DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)

Detalhes bibliográficos
Autor(a) principal: Mejía-Urueta,Rafael
Data de Publicação: 2011
Outros Autores: Mestre-Quintero,Kleyber, Vivas-Reyes,Ricardo
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Journal of the Brazilian Chemical Society (Online)
Texto Completo: http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532011001200005
Resumo: Perfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, 19F nuclear magnetic resonance (NMR 19F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of 19F NMR was performed. In this study we have determined the shielding constant (Σ) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The Σ calculations were made at vacuum and in presence of a solvent. The values of chemical shifts (d), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl3), acetone (CH3COCH3) and methanol (CH3OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS).
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spelling DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)perfluorinated organic compoundsDFT calculationshardness19F NMRPerfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, 19F nuclear magnetic resonance (NMR 19F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of 19F NMR was performed. In this study we have determined the shielding constant (Σ) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The Σ calculations were made at vacuum and in presence of a solvent. The values of chemical shifts (d), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl3), acetone (CH3COCH3) and methanol (CH3OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS).Sociedade Brasileira de Química2011-12-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersiontext/htmlhttp://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532011001200005Journal of the Brazilian Chemical Society v.22 n.12 2011reponame:Journal of the Brazilian Chemical Society (Online)instname:Sociedade Brasileira de Química (SBQ)instacron:SBQ10.1590/S0103-50532011001200005info:eu-repo/semantics/openAccessMejía-Urueta,RafaelMestre-Quintero,KleyberVivas-Reyes,Ricardoeng2012-01-05T00:00:00Zoai:scielo:S0103-50532011001200005Revistahttp://jbcs.sbq.org.brONGhttps://old.scielo.br/oai/scielo-oai.php||office@jbcs.sbq.org.br1678-47900103-5053opendoar:2012-01-05T00:00Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ)false
dc.title.none.fl_str_mv DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
title DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
spellingShingle DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
Mejía-Urueta,Rafael
perfluorinated organic compounds
DFT calculations
hardness
19F NMR
title_short DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
title_full DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
title_fullStr DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
title_full_unstemmed DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
title_sort DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
author Mejía-Urueta,Rafael
author_facet Mejía-Urueta,Rafael
Mestre-Quintero,Kleyber
Vivas-Reyes,Ricardo
author_role author
author2 Mestre-Quintero,Kleyber
Vivas-Reyes,Ricardo
author2_role author
author
dc.contributor.author.fl_str_mv Mejía-Urueta,Rafael
Mestre-Quintero,Kleyber
Vivas-Reyes,Ricardo
dc.subject.por.fl_str_mv perfluorinated organic compounds
DFT calculations
hardness
19F NMR
topic perfluorinated organic compounds
DFT calculations
hardness
19F NMR
description Perfluorinated organic compounds (POCs), such as perfluorooctanesulfonate (PFOS) and perfluoroalkylsulfonamide (PFASA) are compounds that have recently attracted considerable attention worldwide because of its high persistence and wide distribution in the environment. Among the spectroscopic methods used to study the PFASA, 19F nuclear magnetic resonance (NMR 19F) is very effective, due to its ability to determine concentrations of PFASA in biological samples and measure pollution in water samples. For this reason, a theoretical study of the properties of 19F NMR was performed. In this study we have determined the shielding constant (Σ) for different fluorine nucleus of the 18 molecules under study, using density functional theory (DFT) and GIAO method with the B3PW91/6-31+G(d,p) level of calculation. The Σ calculations were made at vacuum and in presence of a solvent. The values of chemical shifts (d), were also calculated in a different level of theory. The best results were obtained with the level of calculation DFT-GIAO/B3PW91/6-31+G(d,p) by considering the solvent such as dimethylsulfoxide (DMSO), chloroform (CHCl3), acetone (CH3COCH3) and methanol (CH3OH). The results were interpreted in terms of calculated hardness at DFT/B3PW91/6-31+G(d, p) level. The behaviour of the hardness was higher in the molecules of four carbons PFASA than eight carbons. This explain theoretically resistance of four carbons PFAS to be transformed into perfluorobutanesulfonate (PFBS).
publishDate 2011
dc.date.none.fl_str_mv 2011-12-01
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
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dc.language.iso.fl_str_mv eng
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dc.relation.none.fl_str_mv 10.1590/S0103-50532011001200005
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
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dc.publisher.none.fl_str_mv Sociedade Brasileira de Química
publisher.none.fl_str_mv Sociedade Brasileira de Química
dc.source.none.fl_str_mv Journal of the Brazilian Chemical Society v.22 n.12 2011
reponame:Journal of the Brazilian Chemical Society (Online)
instname:Sociedade Brasileira de Química (SBQ)
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reponame_str Journal of the Brazilian Chemical Society (Online)
collection Journal of the Brazilian Chemical Society (Online)
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