Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers

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 polyme...
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Autor*in:	Mariagrazia Iacomino [verfasserIn] Juan Mancebo-Aracil [verfasserIn] Mireia Guardingo [verfasserIn] Raquel Martín [verfasserIn] Gerardino D’Errico [verfasserIn] Marco Perfetti [verfasserIn] Paola Manini [verfasserIn] Orlando Crescenzi [verfasserIn] Félix Busqué [verfasserIn] Alessandra Napolitano [verfasserIn] Marco d’Ischia [verfasserIn] Josep Sedó [verfasserIn] Daniel Ruiz-Molina [verfasserIn]

Format:	E-Artikel
Sprache:	Englisch

Erschienen:	2017

Schlagwörter:	eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin

Übergeordnetes Werk:	In: International Journal of Molecular Sciences - MDPI AG, 2003, 18(2017), 10, p 2169
Übergeordnetes Werk:	volume:18 ; year:2017 ; number:10, p 2169

Links:	Link aufrufen Link aufrufen Link aufrufen Journal toc

DOI / URN:	10.3390/ijms18102169

Katalog-ID:	DOAJ03668497X

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allfields	10.3390/ijms18102169 doi (DE-627)DOAJ03668497X (DE-599)DOAJ480c03ae9b79494ba727519b9e70d751 DE-627 ger DE-627 rakwb eng QH301-705.5 QD1-999 Mariagrazia Iacomino verfasserin aut Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers 2017 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier 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. eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry Juan Mancebo-Aracil verfasserin aut Mireia Guardingo verfasserin aut Raquel Martín verfasserin aut Gerardino D’Errico verfasserin aut Marco Perfetti verfasserin aut Paola Manini verfasserin aut Orlando Crescenzi verfasserin aut Félix Busqué verfasserin aut Alessandra Napolitano verfasserin aut Marco d’Ischia verfasserin aut Josep Sedó verfasserin aut Daniel Ruiz-Molina verfasserin aut In International Journal of Molecular Sciences MDPI AG, 2003 18(2017), 10, p 2169 (DE-627)316340715 (DE-600)2019364-6 14220067 nnns volume:18 year:2017 number:10, p 2169 https://doi.org/10.3390/ijms18102169 kostenfrei https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 kostenfrei https://www.mdpi.com/1422-0067/18/10/2169 kostenfrei https://doaj.org/toc/1422-0067 Journal toc kostenfrei GBV_USEFLAG_A SYSFLAG_A GBV_DOAJ GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_105 GBV_ILN_110 GBV_ILN_151 GBV_ILN_161 GBV_ILN_170 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_602 GBV_ILN_2005 GBV_ILN_2009 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2055 GBV_ILN_2111 GBV_ILN_4012 GBV_ILN_4037 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4249 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4700 AR 18 2017 10, p 2169
spelling	10.3390/ijms18102169 doi (DE-627)DOAJ03668497X (DE-599)DOAJ480c03ae9b79494ba727519b9e70d751 DE-627 ger DE-627 rakwb eng QH301-705.5 QD1-999 Mariagrazia Iacomino verfasserin aut Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers 2017 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier 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. eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry Juan Mancebo-Aracil verfasserin aut Mireia Guardingo verfasserin aut Raquel Martín verfasserin aut Gerardino D’Errico verfasserin aut Marco Perfetti verfasserin aut Paola Manini verfasserin aut Orlando Crescenzi verfasserin aut Félix Busqué verfasserin aut Alessandra Napolitano verfasserin aut Marco d’Ischia verfasserin aut Josep Sedó verfasserin aut Daniel Ruiz-Molina verfasserin aut In International Journal of Molecular Sciences MDPI AG, 2003 18(2017), 10, p 2169 (DE-627)316340715 (DE-600)2019364-6 14220067 nnns volume:18 year:2017 number:10, p 2169 https://doi.org/10.3390/ijms18102169 kostenfrei https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 kostenfrei https://www.mdpi.com/1422-0067/18/10/2169 kostenfrei https://doaj.org/toc/1422-0067 Journal toc kostenfrei GBV_USEFLAG_A SYSFLAG_A GBV_DOAJ GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_105 GBV_ILN_110 GBV_ILN_151 GBV_ILN_161 GBV_ILN_170 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_602 GBV_ILN_2005 GBV_ILN_2009 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2055 GBV_ILN_2111 GBV_ILN_4012 GBV_ILN_4037 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4249 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4700 AR 18 2017 10, p 2169
