Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films
Abstract The origin of eumelanin optical properties remains a formidable conundrum preventing a detailed understanding of the complex photo-protective role of these widespread natural pigments and the rational design of innovative bioinspired materials for optoelectronic applications. Here we report...
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Nature Portfolio
2017
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oai:doaj.org-article:9571aa005e624bf68ddd3666479cfdbd2021-12-02T16:06:04ZAnomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films10.1038/s41598-017-00597-82045-2322https://doaj.org/article/9571aa005e624bf68ddd3666479cfdbd2017-03-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-00597-8https://doaj.org/toc/2045-2322Abstract The origin of eumelanin optical properties remains a formidable conundrum preventing a detailed understanding of the complex photo-protective role of these widespread natural pigments and the rational design of innovative bioinspired materials for optoelectronic applications. Here we report the unusual kinetic and thickness-dependent evolution of the optical properties of black eumelanin polymers generated by spontaneous aerial polymerization of 5,6-dihydroxyindole (DHI) thin films (0.1–1 μm), consistent with peculiar solid state reorganization mechanisms governing broadband absorption. The complete reversal of eumelanin UV-visible transmittance spectrum curvature on passing from 0.2 to 0.5 μm thick films, the marked increase in visible extinction coefficients with increasing film thickness and the higher UV extinction coefficients in slowly vs. rapidly generated polymers concur to support distinct dynamic regimes of solid-state molecular reorganization at the nanoscale level and to do affect the development of broadband visible absorption. Solid state control of molecular reorganization disclosed herein may delineate new rational strategies for tuning optical properties in eumelanin thin films for optoelectronic applications.Carmela BonavolontàCorrado de LisioMarco d’IschiaPasqualino MaddalenaPaola ManiniAlessandro PezzellaMassimo ValentinoNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-8 (2017) |
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Medicine R Science Q Carmela Bonavolontà Corrado de Lisio Marco d’Ischia Pasqualino Maddalena Paola Manini Alessandro Pezzella Massimo Valentino Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
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Abstract The origin of eumelanin optical properties remains a formidable conundrum preventing a detailed understanding of the complex photo-protective role of these widespread natural pigments and the rational design of innovative bioinspired materials for optoelectronic applications. Here we report the unusual kinetic and thickness-dependent evolution of the optical properties of black eumelanin polymers generated by spontaneous aerial polymerization of 5,6-dihydroxyindole (DHI) thin films (0.1–1 μm), consistent with peculiar solid state reorganization mechanisms governing broadband absorption. The complete reversal of eumelanin UV-visible transmittance spectrum curvature on passing from 0.2 to 0.5 μm thick films, the marked increase in visible extinction coefficients with increasing film thickness and the higher UV extinction coefficients in slowly vs. rapidly generated polymers concur to support distinct dynamic regimes of solid-state molecular reorganization at the nanoscale level and to do affect the development of broadband visible absorption. Solid state control of molecular reorganization disclosed herein may delineate new rational strategies for tuning optical properties in eumelanin thin films for optoelectronic applications. |
format |
article |
author |
Carmela Bonavolontà Corrado de Lisio Marco d’Ischia Pasqualino Maddalena Paola Manini Alessandro Pezzella Massimo Valentino |
author_facet |
Carmela Bonavolontà Corrado de Lisio Marco d’Ischia Pasqualino Maddalena Paola Manini Alessandro Pezzella Massimo Valentino |
author_sort |
Carmela Bonavolontà |
title |
Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
title_short |
Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
title_full |
Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
title_fullStr |
Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
title_full_unstemmed |
Anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
title_sort |
anomalous evolution of broadband optical absorption reveals dynamic solid state reorganization during eumelanin build-up in thin films |
publisher |
Nature Portfolio |
publishDate |
2017 |
url |
https://doaj.org/article/9571aa005e624bf68ddd3666479cfdbd |
work_keys_str_mv |
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1718385102893875200 |