Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)

Autores
Pissinis, Diego Ezequiel; Linarez Pérez, Omar Ezequiel; Cometto, Fernando Pablo; Lopez Teijelo, Manuel
Año de publicación
2014
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The characterization by cyclic voltammetry, impedance spectroscopy and SERS measurements of 2-mer-captonicotinic acid (2-MNA) monolayers formed under different conditions on Au(111) surfaces, isreported.Self-assembled 2-MNA monolayers on Au(111) in alkaline solutions desorbs reductively from the goldsurface at 0.76 V (vs. ECS). From desorption experiments, the value of the surface concentration wasestimated, resulting similar to that reported for related aromatic molecules.Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show a rather imperfectblocking behavior of the 2-MNA SAMS. This behavior corresponds to that obtained for microelectrodearrays, which is attributed to the access of ions through pinholes, defects and/or pores present in theSAM.The characteristics of ionisable groups exposed to the solution in the 2-MNA monolayers prepared bydipping in alkaline solutions were obtained by impedance measurements at different pH using the[Fe(CN)6]3 /[Fe(CN)6]4 redox probe and the value of pKa(SAM)for the carboxylate group in the surface2-MNA monolayer was estimated. For pH > pKa, the carboxylic acid group is deprotonated and the mono-layer acquires a negative surface charge, meanwhile it remains neutral or positively charged at lower pHvalues due to the beginning of pyridinic nitrogen protonation, which takes place overlapped with the pro-tonation of the carboxylate group. The protonation of the pyridinic nitrogen is accompanied by desorp-tion of this group from the surface. This leads to a change in the orientation of 2-MNA species allowingthe interaction between the carboxylate group and the gold surface, which was further corroborated fromSERS measurements.In alkaline aqueous medium, 2-MNA adsorbs through a thiolate chemical bond on the gold surface andan additional interaction of the pyridinic nitrogen stabilizes the monolayer. One cathodic peak isobtained when reductive desorption is made in alkaline medium, while a splitting in two cathodic cur-rent contributions for pH values lower than ca. 7 indicates that two different molecular structures coexiston the gold surface in neutral or acidic media. This is assigned to the occurrence of an equilibriumbetween the molecular structure bonded through sulfur and nitrogen and the surface-bonded zwitter-ionic species by intramolecular proton transfer from the carboxylic acid group to the ring nitrogen, lead-ing to the protonation of the pyridinic nitrogen and allowing the interaction of the carboxylate groupwith the gold surface.
Fil: Pissinis, Diego Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Linarez Pérez, Omar Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Lopez Teijelo, Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Self Assembled Monolayers
Aromatic Thiols
Reductive Desorption
Sers
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
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CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
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oai:ri.conicet.gov.ar:11336/31538
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/31538
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)Pissinis, Diego EzequielLinarez Pérez, Omar EzequielCometto, Fernando PabloLopez Teijelo, ManuelSelf Assembled MonolayersAromatic ThiolsReductive DesorptionSershttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The characterization by cyclic voltammetry, impedance spectroscopy and SERS measurements of 2-mer-captonicotinic acid (2-MNA) monolayers formed under different conditions on Au(111) surfaces, isreported.Self-assembled 2-MNA monolayers on Au(111) in alkaline solutions desorbs reductively from the goldsurface at 0.76 V (vs. ECS). From desorption experiments, the value of the surface concentration wasestimated, resulting similar to that reported for related aromatic molecules.Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show a rather imperfectblocking behavior of the 2-MNA SAMS. This behavior corresponds to that obtained for microelectrodearrays, which is attributed to the access of ions through pinholes, defects and/or pores present in theSAM.The characteristics of ionisable groups exposed to the solution in the 2-MNA monolayers prepared bydipping in alkaline solutions were obtained by impedance measurements at different pH using the[Fe(CN)6]3 /[Fe(CN)6]4 redox probe and the value of pKa(SAM)for the carboxylate group in the surface2-MNA monolayer was estimated. For pH > pKa, the carboxylic acid group is deprotonated and the mono-layer acquires a negative surface charge, meanwhile it remains neutral or positively charged at lower pHvalues due to the beginning of pyridinic nitrogen protonation, which takes place overlapped with the pro-tonation of the carboxylate group. The protonation of the pyridinic nitrogen is accompanied by desorp-tion of this group from the surface. This leads to a change in the orientation of 2-MNA species allowingthe interaction between the carboxylate group and the gold surface, which was further corroborated fromSERS measurements.In alkaline aqueous medium, 2-MNA adsorbs through a thiolate chemical