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Acylation as a successful derivatization strategy for the analysis of pinacolyl alcohol in a glycerol-rich matrix by GC-MS: application during an OPCW Proficiency Test

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Abstract

A derivatization protocol based on the acylation of pinacolyl alcohol (PA), an important marker for the nerve agent soman, is presented. The procedure provides a convenient means of detecting, by gas chromatography-mass spectrometry (GC-MS), PA when present at a low concentration in a complex glycerol/alcohol-rich matrix. While there are only two reports describing the specific analysis of PA in matrices at low concentrations, the protocol described herein represents the first of its kind in the analysis of PA in a highly reactive matrix. Two alternative paths for the protocol’s execution are presented. The first involves the direct derivatization of the PA with either acetyl or benzoyl chloride; both reactions yield ester products with significantly different retention times than those of the interferences of the reactive glycerol-rich matrix and in areas of the GC-chromatogram featuring lower levels of matrix interferences. A second procedure involved an initial diethyl ether/aqueous extraction of the matrix; while the extraction was found to substantially remove many of the hydrophilic matrix components and improve the overall derivatization, it also led to some loss of PA available for the derivatization. Both protocols were applied to the successful derivatization and analysis of PA by GC-MS when present at a 5 μg.mL−1 concentration in a glycerol-rich matrix sample administered during the 48th Proficiency Test administered by the Organisation for the Prohibition of Chemical Weapons (OPCW).

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Authors and Affiliations

  1. Nuclear and Chemical Sciences Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA

    Carlos A. Valdez, Roald N. Leif, Carolyn L. Fisher, Saphon Hok, Carolyn J. Koester & Armando Alcaraz

  2. Forensic Science Center, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA

    Carlos A. Valdez, Todd H. Corzett, Roald N. Leif, Carolyn L. Fisher, Saphon Hok, Carolyn J. Koester & Armando Alcaraz

  3. Biosciences and Biotechnology Division, Lawrence Livermore National Laboratory, Livermore, CA, 94550, USA

    Todd H. Corzett

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  1. Carlos A. Valdez
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  2. Todd H. Corzett
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  7. Armando Alcaraz
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Correspondence to Carlos A. Valdez.

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This document (LLNL-JRNL-818917) was prepared as an account of work sponsored by an agency of the US government. Neither the US government nor Lawrence Livermore National Security, LLC, nor any of their employees makes any warranty, expressed or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the US government or Lawrence Livermore National Security, LLC. The views and opinions of authors expressed herein do not necessarily state or reflect those of the US government or Lawrence Livermore National Security, LLC, and shall not be used for advertising or product endorsement purposes. This work performed under the auspices of the US Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC5207NA27344.

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Valdez, C.A., Corzett, T.H., Leif, R.N. et al. Acylation as a successful derivatization strategy for the analysis of pinacolyl alcohol in a glycerol-rich matrix by GC-MS: application during an OPCW Proficiency Test. Anal Bioanal Chem 413, 3145–3151 (2021). https://doi.org/10.1007/s00216-021-03296-6

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  • DOI: https://doi.org/10.1007/s00216-021-03296-6

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