Thermodynamic, Spectroscopic, and Computational Evidence for the Irreversible Conversion of β- to α-Endosulfan
Previous studies have provided unequivocal evidence for the symmetry of β-endosulfan and the corresponding asymmetry of α-endosulfan; the conversion of β-endosulfan to α-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NM...
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| Veröffentlicht in: | Journal of agricultural and food chemistry 2001-11, Vol.49 (11), p.5372-5376 |
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| container_end_page | 5376 |
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| container_issue | 11 |
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| container_title | Journal of agricultural and food chemistry |
| container_volume | 49 |
| creator | Schmidt, Walter F Bilboulian, Susanna Rice, Clifford P Fettinger, James C McConnell, Laura L Hapeman, Cathleen J |
| description | Previous studies have provided unequivocal evidence for the symmetry of β-endosulfan and the corresponding asymmetry of α-endosulfan; the conversion of β-endosulfan to α-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative SO configuration between α- and β-isomers can be the intermediate state through which the conformations of α- and β-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in α-endosulfan can induce asymmetry in β-endosulfan, and conversion to α-endosulfan occurs from this transition state. Keywords: α- and β-endosulfan; conformation; NMR; volatility; eutectic mixture; computational chemistry |
| doi_str_mv | 10.1021/jf0102214 |
| format | Article |
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In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative SO configuration between α- and β-isomers can be the intermediate state through which the conformations of α- and β-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in α-endosulfan can induce asymmetry in β-endosulfan, and conversion to α-endosulfan occurs from this transition state. Keywords: α- and β-endosulfan; conformation; NMR; volatility; eutectic mixture; computational chemistry</description><identifier>ISSN: 0021-8561</identifier><identifier>EISSN: 1520-5118</identifier><identifier>DOI: 10.1021/jf0102214</identifier><identifier>PMID: 11714330</identifier><identifier>CODEN: JAFCAU</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Agronomy. Soil science and plant productions ; Applied sciences ; Biological and medical sciences ; Calorimetry, Differential Scanning ; Chromatography, Gas ; Endosulfan - chemistry ; Exact sciences and technology ; Fundamental and applied biological sciences. Psychology ; Hydrocarbons, Chlorinated ; Insecticides - chemistry ; Magnetic Resonance Spectroscopy ; Pollution ; Soil and sediments pollution ; Soil and water pollution ; Soil science ; Thermodynamics</subject><ispartof>Journal of agricultural and food chemistry, 2001-11, Vol.49 (11), p.5372-5376</ispartof><rights>Copyright © 2001 American Chemical Society</rights><rights>2002 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a379t-7befae1bc6420b43a4faac47ca156619f0cc4d9f9ec804660a1079e6982d15583</citedby><cites>FETCH-LOGICAL-a379t-7befae1bc6420b43a4faac47ca156619f0cc4d9f9ec804660a1079e6982d15583</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/jf0102214$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/jf0102214$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>314,780,784,2765,27076,27924,27925,56738,56788</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=14106294$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/11714330$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Schmidt, Walter F</creatorcontrib><creatorcontrib>Bilboulian, Susanna</creatorcontrib><creatorcontrib>Rice, Clifford P</creatorcontrib><creatorcontrib>Fettinger, James C</creatorcontrib><creatorcontrib>McConnell, Laura L</creatorcontrib><creatorcontrib>Hapeman, Cathleen J</creatorcontrib><title>Thermodynamic, Spectroscopic, and Computational Evidence for the Irreversible Conversion of β- to α-Endosulfan</title><title>Journal of agricultural and food chemistry</title><addtitle>J. Agric. Food Chem</addtitle><description>Previous studies have provided unequivocal evidence for the symmetry of β-endosulfan and the corresponding asymmetry of α-endosulfan; the conversion of β-endosulfan to α-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative SO configuration between α- and β-isomers can be the intermediate state through which the conformations of α- and β-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in α-endosulfan can induce asymmetry in β-endosulfan, and conversion to α-endosulfan occurs from this transition state. Keywords: α- and β-endosulfan; conformation; NMR; volatility; eutectic mixture; computational chemistry</description><subject>Agronomy. Soil science and plant productions</subject><subject>Applied sciences</subject><subject>Biological and medical sciences</subject><subject>Calorimetry, Differential Scanning</subject><subject>Chromatography, Gas</subject><subject>Endosulfan - chemistry</subject><subject>Exact sciences and technology</subject><subject>Fundamental and applied biological sciences. Psychology</subject><subject>Hydrocarbons, Chlorinated</subject><subject>Insecticides - chemistry</subject><subject>Magnetic Resonance Spectroscopy</subject><subject>Pollution</subject><subject>Soil