Electron Transfer Mediator Research Articles

ZnxFe3-xO4–ZnO heterojunction interfaced with poly(L-DOPA) electron transfer mediator layer for enhanced visible light photocatalytic activity

Z-scheme heterojunctions comprising ZnxFe3-xO4@poly(L-DOPA)@ZnO (ZF@PD@ZnO) were synthesized using solvothermal and precipitation techniques. The study aimed to investigate the impact of the poly(L-DOPA) electron transfer mediator on the photocatalytic performance of ZnxFe3-xO4@ZnO (ZF@ZnO) nanocomposites under visible light irradiation. X-ray diffraction (XRD) and HRTEM analysis confirmed the formation of heterostructures, identifying the crystalline phases of both ZnO and zinc ferrite. BFTEM images revealed a polyhedral shape for all samples, with a tendency toward mild agglomeration. The partial inversion of the zinc ferrite cubic spinel structure was evidenced by FT-IR, XPS, and VSM analyses. Zinc ferrite was found to be ferromagnetic, with cation distributions between tetrahedral (A) and octahedral (B) positions as [Zn0.62+Fe0.43+]A[Fe0.42+Fe1.63+]BO4. The samples exhibited notable photocatalytic activity against Rhodamine B, serving as a model contaminant. Furthermore, the stability and reusability of the samples were examined. Additionally, the study elucidated the photocatalytic mechanism produced by the ternary Z-scheme ZF@PD@ZnO, involving spin-polarized charge carriers. Energy band alignment was evaluated by combining ultraviolet photoelectron spectroscopy (UPS) with UV-Vis spectroscopy. The interplay between band alignment and reactive oxygen species (ROS) generation was discussed in correlation with EPR results. Enhanced ROS generation under visible light illumination, observed in the ZF@PD@ZnO nanocomposite, is mainly due to the addition of the conductive poly(L-DOPA) layer, acting as an electron transfer mediator in the Z-scheme heterojunction, ensuring enhanced charge separation.

Exploring the peroxydisulfate activation by carbon nanotubes for pollutants degradation: Identification of the primary reaction mechanism and key molecular descriptor

Carbon nanotubes (CNT) have been proposed to activate persulfate over the past decade, resulting in successful degradation performance for organic pollutants in wastewater treatment. However, there is debate over the reaction mechanism involving radical versus non-radical pathways, setting up a roadblock to further developing persulfate activation by carbonaceous materials. This work focused on the carbon nanotubes/peroxydisulfate (CNT/PDS) system, investigated its reaction mechanism, and unveiled the relationship from the aspect of molecular descriptors. The involvement of radicals (e.g., SO4•− and HO•) and 1O2 was ruled out by the observation of quenching effect, oxidation products, chemical probes, solvent exchange, and electron paramagnetic resonance spectra. Then, mediated electron transfer was deemed as the primary reaction mechanism based on linear sweep voltammetry analysis, which was supported by the PDS consumption result. The substrate-dependent treatment capacity was found in the CNT/PDS for multiple contaminants degradation, and it turned out that EB3LYP was the most significant parameter in the relationship between degradation rates and molecular descriptors. Outstanding environmental application was exhibited based on the coexistence of various organic/inorganic substances and repeated degradation experiment. Therefore, the findings from this study would be helpful for both scientific research and technical development of persulfate activation by CNT.

Upcycle polyethylene terephthalate waste by photoreforming: Bifunction of Pt cocatalyst

