Biological Nicotinamide Cofactor as a Redox-Active Motif for Reversible Electrochemical Energy Storage.

Nicotinamide adenine dinucleotide (NAD+ ) is one of the most well-known redox cofactors carrying electrons. Now, it is reported that the intrinsically charged NAD+ motif can serve as an active electrode in electrochemical lithium cells. By anchoring the NAD+ motif by the anion incorporation, redox activity of the NAD+ is successfully implemented in conventional batteries, exhibiting the average voltage of 2.3 V. The operating voltage and capacity are tunable by altering the anchoring anion species without modifying the redox center itself. This work not only demonstrates the redox capability of NAD+ , but also suggests that anchoring the charged molecules with anion incorporation is a viable new approach to exploit various charged biological cofactors in rechargeable battery systems.

Self-Assembled Peptide-Carbon Nitride Hydrogel as a Light-Responsive Scaffold Material.

Peptide self-assembly is a facile route to the development of bioorganic hybrid materials that have sophisticated nanostructures toward diverse applications. Here, we report the synthesis of self-assembled peptide (Fmoc-diphenylalanine, Fmoc-FF)/graphitic carbon nitride (g-C3N4) hydrogels for light harvesting and biomimetic photosynthesis through noncovalent interactions between aromatic rings in Fmoc-FF nanofibers and tris-s-triazine in g-C3N4 nanosheets. According to our analysis, the photocurrent density of the Fmoc-FF/g-C3N4 hydrogel was 1.8× higher (0.82 µA cm-1) than that of the pristine g-C3N4. This is attributed to effective exfoliation of g-C3N4 nanosheets in the Fmoc-FF/g-C3N4 network, facilitating photoinduced electron transfers. The Fmoc-FF/g-C3N4 hydrogel reduced NAD+ to enzymatically active NADH under light illumination at a high rate of 0.130 mol g-1 h-1 and drove light-responsive redox biocatalysis. Moreover, the Fmoc-FF/g-C3N4 scaffold could well-encapsulate key photosynthetic components, such as electron mediators, cofactors, and enzymes, without noticeable leakage, while retaining their functions within the hydrogel. The prominent activity of the Fmoc-FF/g-C3N4 hydrogel for biomimetic photosynthesis resulted from the easy transfer of photoexcited electrons from electron donors to NAD+ via g-C3N4 and electron mediators as well as the hybridization of key photosynthetic components in a confined space of the nanofiber network.

Catecholamine-functionalized graphene as a biomimetic redox shuttle for solar water oxidation.

In natural photosynthesis, solar energy is converted to chemical energy through a cascaded, photoinduced charge transfer chain that consists of primary and secondary acceptor quinones (i.e., QA and QB). This leads to an exceptionally high near-unity quantum yield. Inspired by the unique multistep architecture of charge transfer in nature, we have synthesized a catecholamine-functionalized, reduced graphene oxide (RGO) film as a redox mediator that can mimic quinone acceptors in photosystem II. We used polynorepinephrine (PNE) as a redox-shuttling chemical. We also used it to coat graphene oxide (GO) and to reduce GO to RGO. The quinone ligands in PNE, which are characterized by a charge transfer involving two electrons and two protons, acted as electron acceptors that facilitated charge transfer in photocatalytic water oxidation. Furthermore, PNE-coated RGO film promoted fast charge separation in [Ru(bpy)3]2+ and increased the activity of cobalt phosphate on photocatalytic water oxidation more than two-fold. The results suggest that our bio-inspired strategy for the construction of a forward charge transfer pathway can provide more opportunities to realize efficient artificial photosynthesis.

Graphitic Carbon Nitride as Reinforcement of Photopolymer Resin for 3D Printing.

Digital light processing (DLP) has the advantages of higher printing speed and product precision than other 3D printing technologies. However, DLP products have low mechanical strength owing to the inherent properties of photocurable materials. Graphitic carbon nitride (GCN), which is an abundant hydrogen bonding motif (-NH2, -NH), has low solubility in most solvents; thus, to use GCN as a reinforcement of the polymer matrix, optimal dispersion processes must be applied. In this study, GCN was proposed as a novel reinforcing material to improve the mechanical properties of photocurable epoxy acrylate (EA) resins for DLP. Herein, two-step (planetary mixing and ultrasonication) processes were applied to disperse GCN within EA, and the dispersion performance was identified by checking the degree of precipitation over time. To test the printability of the dispersed GCN/EA composites subjected to DLP 3D printing, cube specimens of GCN/EA composites were prepared, and the dispersed GCN/EA output had a low dimensional error of 0.3-1.3%, while the undispersed composite output showed larger dimensional errors of 27.7-36.2%. Additionally, in the mechanical test of the DLP-3D-printed sample (dispersed GCN/EA composite), the tensile strength and elastic modulus of the dispersed GCN/EA composite specimen were measured to be 75.56 MPa and 3396 MPa, respectively, which were improved by 22% (tensile strength) and 34% (modulus of elasticity) in relation to those of the neat EA specimen. This study is the first to use GCN as a reinforcement and manufacture a composite product for DLP with excellent performance (22% increased tensile strength) through the optimal dispersion of GCN. Considering the high mechanical performance, DLP products using the GCN/EA composites can be used in industries such as automobiles, shipbuilding, and aviation.

CO2 -Reductive, Copper Oxide-Based Photobiocathode for Z-Scheme Semi-Artificial Leaf Structure.

