Ion−Molecule Reactions for the Characterization of Polyols and Polyol Mixtures by ESI/FT-ICR Mass Spectrometry

• Published in: Analytical chemistry (Washington) Vol. 77; no. 5; pp. 1385 - 1392
• Main Authors: Watkins, Michael A, Winger, Brian E, Shea, Ryan C, Kenttämaa, Hilkka I
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01-03-2005
• Subjects: Analytical chemistry; Boron Compounds - chemistry; Chemical reactions; Chemistry; Chromatographic methods and physical methods associated with chromatography; Chromatography, High Pressure Liquid; Cyclotrons; Erythritol - analysis; Erythritol - chemistry; Exact sciences and technology; Fourier Analysis; Ions; Ions - chemistry; Mannitol - analysis; Mannitol - chemistry; Mass spectrometry; Methods; Molecules; Other chromatographic methods; Reproducibility of Results; Spectrometric and optical methods; Spectrometry, Mass, Electrospray Ionization - methods; Sugar Alcohols - analysis; Sugar Alcohols - chemistry; Xylitol - analysis; Xylitol - chemistry; Ion molecule reaction; Fourier transform spectroscopy; HPLC chromatography; Hydroxyl group; Polyol; Ion cyclotron resonance spectrometry; Derivatization; Mass spectrometry; Electrospray
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac049031t

A mass spectrometric method is described for the identification and counting of hydroxyl groups in an analyte. Analytes introduced into a FT-ICR mass spectrometer and ionized by positive mode ESI were allowed to react with the neutral reagent diethylmethoxyborane. This results in derivatization of the hydroxyl groups of the analytes by replacement of a proton with a diethylborenium ion. Protonated polyols react by consecutive derivatization reactions, wherein all, or nearly all, of the hydroxyls are derivatized. The polyol derivatization products are separated by 68 mass units in the mass spectrum. This 68 Da mass shift, along with 30 Da mass shifts arising from intramolecular derivatization of the primary derivatization products, makes it easy to count the number of functional groups present in the analyte. The utility of this method for the analysis of polyols as single-component solutions, as mixtures, or in HPLC effluent (LC−MS analysis) is demonstrated.