"Hypermethylation" of anthranilic acid-labeled sugars confers the selectivity required for liquid chromatography-mass spectrometry

Anal Biochem. 2016 Dec 1:514:24-31. doi: 10.1016/j.ab.2016.09.008. Epub 2016 Sep 14.

Abstract

Analysis of the monosaccharides of complex carbohydrates is often performed by liquid chromatography with fluorescence detection. Unfortunately, methylated sugars, unusual amino- or deoxysugars and incomplete hydrolysis can lead to erroneous assignments of peaks. Here, we demonstrate that a volatile buffer system is suitable for the separation of anthranilic acid labeled sugars. It allows off-line examination of peaks by electrospray mass spectrometry. Approaches towards on-line mass spectrometric detection using reversed-phase or porous graphitic carbon columns fell short of achieving sufficient separation of the relevant isobaric sugars. Adequate chromatographic performance for isomeric sugars was achieved with reversed-phase chromatography of "hyper"-methylated anthranilic acid-labeled monosaccharides. Deuteromethyl iodide facilitates the discovery of naturally methylated sugars and identification of their parent monosaccharide as demonstrated with N-glycans of the snail Achatina fulica, where two thirds of the galactoses and a quarter of the mannoses were methylated.

Keywords: 6-Deoxy talose; Anthranilic acid; Mass spectrometry; Monosaccharide; O-methylation.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbohydrates / analysis
  • Carbohydrates / chemistry
  • Chromatography, High Pressure Liquid / instrumentation
  • Chromatography, High Pressure Liquid / methods*
  • Chromatography, Reverse-Phase / methods
  • Fluorescence
  • Methylation
  • Monosaccharides / analysis*
  • Monosaccharides / chemistry
  • Online Systems
  • Solvents / chemistry
  • Spectrometry, Mass, Electrospray Ionization / methods*
  • Tandem Mass Spectrometry / methods
  • ortho-Aminobenzoates / chemistry*

Substances

  • Carbohydrates
  • Monosaccharides
  • Solvents
  • ortho-Aminobenzoates
  • anthranilic acid