Redox interactions between electroactive bacteria and inorganic materials underpin many emerging technologies, but commonly used materials (e.g., metal oxides) suffer from limited tunability and can be challenging to characterize. In contrast, metal-organic frameworks exhibit well-defined structures, large surface areas, and extensive chemical tunability, but their utility as microbial substrates has not been examined. Here, we report that metal-organic frameworks can support the growth of the metal-respiring bacterium Shewanella oneidensis, specifically through the reduction of Fe(III). In a practical application, we show that cultures containing S. oneidensis and reduced metal-organic frameworks can remediate lethal concentrations of Cr(VI) over multiple cycles, and that pollutant removal exceeds the performance of either component in isolation or bio-reduced iron oxides. Our results demonstrate that frameworks can serve as growth substrates and suggest that they may offer an alternative to metal oxides in applications seeking to combine the advantages of bacterial metabolism and synthetic materials.

Gold is a critical resource in the jewelry and electronics industries and is facing increased consumer demand. Accordingly, methods for its extraction from waste effluents and environmental water sources have been sought to supplement existing mining infrastructure. Redox-mediated treatments, such as Fe(II)-based platforms, offer promise for precipitating soluble Au(III). We hypothesized that microbial generation of Fe(II) in the presence of sorbent metal−organic frameworks could capitalize on the advantages of both biologicaland chemical-driven extraction approaches. Toward this aim, we tested Au(III) removal by Shewanella oneidensis cultured with Fe(III)-based materials (ferrihydrite, Fe-BTC, MIL-100, or MIL-127). Across all tested materials, S. oneidensis generated the highest levels of redox-active Fe(II) (1.99 ± 0.27 mM) when cultured with MIL-127 as a respiratory substrate in a bicarbonate-buffered medium. This translated into superior Au(III) removal performance in terms of both removal rate and capacity (k = 2.55 ± 0.60 h −1 ; Q = 183 mg g −1 ). Unlike other materials tested, MIL-127 also maintained cell viability following repeated Au(III) challenges, enabling the regeneration of Fe(II) in the framework. Together, these effects facilitated the treatment of multiple cycles of Au(III) by S. oneidensis-reduced MIL-127. Overall, this work demonstrates that microbial generation of Fe(II) can facilitate the removal of Au(III), augmenting purely adsorptive platforms. Given the biological and chemical modularity of our system, our results suggest that future optimizations to microbial Fe(II) generation may offer promise for improving Au(III) extraction processes.

9Microbial interactions with redox-active materials are ubiquitous in geochemical cycling and 10 bioelectrochemical devices, but the biotic-abiotic interface has proven challenging to study due to 11 the structural complexity of mineral substrates. In contrast, metal-organic frameworks are a class Cr(VI) adsorption capacity, demonstrating that the framework confers protection to the bacteria 22 and that no regenerative step is needed for continued bioremediation. In sum, our results show 23 that the study of microbial-material interactions can be extended to metal-organic frameworks and 24 suggest that these materials may offer a promising alternative to metal oxides in applications 25 seeking to combine the advantages of bacterial metabolism and synthetic materials.

Melanin-like compounds have been studied in recent years for their electron transport and ultraviolet (UV) light absorbance properties as well as applications as functional, biocompatible catalysts, and material additives. Pyomelanin is a unique form of melanin compounds that has not received significant attention. Here, a strain of Yarrowia lipolytica suitable for the production of nearly 2.8 g L −1 of homogentisic acid (HGA) is metabolically engineered, which can then be oxidized to form pyomelanin either in situ or through altering pH. By using this biosourced material, a series of material traits including spectral analysis/UV-vis absorbance properties, electronic and metal interaction/chelation properties, and effectiveness in polymer dispersions with poly(l-lactide) are evaluated. In all cases, biosourced pyomelanin performs on par with or better than a chemically sourced analog. In a performance application, it is explored how pyomelanin may be blended at low concentrations to increase the elasticity of a rigid commercial polymer. Collectively, this work establishes biosourced pyomelanin as a versatile compound for unique material applications.