title: Hydration effects on the electronic properties of eumelanin building blocks.
abstract: Theoretical results for the electronic properties of eumelanin building blocks in the gas phase and water are presented. The building blocks presently investigated include the monomeric species DHI (5,6-dihydroxyindole) or hydroquinone (HQ), DHICA (5,6-dihydroxyindole-2-carboxylic acid), indolequinone (IQ), quinone methide (MQ), two covalently bonded dimers [HM ≡ HQ + MQ and IM ≡ IQ + MQ], and two tetramers [HMIM ≡ HQ + IM, IMIM ≡ IM + IM]. The electronic properties in water were determined by carrying out sequential Monte Carlo/time dependent density functional theory calculations. The results illustrate the role played by hydrogen bonding and electrostatic interactions in the electronic properties of eumelanin building blocks in a polar environment. In water, the dipole moments of monomeric species are significantly increased ([54-79]%) relative to their gas phase values. Recently, it has been proposed that the observed enhancement of the higher-energy absorption intensity in eumelanin can be explained by excitonic coupling among eumelanin protomolecules [C.-T. Chen et al., Nat. Commun. 5, 3859 (2014)]. Here, we are providing evidence that for DHICA, IQ, and HMIM, the electronic absorption toward the higher-energy end of the spectrum ([180-220] nm) is enhanced by long-range Coulombic interactions with the water environment. It was verified that by superposing the absorption spectra of different eumelanin building blocks corresponding to the monomers, dimers, and tetramers in liquid water, the behaviour of the experimental spectrum, which is characterised by a nearly monotonic decay from the ultraviolet to the infrared, is qualitatively reproduced. This result is in keeping with a "chemical disorder model," where the broadband absorption of eumelanin pigments is determined by the superposition of the spectra associated with the monomeric and oligomeric building blocks.
authors: Instituto de Física da Universidade Federal de Goiás, 74690-900 Goiânia, GO, Brazil.
authors: Leonardo Bruno
authors: LB
authors: Assis Oliveira
authors: Instituto de Física da Universidade Federal de Goiás, 74690-900 Goiânia, GO, Brazil.
authors: Tertius
authors: T
authors: L Fonseca
authors: Grupo de Física Matemática da Universidade de Lisboa and Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade de Lisboa, 1749-016 Lisboa, Portugal.
authors: Benedito J
authors: BJ
authors: Costa Cabral
authors: Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP, Brazil.
authors: Kaline
authors: K
authors: Coutinho
authors: Instituto de Física da Universidade de São Paulo, CP 66318, 05314-970 São Paulo, SP, Brazil.
authors: Sylvio
authors: S
authors: Canuto