Use of carbonyldiimidazole as a derivatization agent for the detection of pinacolyl alcohol, a forensic marker for Soman, by EI-GC–MS and LC-HRMS in official OPCW proficiency test matrices

Valdez, Carlos A.; Kaseman, Derrick C.; Dreyer, Mark L.; Hok, Saphon; Vu, Alexander K.

doi:10.1111/1556-4029.15527

Title: Use of carbonyldiimidazole as a derivatization agent for the detection of pinacolyl alcohol, a forensic marker for Soman, by EI-GC–MS and LC-HRMS in official OPCW proficiency test matrices

Journal Article · 22 April 2024 · Journal of Forensic Sciences

DOI: https://doi.org/10.1111/1556-4029.15527 · OSTI ID:2507140

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Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Pinacolyl alcohol (PA), a key forensic marker for the nerve agent Soman (GD), is a particularly difficult analyte to detect by various analytical methods. In this work, we have explored the reaction between PA and 1,1'-carbonyldiimidazole (CDI) to yield pinacolyl 1H-imidazole-1-carboxylate (PIC), a product that can be conveniently detected by gas chromatography–mass spectrometry (GC–MS) and liquid chromatography-high-resolution mass spectrometry (LC-HRMS). Regarding its GC–MS profile, this new carbamate derivative of PA possesses favorable chromatographic features such as a sharp peak and a longer retention time (RT = 16.62 min) relative to PA (broad peak and short retention time, RT = 4.1 min). Additionally, the derivative can also be detected by LC-HRMS, providing an avenue for the analysis of this chemical using this technique where PA is virtually undetectable unless present in large concentrations. From a forensic science standpoint, detection of this low molecular weight alcohol signals the past or latent presence of the nerve agent Soman (GD) in a given matrix (i.e., environmental or biological). The efficiency of the protocol was tested separately in the analysis and detection of PA by EI-GC–MS and LC-HRMS when present at a 10 μg/mL in a soil matrix featured in the 44th PT and in a glycerol-rich liquid matrix featured in the 48th Official Organization for the Prohibition of Chemical Weapons (OPCW) Proficiency Test when present at a 5 μg/mL concentration. In both scenarios, PA was successfully transformed into PIC, establishing the protocol as an additional tool for the analysis of this unnatural and unique nerve agent marker by GC–MS and LC-HRMS.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 2507140

Report Number(s):: LLNL--JRNL-859572; 1089492

Journal Information:: Journal of Forensic Sciences, Journal Name: Journal of Forensic Sciences Journal Issue: 4 Vol. 69; ISSN 0022-1198

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (33)

