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Selective Hydrolysis (selective + hydrolysis)
Selected AbstractsStabilized and Immobilized Bacillus subtilis Arginase for the Biobased Production of Nitrogen-Containing ChemicalsADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2010Abstract L -Ornithine could serve as an intermediate in the biobased production of 1,4-diaminobutane from L -arginine. Using the concept of biorefinery, L -arginine could become widely available from biomass waste streams via the nitrogen storage polypeptide cyanophycin. Selective hydrolysis of L -arginine to L -ornithine is difficult to perform chemically, therefore the stabilization and immobilization of Bacillus subtilis arginase (EC,3.5.3.1) was studied in a continuously stirred membrane reactor system. Initial pH of the substrate solution, addition of L -aspartic acid and reducing agents all appeared to have an effect on the operational stability of B. subtilis arginase. A remarkably good operational stability (total turnover number, TTN=1.13,108) at the pH of arginine free base (pH,11.0) was observed, which was further improved with the addition of sodium dithionite to the substrate solution (TTN>1,109). B. subtilis arginase was successfully immobilized on three commercially available epoxy-activated supports. Immobilization on Sepabeads EC-EP was most promising, resulting in a recovered activity of 75% and enhanced thermostability. In conclusion, the stabilization and immobilization of B. subtilis arginase has opened up possibilities for its application in the biobased production of nitrogen-containing chemicals as an alternative to the petrochemical production. [source] Synthesis of a Fusion-Isomeric Cellobionoimidazole and Its Evaluation against the syn -Protonating Glycosidase Cel7AHELVETICA CHIMICA ACTA, Issue 12 2005Narinder Mohal The fusion-isomeric cellobinoimidazole 2, a potential inhibitor of the syn -protonating , -glycosidase Cel7A, was synthesised by Koenigs,Knorr glycosylation of the ,- D -arabinopyranoside 32, followed by selective hydrolysis. Glycosylation of 32 with acetobromoglucose 6 proceeded with poor diastereoselectivity, giving the desired 1,3-linked , - d- disaccharide 35 as minor product, besides the major 1,3-linked ,- d- disaccharide 36. Hg2+ -Promoted glycosylation of 32 led predominantly to the 1,2-ortho ester 33. Sequential removal of the silyl, acetyl, and allyl groups of 35 led to a 45,:,55 equilibrium mixture 2 and the manno -configured isomer 39. Similarly, deprotection of 36 gave a mixture of the maltonoimidazole 42 and the manno -configured isomer 43. According to a known protocol, the glycosyl acceptor 32 was synthesised in eleven steps and an overall yield of 8,13% from D -lyxose. The silylated arabinopyranosyl moiety of the ,- d- glucosides 13,19, 33, 34, and 36 adopts a 4C1 conformation, while the arabinopyranosyl moiety of the , - d- glucosides 17 and 35 exists as a 1,:,3,mixture of 4C1 and 1C4 conformers, as a result of the combined preferred axial orientation of bulky vicinal substituents and the anomeric effect. MM3* Modelling evidences a preferred 4C1 conformation of 35 and 36, and stronger steric interactions between the pyranosyl moieties of 35. The equilibrium mixture 2/39 proved a poor inhibitor of Cel7A with an IC50 value of ca. 4,mM. [source] Novel Chemical Transformations of TenoxicamHELVETICA CHIMICA ACTA, Issue 8 2005Kristóf Kóczián Both N - and O -substituted derivatives of the anti-inflammatory drug tenoxicam (=,4-hydroxy-2-methyl- N -(pyridin-2-yl)-2H -thieno[2,3 -e],[1,2]thiazine-3-carboxamide 1,1-dioxide; 1) were synthesized, and various chemical transformations were investigated. Both selective hydrolysis and reaction of 1,- N -methyltenoxicam (5) with a variety of N-nucleophiles were performed (Scheme,1). Also, five new 4- O -acyl derivatives 10 were prepared as potential prodrugs (Scheme,2). The 4-chloro derivatives of 1 and its analog 8 could be successfully transformed into the novel tetra- and tricyclic ring systems 12 and 13, respectively, the latter being a conformationally restricted 1,5-diaryl-pyrazole designed as a potential COX-2 inhibitor. [source] Well-defined amphiphilic graft copolymer consisting of hydrophilic poly(acrylic acid) backbone and hydrophobic poly(vinyl acetate) side chainsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 22 2009Yaogong Li Abstract A series of well-defined amphiphilic graft copolymers containing hydrophilic poly(acrylic acid) (PAA) backbone and hydrophobic poly(vinyl acetate) (PVAc) side chains were synthesized via sequential reversible addition-fragmentation chain transfer (RAFT) polymerization followed by selective hydrolysis of poly(tert -butyl acrylate) backbone. A new Br-containing acrylate monomer, tert -butyl 2-((2-bromopropanoyloxy)methyl) acrylate, was first prepared, which can be polymerized via RAFT in a controlled way to obtain a well-defined homopolymer with narrow molecular weight distribution (Mw/Mn = 1.08). This homopolymer was transformed into xanthate-functionalized macromolecular chain transfer agent by reacting with o -ethyl xanthic acid potassium salt. Grafting-from strategy was employed to synthesize PtBA- g -PVAc well-defined graft copolymers with narrow molecular weight distributions (Mw/Mn < 1.40) via RAFT of vinyl acetate using macromolecular chain transfer agent. The final PAA- g -PVAc amphiphilic graft copolymers were obtained by selective acidic hydrolysis of PtBA backbone in acidic environment without affecting the side chains. The critical micelle concentrations in aqueous media were determined by fluorescence probe technique. The micelle morphologies were found to be spheres. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6032,6043, 2009 [source] An efficient process for synthesizing and hydrolyzing a phosphonated methacrylate: Investigation of the adhesive and anticorrosive propertiesJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2008Zhor El Asri Abstract A new phosphonated methacrylate, namely dimethyl(methacryloyloxy)methyl phosphonate (MAPC1), has been synthesized using paraformaldehyde and potassium carbonate according to the Pudovik reaction. The quantitative synthesis of MAPC1 was followed by selective hydrolysis of the ester group with sodium bromide to replace NaI (imparting non-negligible ecological impact). Pure MAPC1(OH) was obtained in high yield and efficiently copolymerized with MMA. The r1 for MAPC1(OH)) and r2 (for MMA) values are 0.99 and 1.02, respectively, which indicates that the monophosphonic groups are statistically linked to the methacrylate backbone. When blended with PVDF, MMA/MAPC1(OH) copolymers show very good adhesion promoters in both dry and wet conditions and subsequently provide good anticorrosive properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4794,4803, 2008 [source] | ||||||||||