Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies

Detalhes bibliográficos
Autor(a) principal: Ximenes, Valdecir F. [UNESP]
Data de Publicação: 2022
Outros Autores: Pavan, Nathalia M. [UNESP], Souza, Aguinaldo R. de [UNESP], Barros, Gabriel A., Morgon, Nelson H.
Tipo de documento: Artigo
Idioma: eng
Título da fonte: Repositório Institucional da UNESP
Texto Completo: http://dx.doi.org/10.21577/0103-5053.20220088
http://hdl.handle.net/11449/237777
Resumo: There is robust evidence of the hypochlorous acid (HClO)-mediated damage in biomolecules, and nicotine boosts the chlorination potency of HClO. We present experimental and theoretical evidence of the mechanism by which nicotine catalyzes the chlorination of pyranine. The rate constants for chlorination of pyranine by HClO were measured in the presence (5.3 x 10(5) mol(-1) L s(-1)) and absence of nicotine (4.2 x 10(3) mol(-1) L s(-1)), revealing the catalytic effect of the alkaloid. Density functional theory (DFT) calculations, based on B3LYP-GD3(BJ)/6-311++G(3df,2p)/SMD(Water)//B3LYP-GD3(BJ)/6-311++G(2d,p)/SMD(Water) level of theory, were performed and showed a decreased activation energy for chlorine transfer and hydrogen abstraction when nicotine chloramine intermediated the reaction. The atomic polar tensor (APT) charges on the chlorine atom of HClO (+0.084) were lower than the chlorine of nicotine chloramine (+0.149), revealing the higher electrophilic character of nicotine chloramine. In conclusion, the increased electrophilic nature of HClO provoked by nicotine explains its catalytic effect.
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spelling Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical StudiesHypochlorous acidNicotineChlorination of biomoleculesDFT calculationsThere is robust evidence of the hypochlorous acid (HClO)-mediated damage in biomolecules, and nicotine boosts the chlorination potency of HClO. We present experimental and theoretical evidence of the mechanism by which nicotine catalyzes the chlorination of pyranine. The rate constants for chlorination of pyranine by HClO were measured in the presence (5.3 x 10(5) mol(-1) L s(-1)) and absence of nicotine (4.2 x 10(3) mol(-1) L s(-1)), revealing the catalytic effect of the alkaloid. Density functional theory (DFT) calculations, based on B3LYP-GD3(BJ)/6-311++G(3df,2p)/SMD(Water)//B3LYP-GD3(BJ)/6-311++G(2d,p)/SMD(Water) level of theory, were performed and showed a decreased activation energy for chlorine transfer and hydrogen abstraction when nicotine chloramine intermediated the reaction. The atomic polar tensor (APT) charges on the chlorine atom of HClO (+0.084) were lower than the chlorine of nicotine chloramine (+0.149), revealing the higher electrophilic character of nicotine chloramine. In conclusion, the increased electrophilic nature of HClO provoked by nicotine explains its catalytic effect.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)National Institute of Science and Technology -INCT BioNatFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Univ Estadual Paulista UNESP, Fac Ciencia, Dept Quim, BR-17033360 Bauru, SP, BrazilUniv Estadual Campinas UNICAMP, Inst Quim, Dept Fis Quim, BR-13083861 Campinas, SP, BrazilUniv Estadual Paulista UNESP, Fac Ciencia, Dept Quim, BR-17033360 Bauru, SP, BrazilCNPq: 303485/2019-1CNPq: 303581/2018-2CAPES: 001CAPES: 88887.612536/2021-00CAPES: 88887.194785/2018-00National Institute of Science and Technology -INCT BioNat: 465637/2014-0FAPESP: 2019/18445-5FAPESP: 2019/12294-5Soc Brasileira QuimicaUniversidade Estadual Paulista (UNESP)Universidade Estadual de Campinas (UNICAMP)Ximenes, Valdecir F. [UNESP]Pavan, Nathalia M. [UNESP]Souza, Aguinaldo R. de [UNESP]Barros, Gabriel A.Morgon, Nelson H.2022-11-30T13:44:37Z2022-11-30T13:44:37Z2022-06-27info:eu-repo/semantics/publishedVersioninfo:eu-repo/semantics/article6http://dx.doi.org/10.21577/0103-5053.20220088Journal Of The Brazilian Chemical Society. Sao Paulo: Soc Brasileira Quimica, 6 p., 2022.0103-5053http://hdl.handle.net/11449/23777710.21577/0103-5053.20220088WOS:000821247100001Web of Sciencereponame:Repositório Institucional da UNESPinstname:Universidade Estadual Paulista (UNESP)instacron:UNESPengJournal Of The Brazilian Chemical Societyinfo:eu-repo/semantics/openAccess2024-04-29T18:16:46Zoai:repositorio.unesp.br:11449/237777Repositório InstitucionalPUBhttp://repositorio.unesp.br/oai/requestopendoar:29462024-08-05T14:56:28.418053Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)false
dc.title.none.fl_str_mv Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
title Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
spellingShingle Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
Ximenes, Valdecir F. [UNESP]
Hypochlorous acid
Nicotine
Chlorination of biomolecules
DFT calculations
title_short Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
title_full Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
title_fullStr Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
title_full_unstemmed Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
title_sort Nicotine as a Catalyst for Chlorination Promoted by Hypochlorous Acid: Experimental and Theoretical Studies
author Ximenes, Valdecir F. [UNESP]
author_facet Ximenes, Valdecir F. [UNESP]
Pavan, Nathalia M. [UNESP]
Souza, Aguinaldo R. de [UNESP]
Barros, Gabriel A.
