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Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry

PURPOSE: The detection of hydrolysis products of Novichok agents in biological samples from victims is important for confirming exposure to these agents. However, Novichok agents are new class of nerve agent and there have been only few reports on analyses of Novichok agent degradation products. Her...

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Detalles Bibliográficos
Autores principales: Otsuka, Mai, Yamaguchi, Akinori, Miyaguchi, Hajime
Formato: Online Artículo Texto
Lenguaje:English
Publicado: Springer Nature Singapore 2022
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10310577/
https://www.ncbi.nlm.nih.gov/pubmed/36586094
http://dx.doi.org/10.1007/s11419-022-00656-4
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author Otsuka, Mai
Yamaguchi, Akinori
Miyaguchi, Hajime
author_facet Otsuka, Mai
Yamaguchi, Akinori
Miyaguchi, Hajime
author_sort Otsuka, Mai
collection PubMed
description PURPOSE: The detection of hydrolysis products of Novichok agents in biological samples from victims is important for confirming exposure to these agents. However, Novichok agents are new class of nerve agent and there have been only few reports on analyses of Novichok agent degradation products. Here, we developed hydrophilic interaction liquid chromatography (HILIC)–tandem mass spectrometry (MS/MS) methods to detect Novichok agent degradation products in human urine with simple pretreatment and high sensitivity. METHODS: A Poroshell 120 HILIC-Z column was used to analyze six Novichok agent degradation products. For urine samples, we used a simple pretreatment method, which consisted of deproteinization with acetonitrile and microfiltration. We calculated the pK(a) values of the OH groups, the log P values, and the molecular weights to investigate the difference in chromatographic behaviors of the Novichok agent degradation products and the degradation products of conventional nerve agents. RESULTS: Six Novichok agent degradation products, including N-(bis-(diethylamino)methylidene)-methylphosphonamidic acid (MPGA), which could not be detected by our previous method, could be analyzed with sufficient peak shape and mutual separation. The detection limits of six Novichok agent degradation products were sufficiently low (1–50 ng/mL) and the calibration curves showed sufficient linearity. The physicochemical parameters of Novichok agent degradation products were different from those of conventional nerve agent degradation products, and this explains the difference in chromatographic behaviors. CONCLUSION: Six Novichok agent degradation products were successfully analyzed by HILIC–MS/MS. Due to the absence of a derivatization step, throughput performance was higher than our previous derivatization-liquid chromatography–MS/MS method. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11419-022-00656-4.
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spelling pubmed-103105772023-07-01 Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry Otsuka, Mai Yamaguchi, Akinori Miyaguchi, Hajime Forensic Toxicol Original Article PURPOSE: The detection of hydrolysis products of Novichok agents in biological samples from victims is important for confirming exposure to these agents. However, Novichok agents are new class of nerve agent and there have been only few reports on analyses of Novichok agent degradation products. Here, we developed hydrophilic interaction liquid chromatography (HILIC)–tandem mass spectrometry (MS/MS) methods to detect Novichok agent degradation products in human urine with simple pretreatment and high sensitivity. METHODS: A Poroshell 120 HILIC-Z column was used to analyze six Novichok agent degradation products. For urine samples, we used a simple pretreatment method, which consisted of deproteinization with acetonitrile and microfiltration. We calculated the pK(a) values of the OH groups, the log P values, and the molecular weights to investigate the difference in chromatographic behaviors of the Novichok agent degradation products and the degradation products of conventional nerve agents. RESULTS: Six Novichok agent degradation products, including N-(bis-(diethylamino)methylidene)-methylphosphonamidic acid (MPGA), which could not be detected by our previous method, could be analyzed with sufficient peak shape and mutual separation. The detection limits of six Novichok agent degradation products were sufficiently low (1–50 ng/mL) and the calibration curves showed sufficient linearity. The physicochemical parameters of Novichok agent degradation products were different from those of conventional nerve agent degradation products, and this explains the difference in chromatographic behaviors. CONCLUSION: Six Novichok agent degradation products were successfully analyzed by HILIC–MS/MS. Due to the absence of a derivatization step, throughput performance was higher than our previous derivatization-liquid chromatography–MS/MS method. SUPPLEMENTARY INFORMATION: The online version contains supplementary material available at 10.1007/s11419-022-00656-4. Springer Nature Singapore 2022-12-31 2023 /pmc/articles/PMC10310577/ /pubmed/36586094 http://dx.doi.org/10.1007/s11419-022-00656-4 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open AccessThis article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) .
spellingShingle Original Article
Otsuka, Mai
Yamaguchi, Akinori
Miyaguchi, Hajime
Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title_full Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title_fullStr Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title_full_unstemmed Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title_short Analysis of degradation products of Novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
title_sort analysis of degradation products of novichok agents in human urine by hydrophilic interaction liquid chromatography–tandem mass spectrometry
topic Original Article
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10310577/
https://www.ncbi.nlm.nih.gov/pubmed/36586094
http://dx.doi.org/10.1007/s11419-022-00656-4
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