Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage

Autores
Azcárate, Julio César; Aagaard, Natalia Desiré; Zampieri, Guillermo Enrique; Zelaya, Maria Eugenia; Fonticelli, Mariano Hernan
Año de publicación
2019
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Self-assembled monolayers (SAMs) of ω-carboxylic acid thiols are very important in the surface modification of metals, especially on gold surfaces. Indeed, the 3-mercaptopropanoic acid (MPA) and its ester or amide derivatives are widely used for SAM-based sensor design. It was already shown that MPA does not suffer C–S bond scission when adsorbed on Au. On the other hand, in this work we demonstrate that its simplest derivative, methyl 3-mercapto propionate (Me-MPA), is prone to form significant amounts of atomic sulfur when adsorbed on Au. The MPA derivatives are more sensible than MPA itself to alkaline solutions, and its SAM-based sensors will rapidly degrade given atomic sulfur. In this work, we study the simplest MPA derivative Me-MPA SAMs on preferentially oriented Au(111) surfaces by XPS and electrochemical measurements. It was found that the desulfuration of Me-MPA depends on its preparation conditions (grown from ethanol or toluene solution) and on its post-treatment with alkaline solution. In order to explain the S–C bond scission on Me-MPA SAMs, we discuss different reaction mechanisms. We concluded that the reaction mechanism involves an E1cB elimination pathway (β-elimination). This reaction mechanism also explains the desulfuration behavior of other important related molecules like l-cysteine and glutathione.
Fil: Azcárate, Julio César. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Aagaard, Natalia Desiré. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Zampieri, Guillermo Enrique. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina
Fil: Zelaya, Maria Eugenia. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
Materia
Self-Assembled Monolayers
methyl 3-mercaptopropanoate
XPS
C-S bond cleavage
Nivel de accesibilidad
acceso abierto
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:11336/118670
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/118670
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond CleavageAzcárate, Julio CésarAagaard, Natalia DesiréZampieri, Guillermo EnriqueZelaya, Maria EugeniaFonticelli, Mariano HernanSelf-Assembled Monolayersmethyl 3-mercaptopropanoateXPSC-S bond cleavagehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Self-assembled monolayers (SAMs) of ω-carboxylic acid thiols are very important in the surface modification of metals, especially on gold surfaces. Indeed, the 3-mercaptopropanoic acid (MPA) and its ester or amide derivatives are widely used for SAM-based sensor design. It was already shown that MPA does not suffer C–S bond scission when adsorbed on Au. On the other hand, in this work we demonstrate that its simplest derivative, methyl 3-mercapto propionate (Me-MPA), is prone to form significant amounts of atomic sulfur when adsorbed on Au. The MPA derivatives are more sensible than MPA itself to alkaline solutions, and its SAM-based sensors will rapidly degrade given atomic sulfur. In this work, we study the simplest MPA derivative Me-MPA SAMs on preferentially oriented Au(111) surfaces by XPS and electrochemical measurements. It was found that the desulfuration of Me-MPA depends on its preparation conditions (grown from ethanol or toluene solution) and on its post-treatment with alkaline solution. In order to explain the S–C bond scission on Me-MPA SAMs, we discuss different reaction mechanisms. We concluded that the reaction mechanism involves an E1cB elimination pathway (β-elimination). This reaction mechanism also explains the desulfuration behavior of other important related molecules like l-cysteine and glutathione.Fil: Azcárate, Julio César. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Aagaard, Natalia Desiré. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Zampieri, Guillermo Enrique. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; ArgentinaFil: Zelaya, Maria Eugenia. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaAmerican Chemical Society2019-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/118670Azcárate, Julio César; Aagaard, Natalia Desiré; Zampieri, Guillermo Enrique; Zelaya, Maria Eugenia; Fonticelli, Mariano Hernan; Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage; American Chemical Society; Journal of Physical Chemistry C; 123; 39; 9-2019; 24156-241641932-7447CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.jpcc.9b07271info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b07271info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:11:41Zoai:ri.conicet.gov.ar:11336/118670instacron: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:34982025-09-10 13:11:41.655CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
title Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
spellingShingle Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
Azcárate, Julio César
Self-Assembled Monolayers
methyl 3-mercaptopropanoate
XPS
C-S bond cleavage
title_short Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
title_full Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
title_fullStr Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
title_full_unstemmed Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
