- Kinetic chiral resolutions of 1,2-diols and desymmetrization of glycerol catalyzed by glycerol kinase
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Enantioselective phosphorylation catalyzed by glycerol kinase (EC 2.7.1.30) facilitated the kinetic chiral resolution of 3-chloro-1,2- propanediol, 3-fluoro-1,2-propanediol, 3-butene-1,2-diol, and 1,2,4- butanetriol. Both enantiomers of each compound were isolated is free diol or triol form, in excellent enantiomeric purity (91 to > 99.5% ee) and in moderate to good yield (60-94% of theoretical). The enantioselectivities of glycerol kinase from different sources were compared using 1,2,4-butanetriol as the substrate. The effect of elevated temperatures on enzymatic activity, stability, and enantioselectivity were studied, and procedures for the isolation of diol and triol products were optimized. Glycerol kinase- catalyzed phosphorylation facilitated the three-step chemoenzymatic conversion of glycerol to (S)-1,2-O-isopropylideneglycerol in 83% yield and > 99.5% ee).
- Keith Chenault,Chafin, Laura F.,Liehr, Sebastian
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Read Online
- A toothpaste additive CGP new synthetic process of the (by machine translation)
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The invention relates to a toothpaste additive new synthetic process of the CGP, specifically comprising the following steps: (1) under ice bath, is added to the glycerin in the POCl3 And catalyst, natural recovery to room temperature, stirring the reaction 5 - 6 h after, adds full and sodium bicarbonate solution adjusted to pH 8.0 - 9.0 after, adding calcium chloride, stirring at room temperature the reaction 10 - 12 hours, filter, collecting the filtrate; (2) to the step (1) of the filtrate obtained in adding anhydrous ethanol, stirring 0.5 - 1.0 h after, filtering, deposition and drying to obtain the CGP. (by machine translation)
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Paragraph 0041-0047
(2018/09/28)
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- Novel synthetic method to synthesize intermediate glycerophosphate from calcium glycerophosphate
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The invention relates to a novel synthetic method to synthesize intermediate glycerophosphate from calcium glycerophosphate, comprising the steps: adding glycerol into POCl3 and a catalyst under ice bath, allowing natural restoring to room temperature, stirring to allow reaction for 5-6 h, distilling in vacuum, and collecting glycerophosphate fraction. The catalyst is ionic-liquid-modified silica-supported pyrophosphoric acid catalyst.
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Paragraph 0042; 0043; 0044; 0045
(2018/10/19)
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- Preparation method of L-alpha-glycerophosphoryl choline
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The invention relates to a preparation method of L-alpha-glycerophosphoryl choline. The method comprises the steps of preparing (R)-3-chlorine-1,2-propylene glycol as an initial raw material; preparing (R)-glycerophosphate with calcium phosphate metal salt; then carrying out a reaction with dibromoethane to obtain (R)-3-glyceryl cyclophosphate; finally carrying out a reaction with trimethylamine in an open-loop reaction to obtain L-alpha-glycerophosphoryl choline. With the adoption of the method, the problem of wastewater pollution caused by choline chloride phosphate calcium salt or potassiumsalt is avoided, and the link of removing chloridion of a finished product through ion-exchange columns can be eliminated; the product purity is high; the yield is high; the method is applicable to industrial production and has a good application prospect.
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Paragraph 0041-0044; 0048
(2018/07/28)
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- Darwin's Warm Little Pond: A One-Pot Reaction for Prebiotic Phosphorylation and the Mobilization of Phosphate from Minerals in a Urea-Based Solvent
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The poor reactivity of insoluble phosphates, such as apatite-group minerals, has been a long-appreciated obstacle for proposed models of prebiotic organophosphate formation. This obstacle presents a significant challenge to the nascent development of an RNA world and other models for the origins of life on Earth. Herein, we demonstrate that a scenario based on the formation of a urea/ammonium formate/water (UAFW) eutectic solution leads to an increase in phosphorylation when compared to urea alone for phosphate sources of varying solubility. In addition, under evaporative conditions and in the presence of MgSO4, the UAFW eutectic mobilizes the phosphate sequestered in water-insoluble hydroxyapatite, giving rise to a marked increase in phosphorylation. These results suggest that the prebiotic concentrations of urea in a geologically plausible evaporitic environment could solve the problem of organic phosphorylation on a prebiotic Earth.
