysis caused by oxidation of glyceraldehyde-3-phosphate dehydrogenase. J. Rheumatol. 16, 7-14. 

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