title_sort Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage
dc.creator.none.fl_str_mv Azcárate, Julio César
Aagaard, Natalia Desiré
Zampieri, Guillermo Enrique
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author Azcárate, Julio César
author_facet Azcárate, Julio César
Aagaard, Natalia Desiré
Zampieri, Guillermo Enrique
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author_role author
author2 Aagaard, Natalia Desiré
Zampieri, Guillermo Enrique
Zelaya, Maria Eugenia
Fonticelli, Mariano Hernan
author2_role author
author
author
author
dc.subject.none.fl_str_mv Self-Assembled Monolayers
methyl 3-mercaptopropanoate
XPS
C-S bond cleavage
topic Self-Assembled Monolayers
methyl 3-mercaptopropanoate
XPS
C-S bond cleavage
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Self-assembled monolayers (SAMs) of ω-carboxylic acid thiols are very important in the surface modification of metals, especially on gold surfaces. Indeed, the 3-mercaptopropanoic acid (MPA) and its ester or amide derivatives are widely used for SAM-based sensor design. It was already shown that MPA does not suffer C–S bond scission when adsorbed on Au. On the other hand, in this work we demonstrate that its simplest derivative, methyl 3-mercapto propionate (Me-MPA), is prone to form significant amounts of atomic sulfur when adsorbed on Au. The MPA derivatives are more sensible than MPA itself to alkaline solutions, and its SAM-based sensors will rapidly degrade given atomic sulfur. In this work, we study the simplest MPA derivative Me-MPA SAMs on preferentially oriented Au(111) surfaces by XPS and electrochemical measurements. It was found that the desulfuration of Me-MPA depends on its preparation conditions (grown from ethanol or toluene solution) and on its post-treatment with alkaline solution. In order to explain the S–C bond scission on Me-MPA SAMs, we discuss different reaction mechanisms. We concluded that the reaction mechanism involves an E1cB elimination pathway (β-elimination). This reaction mechanism also explains the desulfuration behavior of other important related molecules like l-cysteine and glutathione.
Fil: Azcárate, Julio César. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Aagaard, Natalia Desiré. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Zampieri, Guillermo Enrique. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Gerencia del Área de Energía Nuclear. Instituto Balseiro; Argentina
Fil: Zelaya, Maria Eugenia. Comision Nacional de Energía Atómica. Gerencia de Área Investigaciones y Aplicaciones no Nucleares. Gerencia de Física (Centro Atómico Bariloche). División Física de Metales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina
Fil: Fonticelli, Mariano Hernan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentina
description Self-assembled monolayers (SAMs) of ω-carboxylic acid thiols are very important in the surface modification of metals, especially on gold surfaces. Indeed, the 3-mercaptopropanoic acid (MPA) and its ester or amide derivatives are widely used for SAM-based sensor design. It was already shown that MPA does not suffer C–S bond scission when adsorbed on Au. On the other hand, in this work we demonstrate that its simplest derivative, methyl 3-mercapto propionate (Me-MPA), is prone to form significant amounts of atomic sulfur when adsorbed on Au. The MPA derivatives are more sensible than MPA itself to alkaline solutions, and its SAM-based sensors will rapidly degrade given atomic sulfur. In this work, we study the simplest MPA derivative Me-MPA SAMs on preferentially oriented Au(111) surfaces by XPS and electrochemical measurements. It was found that the desulfuration of Me-MPA depends on its preparation conditions (grown from ethanol or toluene solution) and on its post-treatment with alkaline solution. In order to explain the S–C bond scission on Me-MPA SAMs, we discuss different reaction mechanisms. We concluded that the reaction mechanism involves an E1cB elimination pathway (β-elimination). This reaction mechanism also explains the desulfuration behavior of other important related molecules like l-cysteine and glutathione.
publishDate 2019
dc.date.none.fl_str_mv 2019-09
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/11336/118670
Azcárate, Julio César; Aagaard, Natalia Desiré; Zampieri, Guillermo Enrique; Zelaya, Maria Eugenia; Fonticelli, Mariano Hernan; Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage; American Chemical Society; Journal of Physical Chemistry C; 123; 39; 9-2019; 24156-24164
1932-7447
CONICET Digital
CONICET
url http://hdl.handle.net/11336/118670
identifier_str_mv Azcárate, Julio César; Aagaard, Natalia Desiré; Zampieri, Guillermo Enrique; Zelaya, Maria Eugenia; Fonticelli, Mariano Hernan; Atomic Sulfur Formation Mechanism on 3-mercaptopropanoic Acid-Derivatives SAMs: Understanding the C-S Bond Cleavage; American Chemical Society; Journal of Physical Chemistry C; 123; 39; 9-2019; 24156-24164
1932-7447
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/10.1021/acs.jpcc.9b07271
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpcc.9b07271
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
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 American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.993085

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