Upcycle polyethylene terephthalate (PET) waste by photoreforming (PR) is a sustainable and green approach to tackle environmental problems but with challenges to obtain valuable oxidation products and high purity hydrogen simultaneously. Noble metal cocatalysts are essential to enhance the overall PR reaction efficacy. In this work, TiO2 nanotubes (TiO2 NTs) decorated with single Pt atoms (Pt1/TiO2) or Pt nanoparticles (PtNPs/TiO2) are used in the photoreforming reaction (in one batch), and the oxidation products from ethylene glycol (EG, hydrolysed product of PET) in liquid phase and hydrogen are detected. With Pt1/TiO2, EG is oxidized to glyoxal, glyoxylate or lactate, and hydrogen evolution rate (r H2) reaches 51.8 μmol⋅h−1⋅gcat−1, that is 30 times higher than that of TiO2. For PtNPs/TiO2 (size of Pt NPs: 1.97 nm), hydrogen evolution reaches 219.1 μmol⋅h−1⋅gcat−1, but with the oxidation product of acetate only. DFT calculation demonstrates that for Pt NPs, the reaction path for hydrogen evolution is preferred thermodynamically, due to the formation of Schottky junction. On the oxidation of EG, theoretical and spectroscopic analysis suggest that bidentate adsorption of EG at the interface is facile on Pt1/TiO2, compared to that on PtNPs/TiO2 (two Pt sites), but oxidation products, adsorb less strongly, compared to PtNPs/TiO2, that eventually regulates the distribution of oxidation products. The results thus demonstrate the bifunctions of Pt in the PR reaction, i.e., electron transfer mediator for hydrogen evolution and reactive sites for molecules adsorption. The oxidation reaction is dominated by the adsorption-desorption behavior of molecules but the reduction reaction is controlled by the electron transfer. In addition, acidification of pretreated PET alkaline solution achieves separation of pure terephthalic acid (PTA), which further improves the reaction efficiency possibly by offering high density of active sites and acidic environment. Our work thus demonstrates that to upcycle PET plastics, an optimized process can be reached by atomic design of photocatalysts and proper treatment on the plastic wastes.

Selective oxidation of cyclohexanol to cyclohexanone with peroxydisulfate over Co/N doped porous carbon

Cyclohexanone serves as a vital chemical intermediate in nylon production and as a solvent in the manufacturing of resins and paints. The quest for facile, environmentally-friendly, and cost-effective methods to achieve selective oxidation of cyclohexanol is highly desirable. In this study, we successfully achieved the oxidation in water solution using peroxydisulfate (PDS) activation. This was accomplished by employing a Co/N doped porous carbon catalyst synthesized through the one-step carbonization of zeolite-imidazolate frameworks (ZIFs). The catalysts derived from ZIFs with various Co/Zn ratios were extensively characterized using XRD, SEM, TEM, N2 adsorption–desorption, and XPS techniques. The catalyst's performance was assessed under different reaction conditions, including reaction temperature, PDS dosage, and water quality. Notably, the results revealed that under mild conditions, a high efficiency was achieved with over 55% cyclohexanol conversion and 80% cyclohexanone selectivity within 3 h. To gain a greater understanding of the reactive oxygen species involved, we conducted further quenching experiments and EPR analysis. Our findings suggested that·SO4-, ·OH, and mediated electron transfer played a dominant role in the oxidation process. The insights obtained from this work have the potential to offer a green and economically viable method for the selective oxidation of cyclohexanol to cyclohexanone.

Catalysis of Indium Ion Electroreduction in the Presence of Acetazolamide in Chlorates(VII) Solutions with Varied Water Activity.

The influence of acetazolamide (ACT) on the kinetics and the mechanism of electroreduction of In(III) ions as a function of changes of the water activity was investigated using electrochemical methods (DC, SWV, CV and EIS, CV). The multi-step mechanism of the electroreduction process should take into account the dehydration step of indium ions and the presence of In-ACT (,,cap-pair" effect) active complexes, mediating electron transfer, located in the adsorption layer. Differences in the electrode mechanism in the presence of ACT were observed for higher chlorates(VII) concentrations (above 4 mol ⋅ dm-3 chlorates(VII)) reflected by a lack of step wise nature of the electrode process. The highest catalytic activity was observed in 4 mol ⋅ dm-3 chlorates(VII).

The dual roles of dissimilatory iron reduction in the carbon cycle: The "iron mesh" effect can increase inorganic carbon sequestration.