Green plants convert sunlight into high-energy chemicals by coupling solar-driven water oxidation in the Z-scheme and CO2 fixation in the Calvin cycle. In this study, formate dehydrogenase from Clostridium ljungdahlii (ClFDH) is interfaced with a TiO2 -coated CuFeO2 and CuO mixed (ClFDH-TiO2 |CFO) electrode. In this biohybrid photocathode, the TiO2 layer enhances the photoelectrochemical (PEC) stability of the labile CFO photocathode and facilitates the transfer of photoexcited electrons from the CFO to ClFDH. Furthermore, inspired by the natural photosynthetic scheme, the photobiocathode is combined with a water-oxidizing, FeOOH-coated BiVO4 (FeOOH|BiVO4 ) photoanode to assemble a wireless Z-scheme biocatalytic PEC device as a semi-artificial leaf. The leaf-like structure effects a bias-free biocatalytic CO2 -to-formate conversion under visible light. Its rate of formate production is 2.45 times faster than that without ClFDH. This work is the first example of a wireless solar-driven semi-biological PEC system for CO2 reduction that uses water as an electron feedstock.

Unbiased biocatalytic solar-to-chemical conversion by FeOOH/BiVO4/perovskite tandem structure.

Redox enzymes catalyze fascinating chemical reactions with excellent regio- and stereo-specificity. Nicotinamide adenine dinucleotide cofactor is essential in numerous redox biocatalytic reactions and needs to be regenerated because it is consumed as an equivalent during the enzymatic turnover. Here we report on unbiased photoelectrochemical tandem assembly of a photoanode (FeOOH/BiVO4) and a perovskite photovoltaic to provide sufficient potential for cofactor-dependent biocatalytic reactions. We obtain a high faradaic efficiency of 96.2% and an initial conversion rate of 2.4 mM h-1 without an external applied bias for the photoelectrochemical enzymatic conversion of α-ketoglutarate to L-glutamate via L-glutamate dehydrogenase. In addition, we achieve a total turnover number and a turnover frequency of the enzyme of 108,800 and 6200 h-1, respectively, demonstrating that the tandem configuration facilitates redox biocatalysis using light as the only energy source.

Nature-Inspired Synthesis of Nanostructured Electrocatalysts through Mineralization of Calcium Carbonate.

Biomineralization is a biogenic process that produces elaborate inorganic and organic hybrid materials in nature. Inspired by the natural process, this study explored a new mineralization approach to create nanostructured CaCO3 films composed of amorphous CaCO3 hemispheres by using catechol-rich polydopamine (PDA) as a biomimetic mediator. The thus synthesized biomimetic CaCO3 was successfully transformed to nanostructured films of metal-oxide minerals, such as FeOOH, CoCO3 , NiCO3 , and MnOOH, through a simple procedure. The CaCO3 -templated metal-oxide minerals functioned as efficient electrocatalysts; a CaCO3 -templated cobalt phosphate (nanoCoPi) film exhibited high stability as a water-oxidation electrocatalyst with a current density of 1.5 mA cm-2 . The nanostructure of nanoCoPi, consisting of individual nanoparticles (≈70 nm) and numerous internal pores (BET surface area: 3.17 m2 g-1 ), facilitated an additional charge-transfer pathway from the electrode to individual active sites of the catalyst. This work demonstrates a plausible strategy for facile and green synthesis of nanostructured electrocatalysts through biomimetic CaCO3 mineralization.

Photoactive g-C3 N4 Nanosheets for Light-Induced Suppression of Alzheimer's ß-Amyloid Aggregation and Toxicity.

Graphitic carbon nitride (g-C3 N4 ) has a suppressive capability toward Alzheimer's Aß aggregation under light-illumination. Photoinduced electrons of g-C3 N4 generate reactive oxygen resulting in photooxidation of amyloid peptides that blocks Aß aggregation. Fe doping of g-C3 N4 frameworks results in enhanced optical properties and even stronger inhibition of Aß aggregation.

Human Urine-Fueled Light-Driven NADH Regeneration for Redox Biocatalysis.

Human urine is considered as an alternative source of hydrogen and electricity owing to its abundance and high energy density. Here we show the utility of human urine as a chemical fuel for driving redox biocatalysis in a photoelectrochemical cell. Ni(OH)2 -modified α-Fe2 O3 is selected as a photoanode for the oxidation of urea in human urine and black silicon (bSi) is used as a photocathode material for nicotinamide cofactor (NADH: hydrogenated nicotinamide adenine dinucleotide) regeneration. The electrons extracted from human urine are used for the regeneration of NADH, an essential hydride mediator that is required for numerous redox biocatalytic reactions. The catalytic reactions at both the photoanode and the photocathode were significantly enhanced by light energy that lowered the overpotential and generated high currents in the full cell system.

Sunlight-assisted, biocatalytic formate synthesis from CO2 and water using silicon-based photoelectrochemical cells.

We report on a silicon-based photoelectrochemical cell that integrates a formate dehydrogenase from Thiobacillus sp. (TsFDH) to convert CO2 to formate using water as an electron donor under visible light irradiation and an applied bias. Our current study suggests that the deliberate integration of biocatalysis to a light-harvesting platform could provide an opportunity to synthesize valuable chemicals with the use of earth-abundant materials and sustainable resources.

Bi-functional RuO2-Co3O4 core-shell nanofibers as a multi-component one-dimensional water oxidation catalyst.

The core-shell structure of RuO2-Co3O4 fibers comprising the inner region of highly conductive RuO2 and the outer region of catalytic Co3O4 provided a fast and effective transport pathway for holes to O2-evolving sites, leading to a highly efficient water oxidation performance.