allfields_unstemmed	10.3390/ijms18102169 doi (DE-627)DOAJ03668497X (DE-599)DOAJ480c03ae9b79494ba727519b9e70d751 DE-627 ger DE-627 rakwb eng QH301-705.5 QD1-999 Mariagrazia Iacomino verfasserin aut Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers 2017 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier 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. eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry Juan Mancebo-Aracil verfasserin aut Mireia Guardingo verfasserin aut Raquel Martín verfasserin aut Gerardino D’Errico verfasserin aut Marco Perfetti verfasserin aut Paola Manini verfasserin aut Orlando Crescenzi verfasserin aut Félix Busqué verfasserin aut Alessandra Napolitano verfasserin aut Marco d’Ischia verfasserin aut Josep Sedó verfasserin aut Daniel Ruiz-Molina verfasserin aut In International Journal of Molecular Sciences MDPI AG, 2003 18(2017), 10, p 2169 (DE-627)316340715 (DE-600)2019364-6 14220067 nnns volume:18 year:2017 number:10, p 2169 https://doi.org/10.3390/ijms18102169 kostenfrei https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 kostenfrei https://www.mdpi.com/1422-0067/18/10/2169 kostenfrei https://doaj.org/toc/1422-0067 Journal toc kostenfrei GBV_USEFLAG_A SYSFLAG_A GBV_DOAJ GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_105 GBV_ILN_110 GBV_ILN_151 GBV_ILN_161 GBV_ILN_170 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_602 GBV_ILN_2005 GBV_ILN_2009 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2055 GBV_ILN_2111 GBV_ILN_4012 GBV_ILN_4037 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4249 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4700 AR 18 2017 10, p 2169
allfieldsGer	10.3390/ijms18102169 doi (DE-627)DOAJ03668497X (DE-599)DOAJ480c03ae9b79494ba727519b9e70d751 DE-627 ger DE-627 rakwb eng QH301-705.5 QD1-999 Mariagrazia Iacomino verfasserin aut Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers 2017 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier 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. eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry Juan Mancebo-Aracil verfasserin aut Mireia Guardingo verfasserin aut Raquel Martín verfasserin aut Gerardino D’Errico verfasserin aut Marco Perfetti verfasserin aut Paola Manini verfasserin aut Orlando Crescenzi verfasserin aut Félix Busqué verfasserin aut Alessandra Napolitano verfasserin aut Marco d’Ischia verfasserin aut Josep Sedó verfasserin aut Daniel Ruiz-Molina verfasserin aut In International Journal of Molecular Sciences MDPI AG, 2003 18(2017), 10, p 2169 (DE-627)316340715 (DE-600)2019364-6 14220067 nnns volume:18 year:2017 number:10, p 2169 https://doi.org/10.3390/ijms18102169 kostenfrei https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 kostenfrei https://www.mdpi.com/1422-0067/18/10/2169 kostenfrei https://doaj.org/toc/1422-0067 Journal toc kostenfrei GBV_USEFLAG_A SYSFLAG_A GBV_DOAJ GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_105 GBV_ILN_110 GBV_ILN_151 GBV_ILN_161 GBV_ILN_170 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_602 GBV_ILN_2005 GBV_ILN_2009 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2055 GBV_ILN_2111 GBV_ILN_4012 GBV_ILN_4037 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4249 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4700 AR 18 2017 10, p 2169
allfieldsSound	10.3390/ijms18102169 doi (DE-627)DOAJ03668497X (DE-599)DOAJ480c03ae9b79494ba727519b9e70d751 DE-627 ger DE-627 rakwb eng QH301-705.5 QD1-999 Mariagrazia Iacomino verfasserin aut Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers 2017 Text txt rdacontent Computermedien c rdamedia Online-Ressource cr rdacarrier 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. eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry Juan Mancebo-Aracil verfasserin aut Mireia Guardingo verfasserin aut Raquel Martín verfasserin aut Gerardino D’Errico verfasserin aut Marco Perfetti verfasserin aut Paola Manini verfasserin aut Orlando Crescenzi verfasserin aut Félix Busqué verfasserin aut Alessandra Napolitano verfasserin aut Marco d’Ischia verfasserin aut Josep Sedó verfasserin aut Daniel Ruiz-Molina verfasserin aut In International Journal of Molecular Sciences MDPI AG, 2003 18(2017), 10, p 2169 (DE-627)316340715 (DE-600)2019364-6 14220067 nnns volume:18 year:2017 number:10, p 2169 https://doi.org/10.3390/ijms18102169 kostenfrei https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 kostenfrei https://www.mdpi.com/1422-0067/18/10/2169 kostenfrei https://doaj.org/toc/1422-0067 Journal toc kostenfrei GBV_USEFLAG_A SYSFLAG_A GBV_DOAJ GBV_ILN_20 GBV_ILN_22 GBV_ILN_23 GBV_ILN_24 GBV_ILN_31 GBV_ILN_39 GBV_ILN_40 GBV_ILN_60 GBV_ILN_62 GBV_ILN_63 GBV_ILN_65 GBV_ILN_69 GBV_ILN_70 GBV_ILN_73 GBV_ILN_74 GBV_ILN_95 GBV_ILN_105 GBV_ILN_110 GBV_ILN_151 GBV_ILN_161 GBV_ILN_170 GBV_ILN_206 GBV_ILN_213 GBV_ILN_224 GBV_ILN_230 GBV_ILN_285 GBV_ILN_293 GBV_ILN_602 GBV_ILN_2005 GBV_ILN_2009 GBV_ILN_2011 GBV_ILN_2014 GBV_ILN_2055 GBV_ILN_2111 GBV_ILN_4012 GBV_ILN_4037 GBV_ILN_4112 GBV_ILN_4125 GBV_ILN_4126 GBV_ILN_4249 GBV_ILN_4305 GBV_ILN_4306 GBV_ILN_4307 GBV_ILN_4313 GBV_ILN_4322 GBV_ILN_4323 GBV_ILN_4324 GBV_ILN_4325 GBV_ILN_4338 GBV_ILN_4367 GBV_ILN_4700 AR 18 2017 10, p 2169