and sediments pollution</subject><subject>Soil and water pollution</subject><subject>Soil science</subject><subject>Thermodynamics</subject><issn>0021-8561</issn><issn>1520-5118</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2001</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNptkMFu1DAQhi0EokvhwAsgXzggEZhJHDs5ou1SKlUFscvZmji2miWxIztb0ceCB-kzkWVX3Qunf0b_p18zP2OvET4g5Phx62DWHMUTtsAyh6xErJ6yBcxmVpUSz9iLlLYAUJUKnrMzRIWiKGDBxs2tjUNo7z0NnXnP16M1UwzJhHG_km_5MgzjbqKpC556vrrrWuuN5S5EPt1afhWjvbMxdU1vZ9b_m4PnwfGHPxmfAn_4na18G9Kud-RfsmeO-mRfHfWc_fi82iy_ZNdfL6-Wn64zKlQ9Zaqxjiw2RoocGlGQcERGKENYSom1A2NEW7vamgqElEAIqrayrvIWy7Iqztm7Q66Zv0nROj3GbqB4rxH0vjX92NrMvjmw464ZbHsijzXNwNsjQMlQ7yJ506UTJxBkXu-DsgPXpcn-evQp_tRSFarUm29rfXO5_H4h10rfnHLJJL0Nuzg3nP5z4F9T45Fh</recordid><startdate>20011101</startdate><enddate>20011101</enddate><creator>Schmidt, Walter F</creator><creator>Bilboulian, Susanna</creator><creator>Rice, Clifford P</creator><creator>Fettinger, James C</creator><creator>McConnell, Laura L</creator><creator>Hapeman, Cathleen J</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</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></search><sort><creationdate>20011101</creationdate><title>Thermodynamic, Spectroscopic, and Computational Evidence for the Irreversible Conversion of β- to α-Endosulfan</title><author>Schmidt, Walter F ; Bilboulian, Susanna ; Rice, Clifford P ; Fettinger, James C ; McConnell, Laura L ; Hapeman, Cathleen J</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a379t-7befae1bc6420b43a4faac47ca156619f0cc4d9f9ec804660a1079e6982d15583</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2001</creationdate><topic>Agronomy. Soil science and plant productions</topic><topic>Applied sciences</topic><topic>Biological and medical sciences</topic><topic>Calorimetry, Differential Scanning</topic><topic>Chromatography, Gas</topic><topic>Endosulfan - chemistry</topic><topic>Exact sciences and technology</topic><topic>Fundamental and applied biological sciences. Psychology</topic><topic>Hydrocarbons, Chlorinated</topic><topic>Insecticides - chemistry</topic><topic>Magnetic Resonance Spectroscopy</topic><topic>Pollution</topic><topic>Soil and sediments pollution</topic><topic>Soil and water pollution</topic><topic>Soil science</topic><topic>Thermodynamics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Schmidt, Walter F</creatorcontrib><creatorcontrib>Bilboulian, Susanna</creatorcontrib><creatorcontrib>Rice, Clifford P</creatorcontrib><creatorcontrib>Fettinger, James C</creatorcontrib><creatorcontrib>McConnell, Laura L</creatorcontrib><creatorcontrib>Hapeman, Cathleen J</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><jtitle>Journal of agricultural and food chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Schmidt, Walter F</au><au>Bilboulian, Susanna</au><au>Rice, Clifford P</au><au>Fettinger, James C</au><au>McConnell, Laura L</au><au>Hapeman, Cathleen J</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Thermodynamic, Spectroscopic, and Computational Evidence for the Irreversible Conversion of β- to α-Endosulfan</atitle><jtitle>Journal of agricultural and food chemistry</jtitle><addtitle>J. Agric. Food Chem</addtitle><date>2001-11-01</date><risdate>2001</risdate><volume>49</volume><issue>11</issue><spage>5372</spage><epage>5376</epage><pages>5372-5376</pages><issn>0021-8561</issn><eissn>1520-5118</eissn><coden>JAFCAU</coden><abstract>Previous studies have provided unequivocal evidence for the symmetry of β-endosulfan and the corresponding asymmetry of α-endosulfan; the conversion of β-endosulfan to α-endosulfan was identified. In this study, evidence from differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR) experiments combined with computational chemistry calculations was used to propose a molecular mechanism for the corresponding conformational changes that occur in this process. DSC and NMR data of mixtures indicated that both isomers can influence the conformer populations in the solid, solution, and vapor phase. Computational chemistry demonstrated that the relative SO configuration between α- and β-isomers can be the intermediate state through which the conformations of α- and β-isomers affect each other. Furthermore, calculations for mixtures indicated that the asymmetrical conformation of the sulfite in α-endosulfan can induce asymmetry in β-endosulfan, and conversion to α-endosulfan occurs from this transition state. Keywords: α- and β-endosulfan; conformation; NMR; volatility; eutectic mixture; computational chemistry</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>11714330</pmid><doi>10.1021/jf0102214</doi><tpages>5</tpages></addata></record> |
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| subjects | Agronomy. Soil science and plant productions Applied sciences Biological and medical sciences Calorimetry, Differential Scanning Chromatography, Gas Endosulfan - chemistry Exact sciences and technology Fundamental and applied biological sciences. Psychology Hydrocarbons, Chlorinated Insecticides - chemistry Magnetic Resonance Spectroscopy Pollution Soil and sediments pollution Soil and water pollution Soil science Thermodynamics |
| title | Thermodynamic, Spectroscopic, and Computational Evidence for the Irreversible Conversion of β- to α-Endosulfan |
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