Enzymatic copolymerization to hybrid glycosaminoglycans: a novel strategy for intramolecular hybridization of polysaccharides

Biomacromolecules. 2007 Jun;8(6):1802-6. doi: 10.1021/bm0700340. Epub 2007 May 10.

Abstract

Hybrid glycosaminoglycans (GAGs) having an intramolecularly hybridized structure of hyaluronan-chondroitin (3a) and hyaluronan-chondroitin 4-sulfate (3b) have been synthesized via enzymatic copolymerization catalyzed by hyaluronidase (HAase). N-Acetylhyalobiuronate (GlcAbeta(1-->3)GlcNAc)-derived oxazoline (1) was copolymerized with N-acetylchondrosine (GlcAbeta(1-->3)GalNAc)-derived oxazoline (2a) by HAase catalysis at pH 7.5 and 30 degrees C, giving rise to copolymer 3a with Mn 7.4 x 103 in a 50% yield. Also, HAase-catalyzed copolymerization of monomer 1 with N-acetylchondrosine oxazoline having a sulfate group at C4 on GalNAc (2b) was carried out to produce copolymer 3b with Mn 1.4 x 104 in a 60% yield. The copolymer compositions were controllable by varying the comonomer feed ratio. These hybrid GAGs were successfully digested by the catalysis of hyaluronan lyase, clearly exhibiting that the products are not a blend of different homopolymers but an intramolecularly hybridized GAG.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbohydrate Conformation
  • Chemistry / methods
  • Chondroitin / chemistry
  • Chondroitin Sulfates / chemistry
  • Disaccharides / chemistry
  • Glycosaminoglycans / chemistry*
  • Hyaluronic Acid / chemistry
  • Magnetic Resonance Spectroscopy
  • Models, Chemical
  • Molecular Conformation
  • Oxazoles / chemistry
  • Polymers / chemistry*
  • Polysaccharides / chemistry*
  • Time Factors

Substances

  • Disaccharides
  • Glycosaminoglycans
  • Oxazoles
  • Polymers
  • Polysaccharides
  • N-acetylchondrosine
  • Hyaluronic Acid
  • Chondroitin
  • Chondroitin Sulfates