Phospho fluoridates from

From Sigma 3-aminoethylcarbazole (AEC) acrylamide/bis-acrylamide (30%) 37.5 1 amino acids alumina bentonite benzamidine bovine fiver tRNA bovine serum albumin (BSA) creatine phosphate (CP) diethyl pyrocarbonate (DEPC) dithiothreitol (DTT) Escherichia coli MRE600 tRNA pyrophosphatase (Ppase) Ca++ salt of folinic acid, (5-formyl THF) IIHPHS K salt of phospho-enol pyruvic acid, (PEP) creatine phospho kinase (CPK) protease inhibitor cocktail for fungal and yeast extracts phenylmethylsulfonyl fluoride (PMSF) spermidine trihydrochloride Tween 20. 

Hexose diphosphate was found by Harden and Young69 in cell-free alcoholic-fermentation liquors. In 1930, it was observed that addition of fluoride to fermenting-yeast extracts leads to an accumulation of 0-phospho-D-glyceronic acid,60 which is also a metabolite of muscle extracts.61 Attention was turned, therefore, to the pathway from hexose diphosphate to 0-phos-pho-D-glyceronic acid. In 1932, Fischer and Baer62 described the synthesis of D-glycerose 3-phosphate, and, in 1933, Smythe and Gerischer63 noted... 

A second mechanism of protection from caries is the incorporation of fluoride into bacterial biofilms where it inhibits enolase. Enolase catalyzes the production of phospho-enolpyruvate, the precursor of lactate in glycolysis, from 2-phosphoglycerate during glycolysis (Fig. 16.7 - see also Fig. 1.7). In addition, oral bacterial uptake of mono- and disaccharides mostly utilizes the phosphoenolpyruvate transport system to transfer them into the cytosol (Sect. 15.2.2). Fluoride therefore inhibits not only lactic acid production, but also the phosphoenolpyruvate transport system-mediated uptake of saccharide substrates. In short, fluoride inhibits saccharolytic fermentation by many oral bacteria. 

Application of fluoride reactivation to serum samples of casualties of the Matsumoto and Tokyo incidents yielded sarin concentrations in the range 0.2 1.1 ng/ml serum (Polhuijs et al, 1997). Hydrolytic displacement of the phospho-nyl residue identified /PrMPA at levels sufficient for full-scan mass spectra to be obtained from samples collected from casualties who died (Nagao et al, 1997) MPA was also identified. MPA was detected in formalin-fixed brain tissues some two years later using a similar procedure (Matsuda et al, 1998). The phosphonylated peptic nonapeptide from BuChE was identified in serum samples from several casualties of the subway attack (Fidder et al, 2002). 

Hydrotetrafluorophosphorane, HPF4, mp = -100°C, and dihydrotrifluoro phosphorane, H2PF3, mp = -52°C, can be made by reacting hydrogen fluoride under anhydrous conditions with phosphorous and hypophosphorous acids, respectively (4.271 through 4.272). Alternatively, these phospho-ranes may be obtained from PF, by reactions (4.273) and (4.274) [26,27]. 

Nucleophilic attack at remote positions of coordinated ligands is observed when these are activated by strongly electron-withdrawing groups. For instance, PEts displaces a fluoride atom from complex 131 affording a phospho-niovinyl complex (Equation (66)). A related reaction is the hydrolysis of coordinated 2,4,6-trifluoropyrimidine, to afford a 4,6-difluoropyrimidin-2-one complex. An unusual reaction is the formal insertion (probably electrophilic attack) of heterocumulenes (GS2 or CO2) into a coordinate Ni-P bond of 70 (Equation (67)). 

Trimethylsilyl phosphites 4 react with sulfuryl chloride fluoride in a fully chemoselective manner (lid) (Scheme 5). Phosphorofluoridates 5 of high purity are formed in almost quantitative yield. The side products are volatile and readily separable. Trimethylsilyl esters of the dinucleoside phosphites can be prepared from hydrogen phospho-nates (12a,b) (Scheme 6) or more conveniently by phosphitylation procedures (13) (Schemes 7 and 8). 

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