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Analysis of neutral isomeric low molecular weight carbohydrates using ferrocenyl boronate derivatization and tandem electrospray mass spectrometry
Author(s) -
Williams Dudley,
Young Mary K.
Publication year - 2000
Publication title -
rapid communications in mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.528
H-Index - 136
eISSN - 1097-0231
pISSN - 0951-4198
DOI - 10.1002/1097-0231(20001130)14:22<2083::aid-rcm136>3.0.co;2-w
Subject(s) - chemistry , diastereomer , tandem mass spectrometry , pyranose , mass spectrometry , electrospray , electrospray ionization , anomer , chromatography , stereochemistry
A new analytical technique for small carbohydrates utilizing the cyclic ferrocenyl boronic esters (F c Bors) of several neutral mono‐ and disaccharides is demonstrated. Distinction between the diastereomers of mono‐ and disaccharides is obtained. Analysis is by tandem electrospray‐mass spectrometry (ES‐MS) using a modified ion‐source that promotes the preformation of ions. Selection of the molecular ion produced during single‐electron oxidation of the ferrocene moiety of a specific population of saccharide isomers permits a variety of collisionally induced dissociation (CID) experiments. The resultant MS 2 /MS 3 spectra reflect the ensemble of possible cyclic esters in equilibrium. An array of stable cross pyranose ring fragment ions representing sequential carbon loss as 30 u is observed. Consequently, the system provides an information‐rich set of MS n spectra containing large amounts of structural information. Identification of D ‐glucose ( D ‐Glc), its two commonly found epimers ( D ‐mannose and D ‐galactose), and the two major L ‐diastereomers of 6‐dideoxymonosaccharides, L ‐fucose ( L ‐Fuc) and L ‐rhamnose ( L ‐Rhm), are demonstrated. Selected pairs of disaccharides can be distinguished in terms of their anomeric linkage by reference to their MS 3 spectra. Copyright © 2000 John Wiley & Sons, Ltd.