Dissimilatory iron reduction (DIR) can drive the release of organic carbon (OC) as carbon dioxide (CO2 ) by mediating electron transfer between organic compounds and microbes. However, DIR is also crucial for carbon sequestration, which can affect inorganic-carbon redistribution via iron abiotic-phase transformation. The formation conditions of modern carbonate-bearing iron minerals (ICFe ) and their potential as a CO2 sink are still unclear. A natural environment with modern ICFe , such as karst lake sediment, could be a good analog to explore the regulation of microbial iron reduction and sequential mineral formation. We find that high porosity is conducive to electron transport and dissimilatory iron-reducing bacteria activity, which can increase the iron reduction rate. The iron-rich environment with high calcium and OC can form a large sediment pore structure to support rapid DIR, which is conducive to the formation and growth of ICFe . Our results further demonstrate that the minimum DIR threshold suitable for ICFe formation is 6.65 μmol g-1 dw day-1 . DIR is the dominant pathway (average 66.93%) of organic anaerobic mineralization, and the abiotic-phase transformation of Fe2+ reduces CO2 emissions by ~41.79%. Our findings indicate that as part of the carbon cycle, DIR not only drives mineralization reactions but also traps carbon, increasing the stability of carbon sinks. Considering the wide geographic distribution of DIR and ICFe , our findings suggest that the "iron mesh" effect may become an increasingly important vector of carbon sequestration.

Direct Electron Transfer-Type Oxidoreductases for Biomedical Applications.

Among the various types of enzyme-based biosensors, sensors utilizing enzymes capable of direct electron transfer (DET) are recognized as the most ideal. However, only a limited number of redox enzymes are capable of DET with electrodes, that is, dehydrogenases harboring a subunit or domain that functions specifically to accept electrons from the redox cofactor of the catalytic site and transfer the electrons to the external electron acceptor. Such subunits or domains act as built-in mediators for electron transfer between enzymes and electrodes; consequently, such enzymes enable direct electron transfer to electrodes and are designated as DET-type enzymes. DET-type enzymes fall into several categories, including redox cofactors of catalytic reactions, built-in mediators for DET with electrodes and by their protein hierarchic structures, DET-type oxidoreductases with oligomeric structures harboring electron transfer subunits, and monomeric DET-type oxidoreductases harboring electron transfer domains. In this review, we cover the science of DET-type oxidoreductases and their biomedical applications. First, we introduce the structural biology and current understanding of DET-type enzyme reactions. Next, we describe recent technological developments based on DET-type enzymes for biomedical applications, such as biosensors and biochemical energy harvesting for self-powered medical devices. Finally, after discussing how to further engineer and create DET-type enzymes, we address the future prospects for DET-type enzymes in biomedical engineering.

Carbon nanotubes mediate electron transfer between Shewanella oneidenis MR-1 and nano zero-valent iron to enhance the elimination of Cr(VI) from aqueous media

Nano zero-valent iron (nZVI) has been widely employed for the elimination of heavy metals from wastewater. However, the practical application of nZVI is greatly limited due to its fast aggregation and surface passivation. In this study, a carbon nanotube-supported nZVI composite (nZVI@CNTs) was synthesized and coupled with Shewanella oneidensis MR-1 to enhance the removal of Cr(VI) from aqueous media. The results demonstrated that the coupling of nZVI@CNTs and MR-1 (nZVI@CNTs/MR-1) exhibited superior performance in eliminating Cr(VI) compared to using nZVI@CNTs or MR-1 alone. Electrochemical characterization demonstrated that CNTs acting as electron shuttles improve the electron transfer from MR-1 to nZVI, thus facilitating the passivation layer dissolution. XRD analysis proved that MR-1 can effectively promote the dissolution of the Fe(III) passivation layer with the existence of CNTs. FTIR and XPS analyses confirmed that CNTs contain many functional groups (such as C − C and C = O) related to extracellular electron transfer, thus promoting the electron transfer of MR-1 to nZVI. Three-dimensional excitation-emission matrix (3D-EEM) analysis showed that the extracellular polymeric substances (EPS) generated from MR-1 participated in the Cr(VI) elimination. The mechanism analysis demonstrated the Fe(II) dissolved from the nZVI passivation layer reduces Cr(VI) to Cr(III) and then removes it by co-precipitation, and the EPS secreted by MR-1 also participates in the Cr(VI) adsorption and reduction. Generally, the coupling of nZVI@CNTs and MR-1 successfully addresses the drawbacks of nZVI and demonstrates a remarkable ability to remove Cr(VI).

