Exploring allomelanin: A comparative analysis via natural product extraction and synthesis.

Abstract

Allomelanin is a nitrogen-free class of melanin commonly found in plants and fungi. Although synthetic analogs have been developed from 1,8-dihydroxynaphthalene (1,8-DHN), detailed physicochemical comparisons with natural allomelanins remain limited. Herein, we extracted allomelanin from black knot fungus, chaga mushroom, and black oat using an acid-base extraction protocol, comparing them against a library of synthetic analogs derived from a range of putative, natural precursors. Spectroscopic analyses indicate that simple homopolymerization of 1,8-DHN does not adequately represent natural allomelanin structures. Instead, heterogeneous copolymerization of 1,8-DHN with catechol or tannic acid yields materials with physicochemical properties more consistent with natural extracts. This is also supported by their enhanced antioxidant and dye/metal adsorption properties. Like their synthetic counterparts, extracted natural allomelanins exhibit intrinsic porosity, reaching a Brunauer-Emmet-Teller area of 155 square meters per gram, potentially facilitating nutrient transport and toxin adsorption, although further studies will be required to probe this.