Stability and Optical Absorption of a Comprehensive Virtual Library of Minimal Eumelanin Oligomer Models
dc.contributor.author
dc.date.accessioned
2021-07-27T11:21:19Z
dc.date.available
2021-07-27T11:21:19Z
dc.date.issued
2021-08-16
dc.identifier.issn
0044-8249
dc.identifier.uri
dc.description.abstract
Eumelanin is responsible for photoprotection in living organisms. It is made of 5,6-dihydroxyindole (DHI) oligomers. However, lack of detailed structural knowledge limits understanding its function and exploiting its potential in material science. To uncover the relationship between structural stability and optical properties, we have studied a virtual library of 830 DHI dimers. We find a preference for oxidized, polycyclic structures which speaks in favor of graphite-like structures for the larger oligomers, and propose an electrocyclic formation mechanism. Besides widely considered quinone oxidation patterns, also structures with interfragment double bonds and zwitterionic resonance structures are stable. Future theoretical melanine models will have to cover this diversity, and we introduce a new representative set of 49 stable dimers. Some stable oxidized dimers have absorption energies as low as 1.3 eV. They may be present as substructures in the naturally found oligomers and contribute to the absorption spectrum of the biopolymer
dc.description.sponsorship
Financial support from the European Commission, project 844230 (MSCA fellowship for J. W.), and Ministerio deCiencia, Innovación y Universidades (Spain), project PID-2019-104654GB-I00, and computational time at Red Española de Supercomputación, projects QSB-2019-3-0006, QSB-2020-1-006, QSB-2020-2-0011, and QSB-2020-3-0015, is grate-fully acknowledged
Open Access funding provided thanks to the CRUE-CSIC agreement with Wiley
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Wiley
dc.relation
PID2019-104654GB-I00
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Reproducció digital del document publicat a: https://doi.org/10.1002/anie.202106289
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Angewandte Chemie International Edition, 2021, vol. 60, núm. 34, p. 18800-18809
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Articles publicats (D-Q)
dc.rights
Attribution-NonCommercial 4.0 International
dc.rights.uri
dc.subject
dc.title
Stability and Optical Absorption of a Comprehensive Virtual Library of Minimal Eumelanin Oligomer Models
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.relation.projectID
info:eu-repo/grantAgreement/EC/H2020/844230/EU/Unraveling the Photoprotecting Mechanism of Melanin/Mel.Photo.Protect
info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PID2019-104654GB-I00/ES/SIMULANDO EFECTOS DE FASE SOBRE ESTADOS EXCITADOS/
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
033862
dc.contributor.funder
dc.type.peerreviewed
peer-reviewed
dc.relation.FundingProgramme
dc.relation.ProjectAcronym
dc.identifier.eissn
1521-3757