Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane
Nerve agents are a class of organophosphorous chemicals that are prohibited under the Chemical Weapons Convention. Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non‐volatile and very polar, their identific...
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Veröffentlicht in: | Journal of mass spectrometry. 2013-07, Vol.48 (7), p.813-822 |
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description | Nerve agents are a class of organophosphorous chemicals that are prohibited under the Chemical Weapons Convention. Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non‐volatile and very polar, their identification by GC‐MS requires a derivatization step prior to analysis. Standard derivatization methods for gas‐chromatography electron‐impact mass‐spectrometry analysis give very similar spectra for many alkyl phosphonic acid isomers, which complicates the identification process. We present a new reagent, 3‐pyridyldiazomethane, for preparing picolinyl ester derivatives of alkyl methylphosphonic acids facilitating the determination of their structure by enhancing predictable fragmentation of the O‐alkyl chain. This fragmentation is directed by the nitrogen nucleus of the pyridyl moiety that s hydrogen from the O‐alkyl chain, inducing radical cleavage of the carbon–carbon bonds and thereby causing extensive fragmentation that can be used for detailed structure elucidation of the O‐alkyl moiety. The separability of related isomers was tested by comparing the spectra of the picolinyl esters formed from twelve hexyl methylphosphonic acid isomers. Spectral library matches and principal component analysis showed that the picolinyl esters were more effectively separated than the corresponding trimethylsilyl derivatives used in the standard operating procedures. The suggested method will improve the unambiguous structural determination process for phosphonic acids. Copyright © 2013 John Wiley & Sons, Ltd. |
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Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non‐volatile and very polar, their identification by GC‐MS requires a derivatization step prior to analysis. Standard derivatization methods for gas‐chromatography electron‐impact mass‐spectrometry analysis give very similar spectra for many alkyl phosphonic acid isomers, which complicates the identification process. We present a new reagent, 3‐pyridyldiazomethane, for preparing picolinyl ester derivatives of alkyl methylphosphonic acids facilitating the determination of their structure by enhancing predictable fragmentation of the O‐alkyl chain. This fragmentation is directed by the nitrogen nucleus of the pyridyl moiety that s hydrogen from the O‐alkyl chain, inducing radical cleavage of the carbon–carbon bonds and thereby causing extensive fragmentation that can be used for detailed structure elucidation of the O‐alkyl moiety. The separability of related isomers was tested by comparing the spectra of the picolinyl esters formed from twelve hexyl methylphosphonic acid isomers. Spectral library matches and principal component analysis showed that the picolinyl esters were more effectively separated than the corresponding trimethylsilyl derivatives used in the standard operating procedures. The suggested method will improve the unambiguous structural determination process for phosphonic acids. Copyright © 2013 John Wiley & Sons, Ltd.</description><identifier>ISSN: 1076-5174</identifier><identifier>EISSN: 1096-9888</identifier><identifier>DOI: 10.1002/jms.3225</identifier><identifier>PMID: 23832937</identifier><language>eng</language><publisher>England: Blackwell Publishing Ltd</publisher><subject>Chains ; Chemical Warfare Agents - analysis ; Chemical Warfare Agents - chemistry ; Derivatives ; diazomethane ; Diazomethane - chemistry ; Esters ; Fragmentation ; Gas Chromatography-Mass Spectrometry - methods ; Isomerism ; Isomers ; nerve agents ; Nerves ; Phosphonic acids ; Phosphorous Acids - analysis ; Phosphorous Acids - chemistry ; Picolinic Acids - chemistry ; picolinyl derivatives ; Pyridines - chemistry ; Soman - chemistry ; soman isomers ; Spectra</subject><ispartof>Journal of mass spectrometry., 2013-07, Vol.48 (7), p.813-822</ispartof><rights>Copyright © 2013 John Wiley & Sons, Ltd.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4205-2fbd8547b1d5aadec685e9a5216b123d81eccf3ec065aed3455fedd9052197f23</citedby><cites>FETCH-LOGICAL-c4205-2fbd8547b1d5aadec685e9a5216b123d81eccf3ec065aed3455fedd9052197f23</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fjms.3225$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fjms.3225$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/23832937$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Nyholm, Jenny Rattfelt</creatorcontrib><creatorcontrib>Gustafsson, Tomas</creatorcontrib><creatorcontrib>Östin, Anders</creatorcontrib><title>Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane</title><title>Journal of mass spectrometry.