Redox Mediator Research Articles

Redox mediator chlorophyll accelerates low-temperature biological denitrification with responses of extracellular polymers and changes in microbial community composition

Low temperatures limit the denitrification wastewater in activated sludge systems, but this can be mitigated by addition of redox mediators (RMs). Here, the effects of chlorophyll (Chl), 1,2-naphthoquinone-4-sulfonic acid (NQS), humic acid (HA), and riboflavin (RF), each tested at three concentrations, were compared for denitrification performance at low temperature, by monitoring the produced extracellular polymeric substances (EPS), and characterizing microbial communities and their metabolic potential. Chl increased the denitrification rate most, namely 4.12-fold compared to the control, followed by NQS (2.62-fold increase) and HA (1.35-fold increase), but RF had an inhibitory effect. Chl promoted the secretion of tryptophan-like and tyrosine-like proteins in the EPS and aided the conversion of protein from tightly bound EPS into loosely bound EPS, which improved the material transfer efficiency. NQS, HA, and RF also altered the EPS components. The four RMs affected the microbial community structure, whereby both conditionally abundant taxa (CAT) and conditionally rare or abundant taxa (CRAT) were key taxa. Among them, CRAT members interacted most with the other taxa. Chl promoted Flavobacterium enrichment in low-temperature activated sludge systems. In addition, Chl promoted the abundance of nitrate reduction genes narGHI and napAB and of nitrite reduction genes nirKS, norBC, and nosZ. Moreover, Chl increased abundance of genes involved in acetate metabolism and in the TCA cycle, thereby improving carbon source utilization. This study increases our understanding of the enhancement of low-temperature activated sludge by RMs, and demonstrates positive effects, in particular by Chl.

The 2.5th generation enzymatic sensors based on the construction of quasi-direct electron transfer type NAD(P)-Dependent dehydrogenases

We introduce a versatile method to convert NAD+ or NADP+ -dependent dehydrogenases into quasi-direct electron transfer (quasi-DET)-type dehydrogenases, by modifying with a mediator on the enzyme surface toward the development of 2.5th generation enzymatic sensors. In this study, we use β-hydroxybutyrate (BHB) dehydrogenase (BHBDh) from Alcaligenes faecalis (AfBHBDh) as a representative NAD+ or NADP+ -dependent dehydrogenase. BHBDhs are important in ketone monitoring, especially for the diagnosis of diabetic ketoacidosis. We modified AfBHBDh with a thiol-reactive phenazine ethosulfate (trPES). We designed, constructed, and modified mutant BHBDhs harboring cysteine residues within 20 Å from the C4 nicotinamide in NAD+/NADH. Mutants Ser65Cys, Thr96Cys, and Lys106Cys showed indistinguishable catalytic activities from the wild-type enzyme, even after trPES modification. These trPES-modified mutants were immobilized on gold disk electrodes via amine coupling with succinimide-groups of dithiobis (succinimidyl hexanoate) self-assembled monolayers for electrochemical measurements. Considering there is a wide range of BHB concentrations, we exploited the linear regression in log scales. The linear range for the sensors with trPES-modified BHBDh mutants Ser65Cys, Thr96Cys, and Lys106Cys were 0.1–4.0 mM in both buffer solution and artificial interstitial fluid (ISF). They have limits of detection of 0.047 mM for Ser65Cys, 0.15 mM for Thr96Cys, and 0.060 mM for Lys106Cys in buffer solution, and 0.12 mM, 0.089 mM, and 0.044 mM in artificial ISF, respectively. These results indicate that redox mediator modification of NAD(P)-dependent dehydrogenases converts them into quasi-DET-type dehydrogenases, thereby enabling their utilization in 2.5th generation enzymatic sensors, which will facilitate the construction of enzymatic sensors suitable for continuous monitoring systems.

A Conductive Microcavity Created by Assembly of Carbon Nanotube Buckypapers for Developing Electrochemically Wired Enzyme Cascades.

We describe the creation of a conductive microcavity based on the assembly of two pieces of carbon nanotube buckypaper for the entrapment of two enzymes, horseradish peroxidase (HRP) and glucose oxidase (GOx), as well as a redox mediator: 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid diammonium salt (ABTS). The hollow electrode, employing GOx, HRP, and the mediator, as an electrochemical enzyme cascade model, is utilized for glucose sensing at a potential of 50 mV vs. Ag/AgCl. This bienzyme electrode demonstrates the ability to oxidize glucose by GOx and subsequently convert H2O2 to water via the electrical wiring of HRP by ABTS. Different redox mediators (ABTS, potassium hexacyanoferrate (III), and hydroquinone) are tested for HRP wiring, with ABTS being the best candidate for the electroenzymatic reduction of H2O2. To demonstrate the possibility to optimize the enzyme cascade configuration, the enzyme ratio is studied with 1 mg HRP combined with variable amounts of GOx (1-4 mg) and 2 mg GOx combined with variable amounts of HRP (0.5-2 mg). The bienzyme electrode shows continuous operational stability for over a week and an excellent storage stability in phosphate buffer, with a decay of catalytic current by only 29% for 1 mM glucose after 100 days.

