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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/57334
Ver los metadatos del registro completo
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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 Técnicas2025-09-03T09:53:08Zoai: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:34982025-09-03 09:53:08.988CONICET 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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1842269204078657536 |
score |
13.13397 |