bond on the gold surface andan additional interaction of the pyridinic nitrogen stabilizes the monolayer. One cathodic peak isobtained when reductive desorption is made in alkaline medium, while a splitting in two cathodic cur-rent contributions for pH values lower than ca. 7 indicates that two different molecular structures coexiston the gold surface in neutral or acidic media. This is assigned to the occurrence of an equilibriumbetween the molecular structure bonded through sulfur and nitrogen and the surface-bonded zwitter-ionic species by intramolecular proton transfer from the carboxylic acid group to the ring nitrogen, lead-ing to the protonation of the pyridinic nitrogen and allowing the interaction of the carboxylate groupwith the gold surface.Fil: Pissinis, Diego Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Linarez Pérez, Omar Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Lopez Teijelo, Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaElsevier Science Sa2014-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/31538Lopez Teijelo, Manuel; Cometto, Fernando Pablo; Linarez Pérez, Omar Ezequiel; Pissinis, Diego Ezequiel; Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1); Elsevier Science Sa; Journal of Electroanalytical Chemistry; 712; 1-2014; 167-1771572-6657CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2013.11.013info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1572665713005109info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:36:04Zoai:ri.conicet.gov.ar:11336/31538instacron: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 09:36:04.322CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
title Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
spellingShingle Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
Pissinis, Diego Ezequiel
Self Assembled Monolayers
Aromatic Thiols
Reductive Desorption
Sers
title_short Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
title_full Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
title_fullStr Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
title_full_unstemmed Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
title_sort Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1)
dc.creator.none.fl_str_mv Pissinis, Diego Ezequiel
Linarez Pérez, Omar Ezequiel
Cometto, Fernando Pablo
Lopez Teijelo, Manuel
author Pissinis, Diego Ezequiel
author_facet Pissinis, Diego Ezequiel
Linarez Pérez, Omar Ezequiel
Cometto, Fernando Pablo
Lopez Teijelo, Manuel
author_role author
author2 Linarez Pérez, Omar Ezequiel
Cometto, Fernando Pablo
Lopez Teijelo, Manuel
author2_role author
author
author
dc.subject.none.fl_str_mv Self Assembled Monolayers
Aromatic Thiols
Reductive Desorption
Sers
topic Self Assembled Monolayers
Aromatic Thiols
Reductive Desorption
Sers
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The characterization by cyclic voltammetry, impedance spectroscopy and SERS measurements of 2-mer-captonicotinic acid (2-MNA) monolayers formed under different conditions on Au(111) surfaces, isreported.Self-assembled 2-MNA monolayers on Au(111) in alkaline solutions desorbs reductively from the goldsurface at 0.76 V (vs. ECS). From desorption experiments, the value of the surface concentration wasestimated, resulting similar to that reported for related aromatic molecules.Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show a rather imperfectblocking behavior of the 2-MNA SAMS. This behavior corresponds to that obtained for microelectrodearrays, which is attributed to the access of ions through pinholes, defects and/or pores present in theSAM.The characteristics of ionisable groups exposed to the solution in the 2-MNA monolayers prepared bydipping in alkaline solutions were obtained by impedance measurements at different pH using the[Fe(CN)6]3 /[Fe(CN)6]4 redox probe and the value of pKa(SAM)for the carboxylate group in the surface2-MNA monolayer was estimated. For pH > pKa, the carboxylic acid group is deprotonated and the mono-layer acquires a negative surface charge, meanwhile it remains neutral or positively charged at lower pHvalues due to the beginning of pyridinic nitrogen protonation, which takes place overlapped with the pro-tonation of the carboxylate group. The protonation of the pyridinic nitrogen is accompanied by desorp-tion of this group from the surface. This leads to a change in the orientation of 2-MNA species allowingthe interaction between the carboxylate group and the gold surface, which was further corroborated fromSERS measurements.In alkaline aqueous medium, 2-MNA adsorbs through a thiolate chemical bond on the gold surface andan additional interaction of the pyridinic nitrogen stabilizes the monolayer. One cathodic peak isobtained when reductive desorption is made in alkaline medium, while a splitting in two cathodic cur-rent contributions for pH values lower than ca. 7 indicates that two different molecular structures coexiston the gold surface in neutral or acidic media. This is assigned to the occurrence of an equilibriumbetween the molecular structure bonded through sulfur and nitrogen and the surface-bonded zwitter-ionic species by intramolecular proton transfer from the carboxylic acid group to the ring nitrogen, lead-ing to the protonation of the pyridinic nitrogen and allowing the interaction of the carboxylate groupwith the gold surface.