Fabricating high-purity graphite disk electrodes as a cost-effective alternative in fundamental electrochemistry research

Graphite electrodes offer remarkable electrochemical properties, emerging as a viable alternative to glassy carbon (GCE) and other carbon-based electrodes for fundamental electrochemistry research. We report the fabrication and characterization of high-purity graphite disk electrodes (GDEs), made from cost-effective materials and a solvent-free methodology employing readily available laboratory equipment. Analysis of their physical properties via SEM, EDX and XPS reveals no metallic interferences and a notably high porosity, emphasizing their potential. The electrochemical performances of GDEs were found to be comparable to those of GCE. Immobilization of peptides and enzymes, both via covalent coupling and surface adsorption, was used to explore potential applications of GDEs in bioelectrochemistry. Enzyme activity could be addressed both via direct electron transfer and mediated electron transfer mechanism. These results highlight the interesting properties of our GDEs and make them a low-cost alternative to other carbon-based electrodes, with potential for future real-world applications.

Humic substances mediated superior photochemical pollutant conversion on defective TiO2 in environmentally relevant matrices: The key roles of oxygen vacancy in surface interactions, oxidant activation and radical generation

Ubiquitous humic substances usually exhibit strong interfering effects on target pollutant removal in advanced water purification. This work aims to develop a photochemical conversion system on the nonstoichiometric TiO2 for pollutant removal in environmentally relevant matrices. In this synergistic reaction system, the redox-reactive humic substances and defective oxygen vacancies can serve as the organic electron transfer mediator and the key surface reactive sites, respectively. This system achieves a superior pollutant degradation in real surface water at low oxidant concentrations. Reactive oxygen vacancies on the TiO2 surface and sub-surface are of considerable interest for this photochemical reaction system. By engineering defective oxygen vacancies on high-energy {001} polar facet, the surface and electronic interactions between tailored TiO2 and humic substances are greatly strengthened for the promoted electron transfer and oxidant activation. Rendered by the strong surface affinity and molecular activation, defective oxygen vacancies thermodynamically and dynamically promote reactive chain reactions for free radical formation, including the selective O2 reduction to ·O2− and the H2O2 activation to ·OH. Our findings take new insights into environmental geochemistry, and provide an effective strategy to in-situ boost the humic substances-mediated water purification without secondary pollution. Environmental implicationHumic substances are widely distributed in aquatic environment, thus playing important roles in environmental geochemistry. For example, humic substances can achieve good surface adsorption through electrostatic adsorption, ligand exchange and electronic interactions with typical TiO2 to form reactive ligand-metal charge transfer complexes for pollutant degradation. Inspired by the unique properties of surface and sub-surface oxygen vacancies, the defective TiO2 was designed to refine the humic substances-mediated photochemical reactions. A superior reactivity was measured for pollutant degradation. Our findings provide an effective strategy to boost naturally photochemical decontamination in environmentally relevant matrices.

Metal–N4 model single‐atom catalyst with electroneutral quadri‐pyridine macrocyclic ligand for CO2 electroreduction

AbstractMetal–N–C single‐atom catalysts, mostly prepared from pyrolysis of metal‐organic precursors, are widely used in heterogeneous electrocatalysis. Since metal sites with diverse local structures coexist in this type of material and it is challenging to characterize the local structure, a reliable structure–property relationship is difficult to establish. Conjugated macrocyclic complexes adsorbed on carbon support are well‐defined models to mimic the single‐atom catalysts. Metal–N4 site with four electroneutral pyridine‐type ligands embedded in a graphene layer is the most commonly proposed structure of the active site of single‐atom catalysts, but its molecular counterpart has not been reported. In this work, we synthesized the conjugated macrocyclic complexes with a metal center (Co, Fe, or Ni) coordinated with four electroneutral pyridinic ligands as model catalysts for CO2 electroreduction. For comparison, the complexes with anionic quadri‐pyridine macrocyclic ligand were also prepared. The Co complex with the electroneutral ligand expressed a turnover frequency of CO formation more than an order of magnitude higher than that of the Co complex with the anionic ligand. Constrained ab initio molecular dynamics simulations based on the well‐defined structures of the model catalysts indicate that the Co complex with the electroneutral ligand possesses a stronger ability to mediate electron transfer from carbon to CO2.