- Burcar, Bradley,Pasek, Matthew,Gull, Maheen,Cafferty, Brian J.,Velasco, Francisco,Hud, Nicholas V.,Menor-Salván, César
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supporting information
p. 13249 - 13253
(2016/10/30)
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- The first nonradioactive fluorescence assay for phosphatidylglycerol: prolipoprotein diacylglyceryl transferase that initiates bacterial lipoprotein biosynthesis
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The unique and physiologically vital bacterial enzyme, prolipoprotein diacylglyceryl transferase (Lgt), which catalyzes the committed first step in the posttranslational transfer of diacylglyceryl group from phosphatidylglycerol to the prospective N-terminal cysteine of prolipoproteins, remains to be characterized for want of a simpler but equally sensitive nonradioactive assay. We, for the first time, report a coupled enzymatic fluorescence assay for Lgt using the de novo synthetic peptide substrate MKATKSAVGSTLAGCSSHHHHHH. The assay is based on the conversion of the by-product, glycerol-1-phosphate, to dihydroxyacetone using an alkaline phosphatase-glycerol dehydrogenase combination and estimating the fluorescence of the coupled reduction of resazurin to resorufin. The minimum amount of glycerol-1-phosphate, and hence the modified peptide, detected by this method is approximately 20 pmol, thereby making this assay a promising alternative to the radioactive assays. The assay is rapid, more convenient, less laborious, and suitable for purification and characterization of Lgt.
- Sundaram, Srividhya,Banerjee, Sanchari,Sankaran, Krishnan
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scheme or table
p. 163 - 170
(2012/07/28)
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- Biocide compositions comprising glycerol(ether)phosphates
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Suggested are biocide compositions, comprising (a) Glycerol(ether)phosphates; (b) Biocides and optionally (c) Oil components or co-solvents and/or (d) Emulsifiers. The compositions show excellent adjuvant and complexing properties.
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- Resolving the enigma of prebiotic C-O-P bond formation: Prebiotic hydrothermal synthesis of important biological phosphate esters
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Important biological phosphate esters such as sn-glycerol-3-phosphate, glycerol-2- phosphate, and phosphoethanolamine were synthesized under hydrothermal conditions. Phosphorus was incorporated into the biomolecules, leading to the formation of C-O-P type compounds hydrother- mally. Only perlite-catalyzed reaction at 180° C could result in the formation of sn-glycerol-3-phosphate, whereas glycerol-2-phosphate could be easily synthesized at 100°C with or without minerals and phos- phoethanolamine was obtained within a temperature range of 100 to 120°.
- Maheen, Gull,Tian, Ge,Wang, Yingwu,He, Chao,Shi, Zhan,Yuan, Hongming,Feng, Shouhua
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scheme or table
p. 161 - 167
(2011/06/28)
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- Rescue of K12G triosephosphate isomerase by ammonium cations: The reaction of an enzyme in pieces
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The K12G mutation at yeast triosephosphate isomerase (TIM) results in a 5.5 × 105-fold decrease in kcat/Km for isomerization of glyceraldehyde 3-phosphate, and the activity of this mutant can be successfully rescued by NH4+ and primary alkylammonium cations. The transition state for the K12G mutant TIM-catalyzed reaction is stabilized by 1.5 kcal/mol by interaction with NH4 +. The larger 3.9 kcal/mol stabilization by CH3CH 2CH2CH2NH3+ is due to hydrophobic interactions between the mutant enzyme and the butyl side chain of the cation activator. There is no significant transfer of a proton from alkylammonium cations to GAP at the transition state for the K12G mutant TIM-catalyzed reaction, because activation by a series of RNH3 + shows little or no dependence on the pKa of RNH 3+. A comparison of kcat/Km = 6.6 × 106 M-1 s-1 for the wildtype TIM-catalyzed isomerization of GAP and the third-order rate constant of 150 M-2 s-1 for activation by NH4+ of the K12G mutant TIM-catalyzed isomerization shows that stabilization of the bound transition state by the effectively intramolecular interaction of the cationic side chain of Lys-12 at wildtype TIM is 6.3 kcal/mol greater than that for the corresponding intermolecular interaction of NH4+ at K12G mutant TIM.
- Go, Maybelle K.,Amyes, Tina L.,Richard, John P.
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experimental part
p. 13525 - 13532
(2010/12/19)
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- An efficient chemoenzymatic route to dihydroxyacetone phosphate from glycidol for the in situ aldolase-mediated synthesis of monosaccharides
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We report a new two-step procedure that uses inexpensive rac-glycidol to obtain valuable dihydroxyacetone phosphate (DHAP), a building block for the synthesis of monosaccharide analogues.
