Enhancing the Response of Alkyl Methylphosphonic Acids in Negative Electrospray Ionization Liquid Chromatography Tandem Mass Spectrometry by Post-Column Addition of Organic Solvents

A method to enhance the signal intensity and signal-to-noise of several alkyl methylphosphonic acids in negative electrospray ionization liquid chromatography tandem mass spectrometry (ESI LC-MS/MS) is presented. This class of compound represents the initial metabolites and environmental degradants...

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Bibliographic Details
Published in:Journal of the American Society for Mass Spectrometry 2007-10, Vol.18 (10), p.1821-1826
Main Authors: Mawhinney, Douglas B., Stanelle, Rayman D., Hamelin, Elizabeth I., Kobelski, Robert J.
Format: Article
Language:English
Subjects:
Alcohols
Alkylation
Analytical chemistry
Chain mobility
Chemistry
Chromatographic methods and physical methods associated with chromatography
Chromatography
Chromatography, High Pressure Liquid - methods
Electrospraying
Ethanol
Exact sciences and technology
Hydrogen bonding
Ionization
Ions
Mass spectrometry
Metabolites
Noise intensity
Organic Chemicals - chemistry
Organophosphorus Compounds - chemistry
Other chromatographic methods
Sarin
Scientific imaging
Sensitivity and Specificity
Solvation
Solvents
Solvents - chemistry
Specimen Handling - methods
Spectrometry, Mass, Electrospray Ionization - methods
Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization - methods
Spectroscopy
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Summary:A method to enhance the signal intensity and signal-to-noise of several alkyl methylphosphonic acids in negative electrospray ionization liquid chromatography tandem mass spectrometry (ESI LC-MS/MS) is presented. This class of compound represents the initial metabolites and environmental degradants of the nerve agents: VX, rVX (Russian VX), GB (Sarin), GF (Cyclosarin), and GD (Soman). Compared with the post-column addition of the mobile phase, the post-column addition of aprotic solvents and longer chain alcohols enhance the signal intensity and signal-to-noise ratio (S/N) of the chromatographic peaks by factors of up to 60 and 19, respectively. The post-column addition of water, methanol, and ethanol resulted in little or no relative signal enhancement. It is proposed that the post-column addition of these solvents do not result in the same enhancements due to stabilization of analyte solvation through hydrogen bonding.
ISSN:1044-0305
1879-1123
DOI:10.1016/j.jasms.2007.07.019