A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase

Autores
Butler, Matias; Cabrera, Gabriela Myriam
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system.
Fil: Butler, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Cabrera, Gabriela Myriam. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Materia
DENSITY FUNCTIONAL THEORY
ELECTROSPRAY IONIZATION MASS SPECTROMETRY
METAL COMPLEXES
PYRITHIONE
REDOX-ACTIVE LIGAND
Nivel de accesibilidad
acceso embargado
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/60933

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network_name_str CONICET Digital (CONICET)
spelling A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phaseButler, MatiasCabrera, Gabriela MyriamDENSITY FUNCTIONAL THEORYELECTROSPRAY IONIZATION MASS SPECTROMETRYMETAL COMPLEXESPYRITHIONEREDOX-ACTIVE LIGANDhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/12-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system.Fil: Butler, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaFil: Cabrera, Gabriela Myriam. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; ArgentinaJohn Wiley & Sons Ltd2017-11info:eu-repo/date/embargoEnd/2018-12-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/60933Butler, Matias; Cabrera, Gabriela Myriam; A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase; John Wiley & Sons Ltd; Journal of Mass Spectrometry; 52; 11; 11-2017; 728-7381076-51741096-9888CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://onlinelibrary.wiley.com/doi/full/10.1002/jms.3976info:eu-repo/semantics/altIdentifier/doi/10.1002/jms.3976info:eu-repo/semantics/embargoedAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:51:10Zoai:ri.conicet.gov.ar:11336/60933instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-09-29 09:51:10.336CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
spellingShingle A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
Butler, Matias
DENSITY FUNCTIONAL THEORY
ELECTROSPRAY IONIZATION MASS SPECTROMETRY
METAL COMPLEXES
PYRITHIONE
REDOX-ACTIVE LIGAND
title_short A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_full A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_fullStr A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_full_unstemmed A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
title_sort A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase
dc.creator.none.fl_str_mv Butler, Matias
Cabrera, Gabriela Myriam
author Butler, Matias
author_facet Butler, Matias
Cabrera, Gabriela Myriam
author_role author
author2 Cabrera, Gabriela Myriam
author2_role author
dc.subject.none.fl_str_mv DENSITY FUNCTIONAL THEORY
ELECTROSPRAY IONIZATION MASS SPECTROMETRY
METAL COMPLEXES
PYRITHIONE
REDOX-ACTIVE LIGAND
topic DENSITY FUNCTIONAL THEORY
ELECTROSPRAY IONIZATION MASS SPECTROMETRY
METAL COMPLEXES
PYRITHIONE
REDOX-ACTIVE LIGAND
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system.
Fil: Butler, Matias. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
Fil: Cabrera, Gabriela Myriam. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Unidad de Microanálisis y Métodos Físicos en Química Orgánica. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Unidad de Microanálisis y Métodos Físicos en Química Orgánica; Argentina
description 2-Mercaptopyridine N-oxide (pyrithione, PTOH) along with several transition metal ions forms coordination compounds displaying notable biological activities. Gas-phase complexes formed between pyrithione and manganese (II), cobalt (II), nickel (II), copper (II), and zinc (II) were investigated by infusion in the electrospray source of a quadrupole-time of flight mass spectrometer. Remarkably, positive ion mode spectra displayed the singly charged metal adduct ion [C10H8MN2O2S2]2+ ([M(PTO)2]+• or [M(DPTO)]+•), where DPTO is dipyrithione, 2,2′-dithiobis(pyridine N-oxide), among the most abundant peaks, implying a change in the oxidation state of whether the metal ion or the ligands. In addition, doubly charged ions were recognized as metal adduct ions containing DPTO ligands, [M(DPTO)n]2+. Generation of [M(PTO)2]+• / [M(DPTO)]+• could be traced by CID of [M(DPTO)2]2+, by observation of the sequential losses of a charged (PTO+) and a radical (PTO•) deprotonated pyrithione ligand. The fragmentation pathways of [M(PTO)2]+• / [M(DPTO)]+• were compared among the different metal ions, and some common features were noticed. Density functional theory (DFT) calculations were employed to study the structures of the observed adduct ions, and especially, to decide in the adduct ion [M(PTO)2]+• / [M(DPTO)]+• whether the ligands are 2 deprotonated pyrithiones or a single dipyrithione as well as the oxidation state of the metal ion in the complex. Characterization of gas-phase pyrithione metal ion complexes becomes important, especially taking into account the presence of a redox-active ligand in the complexes, because redox state changes that produce new species can have a marked effect on the overall toxicological/biological response elicited by the metal system.
publishDate 2017
dc.date.none.fl_str_mv 2017-11
info:eu-repo/date/embargoEnd/2018-12-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/60933
Butler, Matias; Cabrera, Gabriela Myriam; A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase; John Wiley & Sons Ltd; Journal of Mass Spectrometry; 52; 11; 11-2017; 728-738
1076-5174
1096-9888
CONICET Digital
CONICET
url http://hdl.handle.net/11336/60933
identifier_str_mv Butler, Matias; Cabrera, Gabriela Myriam; A mass spectrometry and DFT study of pyrithione complexes with transition metals in the gas phase; John Wiley & Sons Ltd; Journal of Mass Spectrometry; 52; 11; 11-2017; 728-738
1076-5174
1096-9888
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
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info:eu-repo/semantics/altIdentifier/doi/10.1002/jms.3976
dc.rights.none.fl_str_mv info:eu-repo/semantics/embargoedAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv embargoedAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv John Wiley & Sons Ltd
publisher.none.fl_str_mv John Wiley & Sons Ltd
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
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instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
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repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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