language	English
source	In International Journal of Molecular Sciences 18(2017), 10, p 2169 volume:18 year:2017 number:10, p 2169
sourceStr	In International Journal of Molecular Sciences 18(2017), 10, p 2169 volume:18 year:2017 number:10, p 2169
format_phy_str_mv	Article
institution	findex.gbv.de
topic_facet	eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin Biology (General) Chemistry
isfreeaccess_bool	true
container_title	International Journal of Molecular Sciences
authorswithroles_txt_mv	Mariagrazia Iacomino @@aut@@ Juan Mancebo-Aracil @@aut@@ Mireia Guardingo @@aut@@ Raquel Martín @@aut@@ Gerardino D’Errico @@aut@@ Marco Perfetti @@aut@@ Paola Manini @@aut@@ Orlando Crescenzi @@aut@@ Félix Busqué @@aut@@ Alessandra Napolitano @@aut@@ Marco d’Ischia @@aut@@ Josep Sedó @@aut@@ Daniel Ruiz-Molina @@aut@@
publishDateDaySort_date	2017-01-01T00:00:00Z
hierarchy_top_id	316340715
id	DOAJ03668497X
language_de	englisch
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callnumber-first	Q - Science
author	Mariagrazia Iacomino
spellingShingle	Mariagrazia Iacomino misc QH301-705.5 misc QD1-999 misc eumelanin misc polydopamine misc bioinspired polymers misc bioinspired coatings misc thiomelanin misc Biology (General) misc Chemistry Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers
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topic_title	QH301-705.5 QD1-999 Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers eumelanin polydopamine bioinspired polymers bioinspired coatings thiomelanin
topic	misc QH301-705.5 misc QD1-999 misc eumelanin misc polydopamine misc bioinspired polymers misc bioinspired coatings misc thiomelanin misc Biology (General) misc Chemistry
topic_unstemmed	misc QH301-705.5 misc QD1-999 misc eumelanin misc polydopamine misc bioinspired polymers misc bioinspired coatings misc thiomelanin misc Biology (General) misc Chemistry
topic_browse	misc QH301-705.5 misc QD1-999 misc eumelanin misc polydopamine misc bioinspired polymers misc bioinspired coatings misc thiomelanin misc Biology (General) misc Chemistry
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title	Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers
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title_full	Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers
author_sort	Mariagrazia Iacomino
journal	International Journal of Molecular Sciences
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author_browse	Mariagrazia Iacomino Juan Mancebo-Aracil Mireia Guardingo Raquel Martín Gerardino D’Errico Marco Perfetti Paola Manini Orlando Crescenzi Félix Busqué Alessandra Napolitano Marco d’Ischia Josep Sedó Daniel Ruiz-Molina
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doi_str_mv	10.3390/ijms18102169
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title_sort	replacing nitrogen by sulfur: from structurally disordered eumelanins to regioregular thiomelanin polymers
callnumber	QH301-705.5
title_auth	Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers
abstract	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.
abstractGer	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.
abstract_unstemmed	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.
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container_issue	10, p 2169
title_short	Replacing Nitrogen by Sulfur: From Structurally Disordered Eumelanins to Regioregular Thiomelanin Polymers
url	https://doi.org/10.3390/ijms18102169 https://doaj.org/article/480c03ae9b79494ba727519b9e70d751 https://www.mdpi.com/1422-0067/18/10/2169 https://doaj.org/toc/1422-0067
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author2	Juan Mancebo-Aracil Mireia Guardingo Raquel Martín Gerardino D’Errico Marco Perfetti Paola Manini Orlando Crescenzi Félix Busqué Alessandra Napolitano Marco d’Ischia Josep Sedó Daniel Ruiz-Molina
author2Str	Juan Mancebo-Aracil Mireia Guardingo Raquel Martín Gerardino D’Errico Marco Perfetti Paola Manini Orlando Crescenzi Félix Busqué Alessandra Napolitano Marco d’Ischia Josep Sedó Daniel Ruiz-Molina
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up_date	2024-07-03T21:57:03.734Z
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