Peptides acryloyl

Vinylogous urea substrates have also been used in the aza-annulation reaction to form 6-lactam products. This process was illustrated by the condensation of fi-keto amide 366 followed by aza-annulation with acryloyl chloride to give 367 (eq. 75).57-59 Catalytic reduction of the tetrasubstituted double bond led to stereoselective formation of 368. The products formed in this reaction were fi-enamino peptide units, and this chemistry can be extended to the preparation of tri-and tetrapeptide analogs. 

Figure 2. Schematic diagram of the second reaction of the fatty acid P-oxidation pathway catalyzed by co/i enoyl-CoA hydratase. Compounds 1 and 2 are 2-mmr-enoyl-CoA and L-3-hydroxyacyl-CoA, respectively. The protonated Glu transfers a proton to the a carbon of the substrate on the re face, whereas the deprotonated Glu" attracts a proton from water whose oxygen makes a nudeopbilic attack on the P-carbon of the substrate. The amino group of Gly" in the peptide backbone acts as a l rogen donor to form a hydrogen bond with the carbonyl oxygen so that an electronic rearrangement occurs in the acryloyl portion of the sul trate. The transition state is shown in the square brackets The product, L-3-hydroxyacyl-CoA, can then leave the active site. Two general acid-base functional groups, the ycarboxyl groups of Glu and Glu , play a major part in the hydratase catalysis...

Figure 6. Representative multivalent ligands. From top left mannosylated ROMP polymers acrylamide/acryloyl ester copolymers peptide-based dendritic ligands. See text for descriptions.

Resins for peptide synthesis Poly[acryloyl-bis(aminopropyl) polyethylene glycol] (PEGA) [26, 27]. The PEGA resin was obtained from Polymer Laboratories Ltd (Now Agilent, England). 

Free radical induced polymerisation of acryloyl peptides... 

Parallel approaches have been described for the preparation of polyacrylate-protease conjugates [396-400]. Acryloylation of subtilisin and a-chymotrypsin, followed by mixed polymerization with methyl methacrylate, vinyl acetate, styrene, or ethylvinyl ether, provides insoluble, doped polymethyl methacrylate, polyvinyl acetate, polystyrene, and polyethyl vinyl ether polymers [396]. These biocatalytic plastics perform especially well in hydrophilic and hydrophobic solvents, and have been used for peptide synthesis and the regioselective acylation of sugars and nucleosides. Similarly, modification of subtilisin and thermolysin with PEG monomethacrylate, then copolymerization with methyl methacrylate and trimethylolpropane trimethacrylate furnishes protease-polymethyl methacrylate plastics, which show good activities and stabilities in aqueous, mixed, and low-water and anhydrous organic media [397-400]. The protein-acrylate composites are unique in that they enable catalytic densities as high as 50% w/w. 

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