Fabrication and characterization of electrically conducting electrochemically synthesized polypyrrole-based enzymatic biofuel cell anode with biocompatible redox mediator vitamin K3

Enzymatic biofuel cells (EBFCs) hold tremendous potential to power biomedical devices, biosensors, and bioelectronics. Unlike conventional toxic batteries, these electrochemical devices are biocompatible, harnessing energy from physiological fluids and producing usable electrical energy. But the commercialization of EBFCs is limited by the low operational stability, limited power output and poor electron transport efficiency of the enzymatic electrodes. In this study, a novel bioanode exhibiting a high electron transfer ability and long-term stability was fabricated. For the preparation of the anode, surfactant-assisted polypyrrole (PPy) was electrochemically co-deposited on a platinum wire with the simultaneous entrapment of vitamin K3 (VK3) and GOx (glucose oxidase) in the PPy matrix. Herein, conducting PPy acts as an electron transfer enhancer and provides appropriate electrical communication between the active site of the enzyme glucose oxidase (GOx) and the electrode surface. Biocompatible redox mediator vitamin K3 was employed as an electron transfer mediator to shuttle electrons between the oxidized fuel glucose and surface of the electrode in the electrochemical cell. The electrical conductivity of PPy was measured using the four-probe technique of conductivity measurement of semiconductors. The morphological characterization of as-synthesized anode (PPy/CTAB/VK3/GOx) was performed by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The electrochemical characterization was studied by cyclic voltammetry (CV), linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) techniques. It was observed that the room-temperature conductivity of PPy lies in the semiconducting range and it also shows good stability on exposure to laboratory air, making it a promising material to provide electrical contact. The study developed a bioanode producing a modest current density of 6.35 mA cm–2 in 20 mM glucose solution. The stability, current output and ease of manufacturing process of the electrode make it particularly suitable for employment in biofuel cell applications.

Fe(III) oxyhydroxides mediated electron transfer from thiols to O2 for hydroxyl radical production

Thiols serve as important electron reservoirs in subsurface environments, playing an important role in biogeochemical cycling of redox-sensitive elements. Nevertheless, due to the kinetic constraint on thiol oxidation by O2, hydroxyl radical (•OH) production during thiol oxygenation had long been disregarded. •OH is the most powerful oxidant in natural environment, capable of oxidizing most of inorganic and organic pollutants. This study revealed that Fe(III) oxyhydroxides could mediate electron transfer from thiols to O2, thereby facilitating •OH production within a pH range of 3 to 9. For instance, at pH 7, the presence of 1 g/L ferrihydrite increased •OH accumulation from <0.2 to 15.3 μM within 10 h during the oxygenation of 6 mM cysteine. This enhancement resulted from Fe(III) oxyhydroxides altering the •OH production pathway from the direct oxidation of thiols by O2 to the oxidation of adsorbed Fe(II) by O2. In natural soils, Fe(III) oxyhydroxides were estimated to contribute to 69–81% of thiol removal and to 56–82% of •OH production. Furthermore, the •OH produced during thiol oxygenation also exhibited the capability to degrade phenol. This study highlights the previously overlooked catalytic role of Fe(III) oxyhydroxides in facilitating thiol oxidation and •OH production.

