Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers

Autores
Iacomino, Mariagrazia; Mancebo Aracil, Juan; Guardingo, Mireia; Martín, Raquel; D’Errico, Gerardino; Perfetti, Marco; Manini, Paola; Crescenzi, Orlando; Busqué, Félix; Napolitano, Alessandra; d’Ischia, Marco; Sedó, Josep; Ruiz Molina, Daniel
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating.
Fil: Iacomino, Mariagrazia. Università degli Studi di Napoli Federico II; Italia
Fil: Mancebo Aracil, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universitat Autònoma de Barcelona; España. Consejo Superior de Investigaciones Científicas; España
Fil: Guardingo, Mireia. Barcelona Institute of Science and Technology; España. Universitat Autònoma de Barcelona; España
Fil: Martín, Raquel. Universitat Autònoma de Barcelona; España
Fil: D’Errico, Gerardino. Università degli Studi di Napoli Federico II; Italia
Fil: Perfetti, Marco. Università degli Studi di Napoli Federico II; Italia
Fil: Manini, Paola. Università degli Studi di Napoli Federico II; Italia
Fil: Crescenzi, Orlando. Università degli Studi di Napoli Federico II; Italia
Fil: Busqué, Félix. Universitat Autònoma de Barcelona; España
Fil: Napolitano, Alessandra. Università degli Studi di Napoli Federico II; Italia
Fil: d’Ischia, Marco. Università degli Studi di Napoli Federico II; Italia
Fil: Sedó, Josep. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; España
Fil: Ruiz Molina, Daniel. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; España
Materia
BIOINSPIRED COATINGS
BIOINSPIRED POLYMERS
EUMELANIN
POLYDOPAMINE
THIOMELANIN
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/57334
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/57334
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymersIacomino, MariagraziaMancebo Aracil, JuanGuardingo, MireiaMartín, RaquelD’Errico, GerardinoPerfetti, MarcoManini, PaolaCrescenzi, OrlandoBusqué, FélixNapolitano, Alessandrad’Ischia, MarcoSedó, JosepRuiz Molina, DanielBIOINSPIRED COATINGSBIOINSPIRED POLYMERSEUMELANINPOLYDOPAMINETHIOMELANINhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating.Fil: Iacomino, Mariagrazia. Università degli Studi di Napoli Federico II; ItaliaFil: Mancebo Aracil, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universitat Autònoma de Barcelona; España. Consejo Superior de Investigaciones Científicas; EspañaFil: Guardingo, Mireia. Barcelona Institute of Science and Technology; España. Universitat Autònoma de Barcelona; EspañaFil: Martín, Raquel. Universitat Autònoma de Barcelona; EspañaFil: D’Errico, Gerardino. Università degli Studi di Napoli Federico II; ItaliaFil: Perfetti, Marco. Università degli Studi di Napoli Federico II; ItaliaFil: Manini, Paola. Università degli Studi di Napoli Federico II; ItaliaFil: Crescenzi, Orlando. Università degli Studi di Napoli Federico II; ItaliaFil: Busqué, Félix. Universitat Autònoma de Barcelona; EspañaFil: Napolitano, Alessandra. Università degli Studi di Napoli Federico II; ItaliaFil: d’Ischia, Marco. Università degli Studi di Napoli Federico II; ItaliaFil: Sedó, Josep. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; EspañaFil: Ruiz Molina, Daniel. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; EspañaMolecular Diversity Preservation International2017-10-17info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/57334Iacomino, Mariagrazia; Mancebo Aracil, Juan; Guardingo, Mireia; Martín, Raquel; D’Errico, Gerardino; et al.; Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 18; 10; 17-10-2017; 2169-21841422-0067CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5666850/info:eu-repo/semantics/altIdentifier/doi/10.3390/ijms18102169info:eu-repo/semantics/altIdentifier/url/http://www.mdpi.com/1422-0067/18/10/2169info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:51:52Zoai:ri.conicet.gov.ar:11336/57334instacron: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 09:51:52.557CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
title Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
spellingShingle Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
Iacomino, Mariagrazia
BIOINSPIRED COATINGS
BIOINSPIRED POLYMERS
EUMELANIN
POLYDOPAMINE
THIOMELANIN
title_short Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
title_full Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
title_fullStr Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
title_full_unstemmed Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
title_sort Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers
dc.creator.none.fl_str_mv Iacomino, Mariagrazia
Mancebo Aracil, Juan
Guardingo, Mireia
Martín, Raquel
D’Errico, Gerardino
Perfetti, Marco
Manini, Paola
Crescenzi, Orlando
Busqué, Félix
Napolitano, Alessandra
d’Ischia, Marco
Sedó, Josep
Ruiz Molina, Daniel
author Iacomino, Mariagrazia
author_facet Iacomino, Mariagrazia
Mancebo Aracil, Juan
Guardingo, Mireia
Martín, Raquel
D’Errico, Gerardino
Perfetti, Marco
Manini, Paola
Crescenzi, Orlando
Busqué, Félix
Napolitano, Alessandra
d’Ischia, Marco
Sedó, Josep
Ruiz Molina, Daniel
author_role author
author2 Mancebo Aracil, Juan
Guardingo, Mireia
Martín, Raquel
D’Errico, Gerardino
Perfetti, Marco
Manini, Paola
Crescenzi, Orlando
Busqué, Félix
Napolitano, Alessandra
d’Ischia, Marco
Sedó, Josep
Ruiz Molina, Daniel
author2_role author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv BIOINSPIRED COATINGS
BIOINSPIRED POLYMERS
EUMELANIN
POLYDOPAMINE
THIOMELANIN
topic BIOINSPIRED COATINGS
BIOINSPIRED POLYMERS
EUMELANIN
POLYDOPAMINE
THIOMELANIN
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 oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating.
