title: Endo-beta-N-acetylglucosaminidase-catalyzed polymerization of beta-Glcp-(1-->4)-GlcpNAc oxazoline: a revisit to enzymatic transglycosylation.
abstract: An alternative synthesis of beta-Glcp-(1-->4)-GlcpNAc oxazoline is described, and its enzymatic reaction with the endo-beta-N-acetylglucosaminidase from Arthrobacter protophormiae (Endo-A) was re-investigated. Under normal transglycosylation conditions with a catalytic amount of enzyme, Endo-A showed only marginal activity for transglycosylation with the disaccharide oxazoline, consistent with our previous observations. However, when used in a relatively large quantity, Endo-A could promote the transglycosylation of the disaccharide oxazoline to a GlcpNAc-Asn acceptor. In addition to the initial transglycosylation product, a series of large oligosaccharides were also formed due to the tandem transglycosylation to the terminal glucose residues in the intermediate products. In the absence of an external acceptor, Endo-A could polymerize the disaccharide oxazoline to form oligo- and polysaccharides having the -4-beta-(Glcp-(1-->4)-beta -GlcpNAc)-1-repeating units. This is the first example of an endo-beta-N-acetylglucosaminidase-promoted polymerization of activated oligosaccharide substrates. This enzymatic polymerization may find useful applications for the synthesis of novel artificial polysaccharides.
authors.affiliation: Institute of Human Virology and Department of Biochemistry & Molecular Biology, University of Maryland School of Medicine, 725 West Lombard Street, Baltimore, MD 21201, United States.
authors.forename: Hirofumi
authors.initials: H
authors.lastname: Ochiai
authors.forename: Wei
authors.initials: W
authors.lastname: Huang
authors.forename: Lai-Xi
authors.initials: LX
authors.lastname: Wang
mesh_terms: D001173:Arthrobacter / Q000201:enzymology; D002240:Carbohydrate Sequence; D002851:Chromatography, High Pressure Liquid; D004187:Disaccharides / Q000737:chemistry* / Q000378:metabolism*; D006020:Glycopeptides / Q000737:chemistry* / Q000378:metabolism*; D006031:Glycosylation; D017038:Mannosyl-Glycoprotein Endo-beta-N-Acetylglucosaminidase / Q000378:metabolism; D008958:Models, Molecular; D008969:Molecular Sequence Data; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization
chemical_list: D004187:Disaccharides; D006020:Glycopeptides; D017038:Mannosyl-Glycoprotein Endo-beta-N-Acetylglucosaminidase