PMID- 35901667 OWN - NLM STAT- MEDLINE DCOM- 20220816 LR - 20220816 IS - 1873-3778 (Electronic) IS - 0021-9673 (Linking) VI - 1678 DP - 2022 Aug 16 TI - Simultaneous quantification of multiple amino acid adducts from sulfur mustard-modified human serum albumin in plasma at trace exposure levels by ultra-high performance liquid chromatography-triple quadrupole mass spectrometry after propionyl derivatization. PG - 463354 LID - S0021-9673(22)00547-7 [pii] LID - 10.1016/j.chroma.2022.463354 [doi] AB - Sulfur mustard (HD) is a highly toxic vesicant and is prohibited by the Organisation for the Prohibition of Chemical Weapons (OPCW). HD can modify human serum albumin (HSA) to generate hydroxyethylthioethyl (HETE) adducts, which could be utilized as biomarkers for verifying HD exposure in forensic analysis. Here, five amino acid adducts generated from pronase digestion of HD-exposed human serum albumin (HD-HSA) in plasma were selected as biomarkers to retrospectively detect HD exposure. HD-HSA was precipitated from plasma with acetone, digested by pronase, derivatized with propionic anhydride (PA), and analysed with ultra-high performance liquid chromatography coupled with triple quadrupole mass spectrometry (UHPLC-TQ MS). The limits of detection (LODs) and limits of quantification (LOQs) of the HD exposure concentrations were evaluated as 1.00 ng/mL at S/N>/=3 and 3.00 ng/mL at S/N>/=10, respectively, which are approximately 60 times lower than those of the reported method. The approach shows good linearity (R(2)>/=0.997) from 3.00 ng/mL to 10.0 microg/mL of HD-exposed human plasma with satisfactory precision and accuracy. The developed approach was applied to analysing samples from the 6(th) OPCW Biomedical Proficiency Test (BioPT). The study showed that the developed approach was also suitable for analysing human plasma samples that were exposed to six of HD analogues, which were common impurities in sulfur mustard mixtures. Moreover, the method was successfully applied to plasma from other species, including rabbits, rats and cattle. This study provides a reliable and sensitive tool for the retrospective detection of vesicants exposure based on multiple biomarkers. CI - Copyright (c) 2022. Published by Elsevier B.V. FAU - Chen, Bo AU - Chen B AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. FAU - Ren, Zhe AU - Ren Z AD - School of Chemistry and Chemical Engineering, Nanjing University of Sciences & Technology, Nanjing, 210094, P. R. China. FAU - Zhang, Tao AU - Zhang T AD - State Key Laboratory of Proteomics, Beijing Proteome Research Center, National Center for Protein Sciences (Beijing), Research Unit of Proteomics & Research and Development of New Drug of Chinese Academy of Medical Sciences, Institute of Lifeomics, Beijing, 102206, P. R. China. FAU - Yu, Huilan AU - Yu H AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. FAU - Shu, ZhiBin AU - Shu Z AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. FAU - Liu, Changcai AU - Liu C AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. FAU - Yang, Yang AU - Yang Y AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. FAU - Xu, Ping AU - Xu P AD - State Key Laboratory of Proteomics, Beijing Proteome Research Center, National Center for Protein Sciences (Beijing), Research Unit of Proteomics & Research and Development of New Drug of Chinese Academy of Medical Sciences, Institute of Lifeomics, Beijing, 102206, P. R. China. Electronic address: xuping_bprc@126.com. FAU - Liu, Shilei AU - Liu S AD - State Key Laboratory of NBC Protection for Civilian, Laboratory of Analytical Chemistry, Research Institute of Chemical Defence, Beijing 102205, P. R. China. Electronic address: liu_shilei@lacricd.com. LA - eng PT - Journal Article DEP - 20220719 PL - Netherlands TA - J Chromatogr A JT - Journal of chromatography. A JID - 9318488 RN - 0 (Amino Acids) RN - 0 (Biomarkers) RN - 0 (Chemical Warfare Agents) RN - 0 (Irritants) RN - EC 3.4.24.- (Pronase) RN - T8KEC9FH9P (Mustard Gas) RN - ZIF514RVZR (Serum Albumin, Human) SB - IM MH - Amino Acids MH - Animals MH - Biomarkers MH - Cattle MH - *Chemical Warfare Agents/analysis MH - Chromatography, High Pressure Liquid/methods MH - Humans MH - Irritants/analysis MH - *Mustard Gas/analysis MH - Pronase/chemistry MH - Rabbits MH - Rats MH - Retrospective Studies MH - Serum Albumin, Human/analysis MH - Tandem Mass Spectrometry/methods OTO - NOTNLM OT - Human serum albumin OT - Multiple biomarkers OT - Retrospective detection OT - Sulfur mustard OT - Trace exposure COIS- Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. EDAT- 2022/07/29 06:00 MHDA- 2022/08/17 06:00 CRDT- 2022/07/28 18:23 PHST- 2022/05/31 00:00 [received] PHST- 2022/07/17 00:00 [revised] PHST- 2022/07/18 00:00 [accepted] PHST- 2022/07/29 06:00 [pubmed] PHST- 2022/08/17 06:00 [medline] PHST- 2022/07/28 18:23 [entrez] AID - S0021-9673(22)00547-7 [pii] AID - 10.1016/j.chroma.2022.463354 [doi] PST - ppublish SO - J Chromatogr A. 2022 Aug 16;1678:463354. doi: 10.1016/j.chroma.2022.463354. Epub 2022 Jul 19.