</title><addtitle>J. Mass Spectrom</addtitle><description>Nerve agents are a class of organophosphorous chemicals that are prohibited under the Chemical Weapons Convention. Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non‐volatile and very polar, their identification by GC‐MS requires a derivatization step prior to analysis. Standard derivatization methods for gas‐chromatography electron‐impact mass‐spectrometry analysis give very similar spectra for many alkyl phosphonic acid isomers, which complicates the identification process. We present a new reagent, 3‐pyridyldiazomethane, for preparing picolinyl ester derivatives of alkyl methylphosphonic acids facilitating the determination of their structure by enhancing predictable fragmentation of the O‐alkyl chain. This fragmentation is directed by the nitrogen nucleus of the pyridyl moiety that s hydrogen from the O‐alkyl chain, inducing radical cleavage of the carbon–carbon bonds and thereby causing extensive fragmentation that can be used for detailed structure elucidation of the O‐alkyl moiety. The separability of related isomers was tested by comparing the spectra of the picolinyl esters formed from twelve hexyl methylphosphonic acid isomers. Spectral library matches and principal component analysis showed that the picolinyl esters were more effectively separated than the corresponding trimethylsilyl derivatives used in the standard operating procedures. The suggested method will improve the unambiguous structural determination process for phosphonic acids. Copyright © 2013 John Wiley & Sons, Ltd.</description><subject>Chains</subject><subject>Chemical Warfare Agents - analysis</subject><subject>Chemical Warfare Agents - chemistry</subject><subject>Derivatives</subject><subject>diazomethane</subject><subject>Diazomethane - chemistry</subject><subject>Esters</subject><subject>Fragmentation</subject><subject>Gas Chromatography-Mass Spectrometry - methods</subject><subject>Isomerism</subject><subject>Isomers</subject><subject>nerve agents</subject><subject>Nerves</subject><subject>Phosphonic acids</subject><subject>Phosphorous Acids - analysis</subject><subject>Phosphorous Acids - chemistry</subject><subject>Picolinic Acids - chemistry</subject><subject>picolinyl derivatives</subject><subject>Pyridines - chemistry</subject><subject>Soman - chemistry</subject><subject>soman isomers</subject><subject>Spectra</subject><issn>1076-5174</issn><issn>1096-9888</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNqF0ctu1DAYhmELgWgpSFwBssSGTYoPcRwvoYICKrAolO4sj_1nxkNOtZ2W9BK4ahzNUCQkxCpW9OhV4g-hp5QcU0LYy20Xjzlj4h46pERVharr-v5yllUhqCwP0KMYt4QQpcrqITpgvOZMcXmIfp6nMNk0BdNiBwlC53uT_NDjocE9hGvAZg19wp0J3yFEPEXfr_HaRGw3YehMGtbBjJs5gxhxHMGm_BpSmLFpci9Xg7_Oydtd9sanDebFOAfv5tZ5c7vojenhMXrQmDbCk_3zCH19--bLybvi7PPp-5NXZ4UtGREFa1auFqVcUSeMcWCrWoAygtFqRRl3NQVrGw6WVMKA46UQDTinSBZKNowfoRe77hiGqwli0p2PFto2f8MwRU1LrvIFMaX-T7nK3aoUVabP_6LbYQp9_pFFSUlZWcs_QRuGGAM0egw-X-2sKdHLlDpPqZcpM322D06rDtwd_L1dBsUO3PgW5n-G9IeP5_vg3vuY4Medz7vqSnIp9LdPp1pcvKYXVF7qS_4L6my6hQ</recordid><startdate>201307</startdate><enddate>201307</enddate><creator>Nyholm, Jenny Rattfelt</creator><creator>Gustafsson, Tomas</creator><creator>Östin, Anders</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QF</scope><scope>7QO</scope><scope>7QP</scope><scope>7QQ</scope><scope>7QR</scope><scope>7SC</scope><scope>7SE</scope><scope>7SP</scope><scope>7SR</scope><scope>7TA</scope><scope>7TB</scope><scope>7TK</scope><scope>7U5</scope><scope>7U7</scope><scope>8BQ</scope><scope>8FD</scope><scope>C1K</scope><scope>F1W</scope><scope>F28</scope><scope>FR3</scope><scope>H8D</scope><scope>H8G</scope><scope>H97</scope><scope>JG9</scope><scope>JQ2</scope><scope>K9.</scope><scope>KR7</scope><scope>L.G</scope><scope>L7M</scope><scope>L~C</scope><scope>L~D</scope><scope>P64</scope><scope>7X8</scope></search><sort><creationdate>201307</creationdate><title>Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane</title><author>Nyholm, Jenny Rattfelt ; Gustafsson, Tomas ; Östin, Anders</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4205-2fbd8547b1d5aadec685e9a5216b123d81eccf3ec065aed3455fedd9052197f23</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2013</creationdate><topic>Chains</topic><topic>Chemical Warfare Agents - analysis</topic><topic>Chemical Warfare Agents - chemistry</topic><topic>Derivatives</topic><topic>diazomethane</topic><topic>Diazomethane - chemistry</topic><topic>Esters</topic><topic>Fragmentation</topic><topic>Gas Chromatography-Mass Spectrometry - methods</topic><topic>Isomerism</topic><topic>Isomers</topic><topic>nerve agents</topic><topic>Nerves</topic><topic>Phosphonic acids</topic><topic>Phosphorous Acids - analysis</topic><topic>Phosphorous Acids - chemistry</topic><topic>Picolinic Acids - chemistry</topic><topic>picolinyl derivatives</topic><topic>Pyridines - chemistry</topic><topic>Soman - chemistry</topic><topic>soman isomers</topic><topic>Spectra</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Nyholm, Jenny Rattfelt</creatorcontrib><creatorcontrib>Gustafsson, Tomas</creatorcontrib><creatorcontrib>Östin, Anders</creatorcontrib><collection>Istex</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Aluminium Industry Abstracts</collection><collection>Biotechnology Research Abstracts</collection><collection>Calcium & Calcified Tissue Abstracts</collection><collection>Ceramic Abstracts</collection><collection>Chemoreception Abstracts</collection><collection>Computer and Information Systems Abstracts</collection><collection>Corrosion Abstracts</collection><collection>Electronics & Communications Abstracts</collection><collection>Engineered Materials Abstracts</collection><collection>Materials Business File</collection><collection>Mechanical & Transportation Engineering Abstracts</collection><collection>Neurosciences Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>Toxicology Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>ASFA: Aquatic Sciences and Fisheries Abstracts</collection><collection>ANTE: Abstracts in New Technology & Engineering</collection><collection>Engineering Research Database</collection><collection>Aerospace Database</collection><collection>Copper Technical Reference Library</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) 3: Aquatic Pollution & Environmental Quality</collection><collection>Materials Research Database</collection><collection>ProQuest Computer Science Collection</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>Civil Engineering Abstracts</collection><collection>Aquatic Science & Fisheries Abstracts (ASFA) Professional</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>Computer and Information Systems Abstracts Academic</collection><collection>Computer and Information Systems Abstracts Professional</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of mass spectrometry.</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Nyholm, Jenny Rattfelt</au><au>Gustafsson, Tomas</au><au>Östin, Anders</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane</atitle><jtitle>Journal of mass spectrometry.</jtitle><addtitle>J. Mass Spectrom</addtitle><date>2013-07</date><risdate>2013</risdate><volume>48</volume><issue>7</issue><spage>813</spage><epage>822</epage><pages>813-822</pages><issn>1076-5174</issn><eissn>1096-9888</eissn><abstract>Nerve agents are a class of organophosphorous chemicals that are prohibited under the Chemical Weapons Convention. Their degradation products, phosphonic acids, are analyzed as markers of nerve agent contamination and use. Because the phosphonic acids are non‐volatile and very polar, their identification by GC‐MS requires a derivatization step prior to analysis. Standard derivatization methods for gas‐chromatography electron‐impact mass‐spectrometry analysis give very similar spectra for many alkyl phosphonic acid isomers, which complicates the identification process. We present a new reagent, 3‐pyridyldiazomethane, for preparing picolinyl ester derivatives of alkyl methylphosphonic acids facilitating the determination of their structure by enhancing predictable fragmentation of the O‐alkyl chain. This fragmentation is directed by the nitrogen nucleus of the pyridyl moiety that s hydrogen from the O‐alkyl chain, inducing radical cleavage of the carbon–carbon bonds and thereby causing extensive fragmentation that can be used for detailed structure elucidation of the O‐alkyl moiety. The separability of related isomers was tested by comparing the spectra of the picolinyl esters formed from twelve hexyl methylphosphonic acid isomers. Spectral library matches and principal component analysis showed that the picolinyl esters were more effectively separated than the corresponding trimethylsilyl derivatives used in the standard operating procedures. The suggested method will improve the unambiguous structural determination process for phosphonic acids. Copyright © 2013 John Wiley & Sons, Ltd.</abstract><cop>England</cop><pub>Blackwell Publishing Ltd</pub><pmid>23832937</pmid><doi>10.1002/jms.3225</doi><tpages>10</tpages></addata></record> |
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subjects | Chains Chemical Warfare Agents - analysis Chemical Warfare Agents - chemistry Derivatives diazomethane Diazomethane - chemistry Esters Fragmentation Gas Chromatography-Mass Spectrometry - methods Isomerism Isomers nerve agents Nerves Phosphonic acids Phosphorous Acids - analysis Phosphorous Acids - chemistry Picolinic Acids - chemistry picolinyl derivatives Pyridines - chemistry Soman - chemistry soman isomers Spectra |
title | Structural determination of nerve agent markers using gas chromatography mass spectrometry after derivatization with 3-pyridyldiazomethane |
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