DFT-GIAO calculation of properties of 19F NMR and stability study of environmentally relevant perfluoroalkylsulfonamides (PFASAmide)
Autor(a) principal: | |
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Data de Publicação: | 2011 |
Outros Autores: | , |
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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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 |
format |
article |
status_str |
publishedVersion |
dc.identifier.uri.fl_str_mv |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532011001200005 |
url |
http://old.scielo.br/scielo.php?script=sci_arttext&pid=S0103-50532011001200005 |
dc.language.iso.fl_str_mv |
eng |
language |
eng |
dc.relation.none.fl_str_mv |
10.1590/S0103-50532011001200005 |
dc.rights.driver.fl_str_mv |
info:eu-repo/semantics/openAccess |
eu_rights_str_mv |
openAccess |
dc.format.none.fl_str_mv |
text/html |
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) instacron:SBQ |
instname_str |
Sociedade Brasileira de Química (SBQ) |
instacron_str |
SBQ |
institution |
SBQ |
reponame_str |
Journal of the Brazilian Chemical Society (Online) |
collection |
Journal of the Brazilian Chemical Society (Online) |
repository.name.fl_str_mv |
Journal of the Brazilian Chemical Society (Online) - Sociedade Brasileira de Química (SBQ) |
repository.mail.fl_str_mv |
||office@jbcs.sbq.org.br |
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1750318172762800128 |