Electronic Properties of Random Polymers: Modelling Optical Spectra of Melanins

TL;DR

This study models the optical absorption spectra of eumelanins using theoretical methods, proposing a random polymer structure and successfully reproducing experimental spectral features.

Contribution

It introduces a novel model of eumelanin as random heteropolymer assemblies and applies semiempirical calculations to match experimental spectra.

Findings

INDO/CI method accurately reproduces experimental spectra

Random polymer model aligns with observed optical properties

Model provides insights into eumelanin structure and absorption

Abstract

Melanins are a group of complex pigments of biological origin, widely spread in all species from fungi to man. Among diverse types of melanins, the human melanins, eumelanins,are brown or black nitrogen-containing pigments, mostly known for their photoprotective properties in human skin. We have undertaken theoretical studies aimed to understand absorption spectra of eumelanins and their chemical precursors. The structure of the biopigment is poorly defined, although it is believed to be composed of cross-linked heteropolymers based on indolequinones. As a basic model of the eumelanin structure, we have chosen pentamers containing hydroquinones (HQ) and/or 5,6-indolequinones (IQ) and/or semiquinones (SQ) often listed as structural melanin monomers. The eumelanin oligomers have been constructed as random compositions of basic monomers and opitimized for the energy of bonding. Absorption spectra of model assemblies have been calculated within the semiempirical intermediate neglect of differential overlap (INDO) approximation. Model spectrum of eumelanin has been further obtained by sum of independent spectra of singular polymers. By comparison with experimental data it is shown that the INDO/CI method manages to reproduce well characteristic properties of experimental spectrum of synthetic eumelanins.