A genetic engineering strategy to enhance outer membrane vesicle-mediated extracellular electron transfer of Geobacter sulfurreducens

Bioelectrochemical systems (BESs) are unique devices that harness the metabolic activity of electroactive microorganisms (EAMs) to convert chemical energy stored in organic substrates into electrical energy. Enhancing electron transfer efficiency between EAMs and electrodes is the key to practical implementation of BESs. Considering the role of outer membrane vesicles (OMVs) in mediating electron transfer of EAMs, a genetic engineering strategy to achieve OMVs overproduction was explored to enhance electron transfer efficiency and the underlying mechanisms were investigated. This study constructed a mutant strain of Geobacter sulfurreducens that lacked the ompA gene encoding an outer membrane protein. Experimental results showed that the mutant strain produced more OMVs and possessed higher electron transfer efficiency in Fe(III) reduction, dye degradation and current generation in BESs than the wild-type strain. More cargoes such as c-type cytochromes, functional proteins, eDNA, polysaccharides and signaling molecules that might be favorable for electron transfer and biofilm formation were found in OMVs produced by ompA-deficient anodic biofilm, which possibly contributed to the improved electron transfer efficiency of ompA-deficient biofilm. The results indicate that overproduction of OMVs in EAMs might be a potential strategy to enhance BESs performance.

Pseudocapacitance behavior enables efficient and stable electrochemical energy conversion and storage in glucose/air enzymatic biofuel cells

Constructing an integrated system with high-efficiency and stable energy conversion and storage (ECS) is of great significance but remains challenges. Herein, we report a biodevice consisting of a bioanode of tetrathiafulvalene/glucose oxidase (TTF/GOx) immobilized on asphalt-derived porous carbon (APC) for catalyzing glucose oxidation and a biocathode of 2,2’-azinobis(3-ethylbenzothiazoline-6-sulfonate)/bilirubin oxidase (ABTS/BOD) immobilized on APC for catalyzing oxygen reduction, to achieve ECS with high-efficiency and excellent stability. The redox mediators, TTF and ABTS, used at the bioanode and biocathode, respectively, simultaneously mediate electron transfer to release electric current on discharging and serve as pseudocapacitors to achieve charge storage at open-circuit conditions, enabling high power density and self-charge capability. The biodevice of the above configuration delivers a peak power output of 5.01 mW cm−2 in the pulse discharge mode with cell voltage remaining 93.7 % of its initial value after 100 pulse discharge/self-charge cycles. This work provides a highly efficient solution to address the low power density and poor stability of the conventional enzymatic biofuel cells, showing great implications for small, implantable and wearable electronics.

Overlooked Hydrogen Bond in a Blue Copper Protein Uncovered by Neutron and Sub-Ångström Resolution X-ray Crystallography.

Metalloproteins play fundamental roles in organisms and are utilized as starting points for the directed evolution of artificial enzymes. Knowing the strategies of metalloproteins, by which they exquisitely tune their activities, will not only lead to an understanding of biochemical phenomena but also contribute to various applications. The blue copper protein (BCP) has been a renowned model system to understand the biology, chemistry, and physics of metalloproteins. Pseudoazurin (Paz), a blue copper protein, mediates electron transfer in the bacterial anaerobic respiratory chain. Its redox potential is finely tuned by hydrogen (H) bond networks; however, difficulty in visualizing H atom positions in the protein hinders the detailed understanding of the protein's structure-function relationship. We here used neutron and sub-ångström resolution X-ray crystallography to directly observe H atoms in Paz. The 0.86-Å-resolution X-ray structure shows that the peptide bond between Pro80 and the His81 Cu ligand deviates from the ideal planar structure. The 1.9-Å-resolution neutron structure confirms a long-overlooked H bond formed by the amide of His81 and the S atom of another Cu ligand Cys78. Quantum mechanics/molecular mechanics calculations show that this H bond increases the redox potential of the Cu site and explains the experimental results well. Our study demonstrates the potential of neutron and sub-ångström resolution X-ray crystallography to understand the chemistry of metalloproteins at atomic and quantum levels.