Zinc Promoted Urea Synthesis Using Carbonyldiimidazole as Carbonyl Source and Its Application for the Synthesis of Cariprazine Jadhav, Krishna A.; Itage, Shivanand V.; Bhosle, Siddhanath D. European Journal of Organic Chemistry, Vol. 26, Issue 7 https://doi.org/10.1002/ejoc.202201169	journal	January 2023
A static headspace GC‐MS/MS method for the determination of ethanol, iso‐butanol, and n‐butanol at nanomolar concentrations in aqueous environmental samples Mead, Ralph N.; Cala, John M.; Felix, J. David Limnology and Oceanography: Methods, Vol. 15, Issue 12 https://doi.org/10.1002/lom3.10220	journal	October 2017
Rapid and mild silylation of β -amino alcohols at room temperature mediated by N -methylimidazole for enhanced detectability by gas chromatography/electron ionization mass spectrometry: NMI-mediated in situ silylation of β -aminoethyl alcohols Valdez, Carlos A.; Leif, Roald N.; Hart, Bradley R. Rapid Communications in Mass Spectrometry, Vol. 28, Issue 20 https://doi.org/10.1002/rcm.7012	journal	September 2014
Effective methylation of phosphonic acids related to chemical warfare agents mediated by trimethyloxonium tetrafluoroborate for their qualitative detection and identification by gas chromatography-mass spectrometry Valdez, Carlos A.; Leif, Roald N.; Alcaraz, Armando Analytica Chimica Acta, Vol. 933 https://doi.org/10.1016/j.aca.2016.05.034	journal	August 2016
Modification of N -(6-(2-methoxy-3-(4-fluorophenylsulfonamido)pyridin-5-yl)-[1,2,4]triazolo[1,5- a ]pyridin-2-yl)acetamide as PI3Ks inhibitor by replacement of the acetamide group with alkylurea Wang, Xiao-Meng; Mao, Shuai; Cao, Lei Bioorganic & Medicinal Chemistry, Vol. 23, Issue 17 https://doi.org/10.1016/j.bmc.2015.07.017	journal	September 2015
Thermally assisted methylation and subsequent silylation of scheduled acids of chemical weapon convention for on-site analysis and its comparison with the other methods of methylation Amphaisri, Kanchanavadee; Palit, Meehir; Mallard, Gary Journal of Chromatography A, Vol. 1218, Issue 7 https://doi.org/10.1016/j.chroma.2010.12.065	journal	February 2011
Alkylsilyl derivatives for gas chromatography Poole, Colin F. Journal of Chromatography A, Vol. 1296 https://doi.org/10.1016/j.chroma.2013.01.097	journal	June 2013
In-situ derivatization and headspace solid-phase microextraction for gas chromatography-mass spectrometry analysis of alkyl methylphosphonic acids following solid-phase extraction using thin film Kim, Hyunsuk; Cho, Yungyeong; Lee, Bong Soo Journal of Chromatography A, Vol. 1599 https://doi.org/10.1016/j.chroma.2019.04.010	journal	August 2019
Efficient derivatization of methylphosphonic and aminoethylsulfonic acids related to nerve agents simultaneously in soils using trimethyloxonium tetrafluoroborate for their enhanced, qualitative detection and identification by EI-GC–MS and GC–FPD Valdez, Carlos A.; Marchioretto, Mira K.; Leif, Roald N. Forensic Science International, Vol. 288 https://doi.org/10.1016/j.forsciint.2018.04.041	journal	July 2018
Methylation protocol for the retrospective detection of isopropyl-, pinacolyl- and cyclohexylmethylphosphonic acids, indicative markers for the nerve agents sarin, soman and cyclosarin, at low levels in soils using EI-GC–MS Valdez, Carlos A.; Leif, Roald N.; Hok, Saphon Science of The Total Environment, Vol. 683 https://doi.org/10.1016/j.scitotenv.2019.05.205	journal	September 2019
Part 2: Forensic attribution profiling of Russian VX in food using liquid chromatography-mass spectrometry Jansson, Daniel; Lindström, Susanne Wiklund; Norlin, Rikard Talanta, Vol. 186 https://doi.org/10.1016/j.talanta.2018.02.103	journal	August 2018
Part 1: Tracing Russian VX to its synthetic routes by multivariate statistics of chemical attribution signatures Holmgren, Karin Höjer; Valdez, Carlos A.; Magnusson, Roger Talanta, Vol. 186 https://doi.org/10.1016/j.talanta.2018.02.104	journal	August 2018
Part 3: Solid phase extraction of Russian VX and its chemical attribution signatures in food matrices and their detection by GC-MS and LC-MS Williams, Audrey M.; Vu, Alexander K.; Mayer, Brian P. Talanta, Vol. 186 https://doi.org/10.1016/j.talanta.2018.03.044	journal	August 2018
On the reactivity of imidazole carbamates and ureas and their use as esterification and amidation reagents Heller, Stephen T.; Sarpong, Richmond Tetrahedron, Vol. 67, Issue 46 https://doi.org/10.1016/j.tet.2011.09.057	journal	November 2011
Mechanochemical 1,1′-Carbonyldiimidazole-Mediated Synthesis of Carbamates Lanzillotto, Marialucia; Konnert, Laure; Lamaty, Frédéric ACS Sustainable Chemistry & Engineering, Vol. 3, Issue 11 https://doi.org/10.1021/acssuschemeng.5b00819	journal	October 2015