Fil: Iacomino, Mariagrazia. Università degli Studi di Napoli Federico II; Italia
Fil: Mancebo Aracil, Juan. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Instituto de Química del Sur. Universidad Nacional del Sur. Departamento de Química. Instituto de Química del Sur; Argentina. Universitat Autònoma de Barcelona; España. Consejo Superior de Investigaciones Científicas; España
Fil: Guardingo, Mireia. Barcelona Institute of Science and Technology; España. Universitat Autònoma de Barcelona; España
Fil: Martín, Raquel. Universitat Autònoma de Barcelona; España
Fil: D’Errico, Gerardino. Università degli Studi di Napoli Federico II; Italia
Fil: Perfetti, Marco. Università degli Studi di Napoli Federico II; Italia
Fil: Manini, Paola. Università degli Studi di Napoli Federico II; Italia
Fil: Crescenzi, Orlando. Università degli Studi di Napoli Federico II; Italia
Fil: Busqué, Félix. Universitat Autònoma de Barcelona; España
Fil: Napolitano, Alessandra. Università degli Studi di Napoli Federico II; Italia
Fil: d’Ischia, Marco. Università degli Studi di Napoli Federico II; Italia
Fil: Sedó, Josep. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; España
Fil: Ruiz Molina, Daniel. Consejo Superior de Investigaciones Científicas; España. Barcelona Institute of Science and Technology; España
description The oxidative polymerization of 5,6-dihydroxybenzothiophene (DHBT), the sulfur analog of the key eumelanin building block 5,6-dihydroxyindole (DHI), was investigated to probe the role of nitrogen in eumelanin build-up and properties. Unlike DHI, which gives a typical black insoluble eumelanin polymer on oxidation, DHBT is converted to a grayish amorphous solid (referred to as thiomelanin) with visible absorption and electron paramagnetic resonance properties different from those of DHI melanin. Mass spectrometry experiments revealed gradational mixtures of oligomers up to the decamer level. Quite unexpectedly, nuclear magnetic resonance (NMR) analysis of the early oligomer fractions indicated linear, 4-, and 7-linked structures in marked contrast with DHI, which gives highly complex mixtures of partially degraded oligomers. Density functional theory (DFT) calculations supported the tendency of DHBT to couple via the 4- and 7-positions. These results uncover the role of nitrogen as a major determinant of the structural diversity generated by the polymerization of DHI, and point to replacement by sulfur as a viable entry to regioregular eumelanin-type materials for potential applications for surface functionalization by dip coating.
publishDate 2017
dc.date.none.fl_str_mv 2017-10-17
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/11336/57334
Iacomino, Mariagrazia; Mancebo Aracil, Juan; Guardingo, Mireia; Martín, Raquel; D’Errico, Gerardino; et al.; Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 18; 10; 17-10-2017; 2169-2184
1422-0067
CONICET Digital
CONICET
url http://hdl.handle.net/11336/57334
identifier_str_mv Iacomino, Mariagrazia; Mancebo Aracil, Juan; Guardingo, Mireia; Martín, Raquel; D’Errico, Gerardino; et al.; Replacing nitrogen by sulfur: From structurally disordered eumelanins to regioregular thiomelanin polymers; Molecular Diversity Preservation International; International Journal of Molecular Sciences; 18; 10; 17-10-2017; 2169-2184
1422-0067
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5666850/
info:eu-repo/semantics/altIdentifier/doi/10.3390/ijms18102169
info:eu-repo/semantics/altIdentifier/url/http://www.mdpi.com/1422-0067/18/10/2169
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv Molecular Diversity Preservation International
publisher.none.fl_str_mv Molecular Diversity Preservation International
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 13.069144

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