Issue 5, 2020

Ultrafast spectral hole burning reveals the distinct chromophores in eumelanin and their common photoresponse

Abstract

Eumelanin, the brown-black pigment found in organisms from bacteria to humans, dissipates solar energy and prevents photochemical damage. While the structure of eumelanin is unclear, it is thought to consist of an extremely heterogeneous collection of chromophores that absorb from the UV to the infrared, additively producing its remarkably broad absorption spectrum. However, the chromophores responsible for absorption by eumelanin and their excited state decay pathways remain highly uncertain. Using femtosecond broadband transient absorption spectroscopy, we address the excited state behavior of chromophore subsets that make up a synthetic eumelanin, DOPA melanin, and probe the heterogeneity of its chromophores. Tuning the excitation light over more than an octave from the UV to the visible and probing with the broadest spectral window used to study any form of melanin to date enable the detection of spectral holes with a linewidth of 0.6 eV that track the excitation wavelength. Transient spectral hole burning is a manifestation of extreme chemical heterogeneity, yet exciting these diverse chromophores unexpectedly produces a common photoinduced absorption spectrum and similar kinetics. This common photoresponse is assigned to the ultrafast formation of immobile charge transfer excitons that decay locally and that are formed among graphene-like chromophores in less than 200 fs. Raman spectroscopy reveals that chromophore heterogeneity in DOPA melanin arises from different sized domains of sp2-hybridized carbon and nitrogen atoms. Furthermore, we identify for the first time striking parallels between the excited state dynamics of eumelanin and disordered carbon nanomaterials, suggesting that they share common structural attributes.

Graphical abstract: Ultrafast spectral hole burning reveals the distinct chromophores in eumelanin and their common photoresponse

Supplementary files

Article information

Article type
Edge Article
Submitted
06 9月 2019
Accepted
24 11月 2019
First published
18 12月 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 1248-1259

Ultrafast spectral hole burning reveals the distinct chromophores in eumelanin and their common photoresponse

F. R. Kohl, C. Grieco and B. Kohler, Chem. Sci., 2020, 11, 1248 DOI: 10.1039/C9SC04527A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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