- Charmantray, Franck,Dellis, Phillipe,Samreth, Soth,Hecquet, Laurence
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p. 3261 - 3263
(2007/10/03)
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- Regioselective phosphorylation of carbohydrates and various alcohols by bacterial acid phosphatases; probing the substrate specificity of the enzyme from Shigella flexneri
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Bacterial non-specific acid phosphatases normally catalyze the dephosphorylation of a variety of substrates. As shown previously the enzymes from Shigella flexneri and Salmonella enterica are also able to catalyze the phosphorylation of inosine to inosine monophosphate and D-glucose to D-glucose 6-phosphate (D-G6P) using cheap pyrophosphate as the phosphate donor. After optimization high yields (95%) are achieved in the latter reaction and we show here that it is possible to use these enzymes in a preparative manner. This prompted us to investigate by using 31P NMR and HPLC also the phosphorylation of a broad range of carbohydrates and alcohols. Many cyclic carbohydrates are phosphorylated in a regioselective manner. Non-cyclic carbohydrates are phosphorylated as well. Phosphorylation of linear alcohols, cyclic and aromatic alcohols is also possible. In all cases the acid phosphatase from Shigella prefers a primary alcohol function above a secondary one. We conclude that these enzymes are an attractive alternative to existing chemical and enzymatic methods in the phosphorylation of a broad range of compounds.
- Van Herk, Teunie,Hartog, Aloysius F.,Van Der Burg, Alida M.,Wever, Ron
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p. 1155 - 1162
(2007/10/03)
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- Cationic, amphipathic beta-sheet peptides and uses thereof
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This invention relates to an antimicrobial compound which is (a) a peptide having a length of 8-50 amino acids, a net charge of at least four, a hydrophobic moment as a beta sheet which is at least 0.2 higher than its hydrophobic moment as an alpha helix, and having detectable membrane disrupting activity against at least one microbial pathogen, and substantially no membrane disrupting activity against mammalian cells, or (b) a peptoid, peptidomimetic or nonpeptidic analogue of a peptide according to (a) above. And to antimicrobial use thereof.
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- Carbohydrates from glycerol: An enzymatic four-step, one-pot synthesis
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A novel one-pot procedure, involving a cascade of four enzymatic steps, for the synthesis of carbohydrates from glycerol and an aldehyde is reported.
- Schoevaart, Rob,Van Rantwijk, Fred,Sheldon, Roger A.
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p. 2465 - 2466
(2007/10/03)
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- Reactivities of some energy rich organic orthophosphates towards transition metal ion oxidants
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The orthophosphates, α- and β-glycerophosphates, react with HCrO-4 in HClO4 medium to give 1:1 intermediates which subsequently decomposes to give products of the reactions.The rate is directly proportional to +> in each reaction.Thermodynamic parameters associated with the equilibrium step and the activation parameters associated with the slowest step has been evaluated for each substrate.An attempt has been made to correlate the results obtained earlier with other transition metal ion oxidants.
- Gupta, Kalyan Kali Sen,Mahapatra, Ambikesh,Sanyal, Ankan
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p. 332 - 334
(2007/10/02)
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- Carbocyclic Adenosine Phosphates as Nucleotide Mimics in Some Enzyme-catalysed Reactions
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The carbocyclic nucleotides 1-4 have been synthesised and shown to be good mimics of adenosine phosphates in some enzyme-catalysed reactions.
- Grand, Darren M. Le,Roberts, Stanley M.
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p. 1284 - 1285
(2007/10/02)
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- Reversible and in Situ Formation of Organic Arsenates and Vanadates as Organic Phosphate Mimics in Enzymatic Reactions: Mechanistic Investigation of Aldol Reactions and Synthetic Applications
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A synthetic strategy is developed that uses organic phosphate utilizing enzymes as catalysts and a mixture of an organic alcohol and inorganic arsenate or vanadate to replace the organic phosphate substrate.In this process, inorganic arsenate or vanadate reacts with the alcohol reversibly in situ to form a mixture of esters, one of which is accepted by the enzyme as a substrate.Examples of the utility of this approach are demonstrated in enzymatic aldol condensations catalyzed by fructose-1,6-diphosphate aldolase, fuculose-1-phosphate aldolase, and rhamnulose-1-phosphate aldolase with a mixture of dihydroxyacetone and inorganic arsenate as substrate.Several uncommon sugars and deoxy sugars are prepared on 5-17-mmol scales.Mechanistic studies on an aldol reaction indicate that the redox reaction between dihydroxyacetone and inorganic vanadate prohibits the use of such a mixture to replace dihydroxyacetone phosphate in enzymatic aldol condensations.
- Drueckhammer, Dale G.,Durrwachter, J. Robert,Pederson, Richard L.,Crans, Debbie C.,Daniels, Lacy,Wong, Chi-Huey
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