N,N'-Carbonyldiimidazole, a New Peptide Forming Reagent¹ Paul, Rolf; Anderson, George W. Journal of the American Chemical Society, Vol. 82, Issue 17 https://doi.org/10.1021/ja01502a038	journal	September 1960
Diazeniumdiolate Ions as Leaving Groups in Anomeric Displacement Reactions: A Protection−Deprotection Strategy for Ionic Diazeniumdiolates Showalter, Brett M.; Reynolds, Melissa M.; Valdez, Carlos A. Journal of the American Chemical Society, Vol. 127, Issue 41 https://doi.org/10.1021/ja054510a	journal	September 2005
Approaches to protection against nerve agent poisoning. (Naphthylvinyl)pyridine derivatives as potential antidotes Gray, Allan P.; Platz, Robert D.; Henderson, Theresa R. Journal of Medicinal Chemistry, Vol. 31, Issue 4 https://doi.org/10.1021/jm00399a022	journal	April 1988
Simple Method for the Preparation of Esters from Grignard Reagents and Alkyl 1-Imidazolecarboxylates Werner, Thomas; Barrett, Anthony G. M. The Journal of Organic Chemistry, Vol. 71, Issue 11 https://doi.org/10.1021/jo060562m	journal	May 2006
Formation of Urea Dipeptides from Carbonyldiimidazole: Application toward the Protease Inhibitors GE 20372 and MAPI Zhang, Xiaowei; Rodrigues, Jason; Evans, Lawrence The Journal of Organic Chemistry, Vol. 62, Issue 18 https://doi.org/10.1021/jo970514p	journal	September 1997
Controlled Synthesis of Asymmetric Dialkyl and Cyclic Carbonates Using the Highly Selective Reactions of Imidazole Carboxylic Esters Rannard, Steve P.; Davis, Nicola J. Organic Letters, Vol. 1, Issue 6 https://doi.org/10.1021/ol9908528	journal	September 1999
Chemical ionization mass spectral analysis of pinacolyl alcohol and development of derivatization method using p-tolyl isocyanate Murty, M. R. V. S.; Prasada Raju, N.; Prabhakar, S. Analytical Methods, Vol. 2, Issue 10 https://doi.org/10.1039/C0AY00346H	journal	January 2010
Reactive imidazole intermediates: simplified synthetic approach to functional aliphatic cyclic carbonates Olsson, Johan V.; Hult, Daniel; Cai, Yanling Polym. Chem., Vol. 5, Issue 23 https://doi.org/10.1039/C4PY00911H	journal	January 2014
Method for the synthesis of N-alkyl-O-alkyl carbamates Vaillard, Victoria A.; González, Marianela; Perotti, Jesica P. RSC Adv., Vol. 4, Issue 25 https://doi.org/10.1039/C4RA00373J	journal	January 2014
Detection of low molecular weight adulterants in beverages by direct analysis in real time mass spectrometry Sisco, Edward; Dake, Jeffrey Analytical Methods, Vol. 8, Issue 14 https://doi.org/10.1039/C6AY00292G	journal	January 2016
Determination of 2-Ethyl-l-Hexanol as Contaminant in Drinking Water Vitali, M.; Leoni, V.; Chiavarini, S. Journal of AOAC INTERNATIONAL, Vol. 76, Issue 5 https://doi.org/10.1093/jaoac/76.5.1133	journal	September 1993
OPCW Proficiency Test: A Practical Approach Also for Interlaboratory Test on Detection and Identification of Pesticides in Environmental Matrices Konopski, Leszek; Liu, Pingfeng; Wuryani, Wuri The Scientific World Journal, Vol. 2014 https://doi.org/10.1155/2014/542357	journal	January 2014
An improved and convenient synthesis of esters using 1,1'-carbonyldiimidazole and a reactive halide. Kamijo, Tetsuhide; Harada, Hiromu; Iizuka, Kinji Chemical and Pharmaceutical Bulletin, Vol. 32, Issue 12 https://doi.org/10.1248/cpb.32.5044	journal	January 1984
Mass Spectrometric Analysis of Chemical Warfare Agents and Their Degradation Products in Soil and Synthetic Samples D'Agostino, Paul A.; Hancock, James R.; Chenier, Claude L. European Journal of Mass Spectrometry, Vol. 9, Issue 6 https://doi.org/10.1255/ejms.583	journal	December 2003
Analysis, identification and confirmation of synthetic opioids using chloroformate chemistry: Retrospective detection of fentanyl and acetylfentanyl in urine and plasma samples by EI-GC-MS and HR-LC-MS Valdez, Carlos A.; Leif, Roald N.; Corzett, Todd H. PLOS ONE, Vol. 17, Issue 11 https://doi.org/10.1371/journal.pone.0275931	journal	November 2022
A Novel Method for the Conversion of Carboxylic Acids to N,N-dimethylamides Using N,N-dimethylacetamide as a Dimethylamine Source Aavula, Sanjeev Kumar; Chikkulapally, Anil; Hanumanthappa, N. Journal of Chemical Research, Vol. 37, Issue 3 https://doi.org/10.3184/174751913X13602686612047	journal	March 2013
Target, Suspect and Non-Target Screening of Silylated Derivatives of Polar Compounds Based on Single Ion Monitoring GC-MS Gumbi, Bhekumuzi Prince; Moodley, Brenda; Birungi, Grace International Journal of Environmental Research and Public Health, Vol. 16, Issue 20 https://doi.org/10.3390/ijerph16204022	journal	October 2019
Analysis of Organophosphorus-Based Nerve Agent Degradation Products by Gas Chromatography-Mass Spectrometry (GC-MS): Current Derivatization Reactions in the Analytical Chemist’s Toolbox Valdez, Carlos A.; Leif, Roald N. Molecules, Vol. 26, Issue 15 https://doi.org/10.3390/molecules26154631	journal	July 2021