Transglycosylation specificity of Acremonium sp. α-rhamnosyl-β-glucosidase and its application to the synthesis of the new fluorogenic substrate 4-methylumbelliferyl-rutinoside

Carbohydr Res. 2012 Jan 10;347(1):69-75. doi: 10.1016/j.carres.2011.11.008. Epub 2011 Nov 19.

Abstract

Transglycosylation potential of the fungal diglycosidase α-rhamnosyl-β-glucosidase was explored. The biocatalyst was shown to have broad acceptor specificity toward aliphatic and aromatic alcohols. This feature allowed the synthesis of the diglycoconjugated fluorogenic substrate 4-methylumbelliferyl-rutinoside. The synthesis was performed in one step from the corresponding aglycone, 4-methylumbelliferone, and hesperidin as rutinose donor. 4-Methylumbelliferyl-rutinoside was produced in an agitated reactor using the immobilized biocatalyst with a 16% yield regarding the sugar acceptor. The compound was purified by solvent extraction and silica gel chromatography. MALDI-TOF/TOF data recorded for the [M+Na](+) ions correlated with the theoretical monoisotopic mass (calcd [M+Na](+): 507.44 m/z; obs. [M+Na](+): 507.465 m/z). 4-Methylumbelliferyl-rutinoside differs from 4-methylumbelliferyl-glucoside in the rhamnosyl substitution at the C-6 of glucose, and this property brings about the possibility to explore in nature the occurrence of endo-β-glucosidases by zymographic analysis.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Acremonium / enzymology*
  • Disaccharides / chemical synthesis*
  • Disaccharides / chemistry*
  • Fluorescent Dyes / chemical synthesis*
  • Fluorescent Dyes / chemistry*
  • Glucosidases / metabolism*
  • Glycosides / chemical synthesis*
  • Glycosides / chemistry*
  • Glycosylation
  • Hymecromone / chemical synthesis
  • Hymecromone / chemistry
  • Solubility
  • Solvents / chemistry
  • Substrate Specificity
  • Water / chemistry

Substances

  • 4-methylumbelliferyl-rutinoside
  • Disaccharides
  • Fluorescent Dyes
  • Glycosides
  • Solvents
  • Water
  • Hymecromone
  • Glucosidases