Morgon, Nelson H.
author_role author
author2 Pavan, Nathalia M. [UNESP]
Souza, Aguinaldo R. de [UNESP]
Barros, Gabriel A.
Morgon, Nelson H.
author2_role author
author
author
author
dc.contributor.none.fl_str_mv Universidade Estadual Paulista (UNESP)
Universidade Estadual de Campinas (UNICAMP)
dc.contributor.author.fl_str_mv Ximenes, Valdecir F. [UNESP]
Pavan, Nathalia M. [UNESP]
Souza, Aguinaldo R. de [UNESP]
Barros, Gabriel A.
Morgon, Nelson H.
dc.subject.por.fl_str_mv Hypochlorous acid
Nicotine
Chlorination of biomolecules
DFT calculations
topic Hypochlorous acid
Nicotine
Chlorination of biomolecules
DFT calculations
description There is robust evidence of the hypochlorous acid (HClO)-mediated damage in biomolecules, and nicotine boosts the chlorination potency of HClO. We present experimental and theoretical evidence of the mechanism by which nicotine catalyzes the chlorination of pyranine. The rate constants for chlorination of pyranine by HClO were measured in the presence (5.3 x 10(5) mol(-1) L s(-1)) and absence of nicotine (4.2 x 10(3) mol(-1) L s(-1)), revealing the catalytic effect of the alkaloid. Density functional theory (DFT) calculations, based on B3LYP-GD3(BJ)/6-311++G(3df,2p)/SMD(Water)//B3LYP-GD3(BJ)/6-311++G(2d,p)/SMD(Water) level of theory, were performed and showed a decreased activation energy for chlorine transfer and hydrogen abstraction when nicotine chloramine intermediated the reaction. The atomic polar tensor (APT) charges on the chlorine atom of HClO (+0.084) were lower than the chlorine of nicotine chloramine (+0.149), revealing the higher electrophilic character of nicotine chloramine. In conclusion, the increased electrophilic nature of HClO provoked by nicotine explains its catalytic effect.
publishDate 2022
dc.date.none.fl_str_mv 2022-11-30T13:44:37Z
2022-11-30T13:44:37Z
2022-06-27
dc.type.status.fl_str_mv info:eu-repo/semantics/publishedVersion
dc.type.driver.fl_str_mv info:eu-repo/semantics/article
format article
status_str publishedVersion
dc.identifier.uri.fl_str_mv http://dx.doi.org/10.21577/0103-5053.20220088
Journal Of The Brazilian Chemical Society. Sao Paulo: Soc Brasileira Quimica, 6 p., 2022.
0103-5053
http://hdl.handle.net/11449/237777
10.21577/0103-5053.20220088
WOS:000821247100001
url http://dx.doi.org/10.21577/0103-5053.20220088
http://hdl.handle.net/11449/237777
identifier_str_mv Journal Of The Brazilian Chemical Society. Sao Paulo: Soc Brasileira Quimica, 6 p., 2022.
0103-5053
10.21577/0103-5053.20220088
WOS:000821247100001
dc.language.iso.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv Journal Of The Brazilian Chemical Society
dc.rights.driver.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv 6
dc.publisher.none.fl_str_mv Soc Brasileira Quimica
publisher.none.fl_str_mv Soc Brasileira Quimica
dc.source.none.fl_str_mv Web of Science
reponame:Repositório Institucional da UNESP
instname:Universidade Estadual Paulista (UNESP)
instacron:UNESP
instname_str Universidade Estadual Paulista (UNESP)
instacron_str UNESP
institution UNESP
reponame_str Repositório Institucional da UNESP
collection Repositório Institucional da UNESP
repository.name.fl_str_mv Repositório Institucional da UNESP - Universidade Estadual Paulista (UNESP)
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