Efficient hydroxyl radical production and sulfanilamide degradation during oxygenation of microbially reduced metal–organic frameworks

Incubation of iron-reducing bacteria with Fe(III) could generate •OH to decompose organic pollutants under redox fluctuation conditions. However, the Fe(III)/Fe(II) transformation efficiency and therefore yields of •OH production in systems using Fe(III)-bearing minerals as respiration substrate of bacteria is unsatisfying. Here, we showed that different iron- and iron-copper-based metal–organic frameworks (Fe-MOFs and FeCu-MOFs) can mediate electron transfer from Shewanella oneidensis MR-1 to O2 through their Fe(III)/Fe(II) cycling during anoxic–oxic transition, resulting in generation of reactive oxygen species including •O2–, H2O2 and •OH. While 3 g/L of MIL-101(Fe) demonstrated faster Fe(III)/Fe(II) cycling, better yields of •OH production (69.0 μmol/mmol Fe(II) oxidation) and sulfanilamide removal (81.5 % in 24 h) than iron-bearing minerals and the rest two Fe-MOFs (MIL-53(Fe) and MIL-88B(Fe)), Fe0.75Cu0.25-B surpassed the performance of MIL-101(Fe) and other FeCu-MOFs with different Fe/Cu ratios, which might be attributed to its larger surface area, higher amounts of associated Fe(II), and synergistic effects between Fe and Cu species. Moreover, both MIL-101(Fe) and Fe0.75Cu0.25-B maintained structure stability and persistent catalytic activity during four continuous redox cycles in 48 h, the •OH production and sulfanilamide degradation of which exceeded those of one-time operation in the same duration. This study revealed the efficacy of combining bacteria and MOFs for •OH production, and provided promising alternatives for oxidative degradation of contaminants.

Mediated electron transfer in a photo-bioreactor: continuous flow hydroxylation using cytochrome P450 BM3 in NADPH-free conditions

We designed a proof-of-concept photo-bioreactor enabling continuous flow NADPH-free activation of cytochrome P450 BM3 via mediated electron transfer.

Nano silver oxide-modified activated carbon as a novel catalyst for efficient removal of bacteria and micropollutants in aquatic environment.

Heterogeneous Fenton process is a promising water treatment technology for sterilization and degradation of organic pollutants, due to the strong oxidation of hydroxyl radicals (OH˙) generated. However, the low H2O2 activation efficiency and the instability of catalyst leading to low OH˙ production restricted development of this technology. Herein, we synthesized a novel porous activated carbon-loaded nano silver oxide (nAg2O/AC) catalyst to enhance the activation of H2O2 for removing bacteria (E. coli) and micropollutants (Tetracycline, TC) from water. In the nAg2O/AC Fenton system, reductive hydroxyl groups on AC accelerated Ag(i)/Ag cycle through mediated electron transfer, which markedly increased H2O2 activation efficiency to 73.7% (About 2.9 times that of traditional Fenton). Hence, nAg2O/AC Fenton achieved up to 6.0 log and 100% removal efficiency for E. coli and TC, respectively. The OH˙ as the major oxidizing species in nAg2O/AC Fenton system was detected and verified by radical scavenging tests and electron spin resonance (ESR) measurement. After 4 and 5 cycles of experiments, the removal of E. coli and TC still reached 5.2 log and 96%, respectively, confirming good stability of nAg2O/AC for considerable application prospects. This study concluded that nAg2O/AC is a promising H2O2 catalyst for simultaneous removal of bacteria and micropollutants in aqueous environment.

Re-assessing viologens for modern bio-electrocatalysis.

Viologens, 1,1'-disubstituted-4,4'-bipyridinium salts, are organic redox species that can be used in place of NADPH as mediators for redox enzymes. In this study, using the reduction of oxidized glutathione by glutathione reductase as a model system, a rationally designed library of viologens covering a range of polarities and functional groups were explored as electron transfer mediators for bio-electrocatalysis. Through a series of electrochemical investigations, the reduction potential was found to be the primary determining factor for electron transfer between the viologen and enzyme. Through enhancing the solubility of viologen such that the fully reduced state remained soluble, we demonstrate a much-widened window of useable viologen potentials. In doing so, we describe for the first time a highly efficient electron transfer to a flavoenzyme promoting the catalytic reaction in the absence of co-factors. As such, our study provides a platform for broadening the scope for using viologens as mediating agents for electrochemically-driven enzymatic processes.