5,6-dihydroxyindole-2-carboxylic acid (DHICA): a First Principles Density-Functional Study

We report first principles density functional calculations for 5,6-dihydroxyindole-2-carboxylic acid (DHICA) and several reduced forms. DHICA and 5,6-dihydroxyindole (DHI) are believed to be the basic building blocks of the eumelanins. Our results show that carboxylation has a significant effect on the physical properties of the molecules. In particular, the relative stabilities and the HOMO-LUMO gaps (calculated with the $\Delta$SCF method) of the various redox forms are strongly affected. We predict that, in contrast to DHI, the density of unpaired electrons, and hence the ESR signal, in DHICA is negligibly small.Comment: 5 pages, 2 figure

Quantitative scattering of melanin solutions

The optical scattering coefficient of a dilute, well solubilised eumelanin solution has been accurately measured as a function of incident wavelength, and found to contribute less than 6% of the total optical attenuation between 210 and 325nm. At longer wavelengths (325nm to 800nm) the scattering was less than the minimum sensitivity of our instrument. This indicates that UV and visible optical density spectra can be interpreted as true absorption with a high degree of confidence. The scattering coefficient vs wavelength was found to be consistent with Rayleigh Theory for a particle radius of 38+-1nm.Comment: 23 pages, 5 figure

Towards Structure-Property-Function Relationships for Eumelanin

We discuss recent progress towards the establishment of important structure-property-function relationships in eumelanins - key functional bio-macromolecular systems responsible for photo-protection and immune response in humans, and implicated in the development of melanoma skin cancer. We focus on the link between eumelanin's secondary structure and optical properties such as broad band UV-visible absorption and strong non-radiative relaxation; both key features of the photo-protective function. We emphasise the insights gained through a holistic approach combining optical spectroscopy with first principles quantum chemical calculations, and advance the hypothesis that the robust functionality characteristic of eumelanin is related to extreme chemical and structural disorder at the secondary level. This inherent disorder is a low cost natural resource, and it is interesting to speculate as to whether it may play a role in other functional bio-macromolecular systems.Comment: 19 pages, 8 figures, Invited highlight article for Soft Matte