Tunichrome-Inspired Gold-Enrichment Dispersion Matrix and Its Application in Water Treatment: A Proof-of-Concept Investigation.

Tunicate, a filter-feeder in seawater, is able to accumulate high amount of metals using intracellular polymer matrices. The woven pyrogallol structures of tunichrome, a small peptide contained in tunicate's blood cells, is believed to be responsible for selective metal sequestration in tunicates from seawater. However, the intriguing tunichrome matrix is difficult both to harvest from the tunicate and to synthesize massively due to the extreme oxidation sensitivity of the pyrogallol moiety which limits the study scope. Here, we succeeded to mimic tunichrome by conjugating two cheap and naturally occurring components: pyrogallol-5-carboxylic acid (gallic acid) and chitin nanofiber. A tunicate-mimetic infiltration matrix of surface-tailored chitin nanofibers with pyrogallol moieties (CGa) demonstrated the versatility of this strategy in generation of ingenious filtration material, especially for unprecedented fine and clean gold recovery inside of the tunicate-mimetic infiltration matrix (>99%, 533 mg gold per gram weight), which exceeds that of the presently most popular materials. Complexation between pyrogallol on the nanofiber and gold was similar to that of a tunichrome's metal sequestration. Extended X-ray absorption fine structure (EXAFS) spectroscopy and data-fitting elucidated the decreased coordination numbers for Au-Au nearest neighbors, demonstrating that gold coordinated to pyrogallol units, followed by an intramolecular association of Au. A catalytic reduction of 4-nitrophenol mediated by the tunicate-mimetic matrix with harvested gold revealed excellent recyclability up to 30 cycles (∼95% reduction), which together with methylene blue reduction and antimicrobial performances indicates the versatile characteristics of sustainable processes by the tunichrome mimetics. This strategy opens the door for fast-developing new biomimetic alternatives for precious metal recovery, which is not restricted to gold and can offer a tool for multifaceted soft/hard nanomaterials.