Analysis of N-acetylated hexosamine monosaccharides by ferrocenyl boronation and tandem electrospray ionization mass spectrometry

A tandem electrospray mass spectrometric (MSn) technique for the analysis o f N-acetylated hexose carbohydrates using ferrocene boronate (F(c)Bor) deri vatization was developed. The biologically important N-acetyl hexosamines c an be readily distinguished utilizing this technique, The analysis is made possible by utilizing the inherent electrochemical properties of the electr ospray device to produce oxidized, pre-formed single-electron ferrocenyl io ns in a non-aqueous solvent system. The electrospray device was modified us ing a custom built cell consisting of concentric stainless steel tubes, whi ch produced an enhanced signal for the molecular ion of each analyte specie s. The MS2 spectra derived from isomeric populations of ferrocenyl boronic est ers of these carbohydrates when generated under the same conditions possess ed features unique to each sugar allowing easy differentiation between a nu mber of N-acetyl hexosamine isomers. Copyright (C) 2000 John Wiley & Sons, Ltd.