Fil: Pissinis, Diego Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Linarez Pérez, Omar Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Cometto, Fernando Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Lopez Teijelo, Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The characterization by cyclic voltammetry, impedance spectroscopy and SERS measurements of 2-mer-captonicotinic acid (2-MNA) monolayers formed under different conditions on Au(111) surfaces, isreported.Self-assembled 2-MNA monolayers on Au(111) in alkaline solutions desorbs reductively from the goldsurface at 0.76 V (vs. ECS). From desorption experiments, the value of the surface concentration wasestimated, resulting similar to that reported for related aromatic molecules.Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) show a rather imperfectblocking behavior of the 2-MNA SAMS. This behavior corresponds to that obtained for microelectrodearrays, which is attributed to the access of ions through pinholes, defects and/or pores present in theSAM.The characteristics of ionisable groups exposed to the solution in the 2-MNA monolayers prepared bydipping in alkaline solutions were obtained by impedance measurements at different pH using the[Fe(CN)6]3 /[Fe(CN)6]4 redox probe and the value of pKa(SAM)for the carboxylate group in the surface2-MNA monolayer was estimated. For pH > pKa, the carboxylic acid group is deprotonated and the mono-layer acquires a negative surface charge, meanwhile it remains neutral or positively charged at lower pHvalues due to the beginning of pyridinic nitrogen protonation, which takes place overlapped with the pro-tonation of the carboxylate group. The protonation of the pyridinic nitrogen is accompanied by desorp-tion of this group from the surface. This leads to a change in the orientation of 2-MNA species allowingthe interaction between the carboxylate group and the gold surface, which was further corroborated fromSERS measurements.In alkaline aqueous medium, 2-MNA adsorbs through a thiolate chemical bond on the gold surface andan additional interaction of the pyridinic nitrogen stabilizes the monolayer. One cathodic peak isobtained when reductive desorption is made in alkaline medium, while a splitting in two cathodic cur-rent contributions for pH values lower than ca. 7 indicates that two different molecular structures coexiston the gold surface in neutral or acidic media. This is assigned to the occurrence of an equilibriumbetween the molecular structure bonded through sulfur and nitrogen and the surface-bonded zwitter-ionic species by intramolecular proton transfer from the carboxylic acid group to the ring nitrogen, lead-ing to the protonation of the pyridinic nitrogen and allowing the interaction of the carboxylate groupwith the gold surface.
publishDate 2014
dc.date.none.fl_str_mv 2014-01
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/11336/31538
Lopez Teijelo, Manuel; Cometto, Fernando Pablo; Linarez Pérez, Omar Ezequiel; Pissinis, Diego Ezequiel; Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1); Elsevier Science Sa; Journal of Electroanalytical Chemistry; 712; 1-2014; 167-177
1572-6657
CONICET Digital
CONICET
url http://hdl.handle.net/11336/31538
identifier_str_mv Lopez Teijelo, Manuel; Cometto, Fernando Pablo; Linarez Pérez, Omar Ezequiel; Pissinis, Diego Ezequiel; Preparation and characterization of self assembled monolayers of 2-mercaptonicotinic acid on Au(1 1 1); Elsevier Science Sa; Journal of Electroanalytical Chemistry; 712; 1-2014; 167-177
1572-6657
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.jelechem.2013.11.013
info:eu-repo/semantics/altIdentifier/url/http://www.sciencedirect.com/science/article/pii/S1572665713005109
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
application/pdf
application/pdf
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dc.publisher.none.fl_str_mv Elsevier Science Sa
publisher.none.fl_str_mv Elsevier Science Sa
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 13.070432

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