title: Enzymatic synthesis of chondroitin 4-sulfate with well-defined structure.
abstract: Synthesis of chondroitin sulfate (ChS) with well-defined structure was achieved for the first time by hyaluronidase-catalyzed polymerization. N-Acetylchondrosine (GlcAbeta(1-->3)GalNAc) oxazoline derivatives sulfated at C4 (1a), C6 (1b), and both C4 and C6 (1c) in the GalNAc unit were synthesized as transition state analogue substrate monomers for hyaluronidase (HAase) catalysis. Compound 1a was effectively polymerized by the enzyme, giving rise to synthetic ChS sulfated perfectly at the C4 position in all N-acetylgalactosamine units (Ch4S, 2a) in good yields. Molecular weights (Mn) of 2a ranged from 4000 to 18,400, which were controlled by varying reaction conditions. Compounds 1b and 1c were not catalyzed by the enzyme, affording the corresponding disaccharides through the oxazoline ring-opening without formation of polysaccharides.
authors.affiliation: Department of Materials Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan.
authors.forename: Shun-ichi
authors.initials: S
authors.lastname: Fujikawa
authors.forename: Masashi
authors.initials: M
authors.lastname: Ohmae
authors.forename: Shiro
authors.initials: S
authors.lastname: Kobayashi
mesh_terms: D000818:Animals; D001672:Biocompatible Materials / Q000737:chemistry; D002417:Cattle; D002809:Chondroitin Sulfates / Q000138:chemical synthesis* / Q000737:chemistry; D004187:Disaccharides / Q000737:chemistry; D006821:Hyaluronoglucosaminidase / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008297:Male; D008956:Models, Chemical; D008970:Molecular Weight; D010080:Oxazoles / Q000737:chemistry; D011108:Polymers / Q000737:chemistry; D011134:Polysaccharides / Q000737:chemistry; D011487:Protein Conformation; D012756:Sheep; D013455:Sulfur / Q000737:chemistry; D013737:Testis / Q000378:metabolism; D013997:Time Factors
chemical_list: D001672:Biocompatible Materials; D004187:Disaccharides; D010080:Oxazoles; D011108:Polymers; D011134:Polysaccharides; C033269:N-acetylchondrosine; D013455:Sulfur; D002809:Chondroitin Sulfates; D006821:Hyaluronoglucosaminidase