Production and immobilization of laccases from monoculture and co-culture of Trametes villosa and Pycnoporus sanguineus for sustainable biodegradation of ciprofloxacin

The presence of antibiotics in water systems and drinking water has detrimental effects on various organisms and poses health risks to both animals and humans. This study describes a sustainable approach using laccases to remove ciprofloxacin from water solutions. Laccases produced by monoculture of Trametes villosa and in co-culture with Pycnoporus sanguineus were immobilized using the method of cross-linked enzyme aggregates (CLEAs). The immobilization process was statistically optimized, and the biocatalysts were characterized and applied for biodegradation of ciprofloxacin at different concentrations. Laccase production was enhanced in co-culture conditions, yielding isoforms of molecular masses ranging from 55 to 45 kDa. Optimum conditions for immobilizing laccases by CLEAs were achieved with ammonium sulfate as a precipitant and glutaraldehyde as a cross-linker. Immobilization improved the thermal stability of the enzymes at 40 °C and 55 °C, and both forms of laccase CLEAs retained approximately 38% of their initial activity after five reuse cycles. Free and immobilized laccases demonstrated comparable efficiency in removing ciprofloxacin from aqueous solutions (at 2.5 mg L−1) with a 53–62% removal rate in the presence of 4-hydroxybenzoic acid as a natural redox mediator. The degradation of ciprofloxacin by laccases also reduced its antimicrobial activity against Escherichia coli.

Evaluation of Antibiotic Biodegradation by a Versatile and Highly Active Recombinant Laccase from the Thermoalkaliphilic Bacterium Bacillus sp. FNT.

Laccases are industrially relevant enzymes that have gained great biotechnological importance. To date, most are of fungal and mesophilic origin; however, enzymes from extremophiles possess an even greater potential to withstand industrial conditions. In this study, we evaluate the potential of a recombinant spore-coat laccase from the thermoalkaliphilic bacterium Bacillus sp. FNT (FNTL) to biodegrade antibiotics from the tetracycline, β-lactams, and fluoroquinolone families. This extremozyme was previously characterized as being thermostable and highly active in a wide range of temperatures (20-90 °C) and very versatile towards several structurally different substrates, including recalcitrant environmental pollutants such as PAHs and synthetic dyes. First, molecular docking analyses were employed for initial ligand affinity screening in the modeled active site of FNTL. Then, the in silico findings were experimentally tested with four highly consumed antibiotics, representatives of each family: tetracycline, oxytetracycline, amoxicillin, and ciprofloxacin. HPLC results indicate that FNTL with help of the natural redox mediator acetosyringone, can efficiently biodegrade 91, 90, and 82% of tetracycline (0.5 mg mL-1) in 24 h at 40, 30, and 20 °C, respectively, with no apparent ecotoxicity of the products on E. coli and B. subtilis. These results complement our previous studies, highlighting the potential of this extremozyme for application in wastewater bioremediation.

Green zinc/galactomannan-based hydrogels push up the photovoltage of quasi solid aqueous dye sensitized solar cells

In the present work, we implement environmentally friendly water-based Quasi-Solid Electrolytes (QSE) for Dye Sensitized Solar Cells (DSSCs), displaying an unprecedent open circuit voltage (VOC) as high as 750 mV. The production of the hydrogel for QSE-DSSCs is achieved by exploiting the concept of fully green design and fabrication, through the selection of components such as the natural polysaccharide galactomannan (GM), biocompatible zinc salts, and the employment of eco-friendly synthetic procedures to produce the hybrid gelating agents. In the process, moderate temperature (<40 °C), only aqueous solutions are employed, and, at most, ethanol is used in some phases of the procedure. Depending on the type of the initial salt, either zinc hydroxysulfate lamellae or zinc oxide nanoparticles are created within the gel matrix, with a more extended nanoporous structure in the latter case. The nanostructures and the gels are investigated by multiple techniques, including X-ray diffraction (XRD), infrared spectroscopy (IR), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Upon ensuing addition of I-/I3- redox mediator and assembling of the device, state-of-the-art aqueous QSE-DSSCs are achieved. The latter couples a 2 % efficiency (limited by charge diffusion as proved by Electrochemical Impedance Spectroscopy) with a good Average Visible Transmittance (AVT), and Light Utilization Efficiency (LUE), a couple of coveted features in wave-selective or semi-transparent devices. Finally, Linear Response-Time Dependent DFT (LR-TDDFT) simulations are carried out on a model iodine/iodide layered zinc hydroxy sulphate structure towards a better understanding of the mechanism responsible for the high AVT.

Effects of Ti3C2Tx MXene Addition to a Co Complex/Ionic Liquid-Based Electrolyte on the Photovoltaic Performance of Solar Cells.

Redox mediators comprising I-, Co3+, and Ti3C2Tx MXene were applied to dye-sensitized solar cells (DSCs). In the as-prepared DSCs (I-DSCs), wherein hole conduction occurred via the redox reaction of I-/I3- ions, the power conversion efficiency (PCE) was not altered by the addition of Ti3C2Tx MXene. The I-DSCs were exposed to light to produce Co2+/Co3+-based cells (Co-DSCs), wherein the holes were transferred via the redox reaction of Co2+/Co3+ ions. A PCE of 9.01% was achieved in a Co-DSC with Ti3C2Tx MXene (Ti3C2Tx-Co-DSC), which indicated an improvement from the PCE of a bare Co-DSC without Ti3C2Tx MXene (7.27%). It was also found that the presence of Ti3C2Tx MXene in the redox mediator increased the hole collection, dye regeneration, and electron injection efficiencies of the Ti3C2Tx-Co-DSC, leading to an improvement in both the short-circuit current and the PCE when compared with those of the bare Co-DSC without MXene.

Chemoorganotrophic electrofermentation by Cupriavidus necator using redox mediators

The non-pathogenic β-proteobacterium Cupriavidus necator has the ability to switch between chemoorganotrophic, chemolithoautotrophic and electrotrophic growth modes, making this microorganism a widely used host for cellular bioprocesses. Oxygen usually acts as the terminal electron acceptor in all growth modes. However, several challenges are associated with aeration, such as foam formation, oxygen supply costs, and the formation of an explosive gas mixture in chemolithoautotrophic cultivation with H2, CO2 and O2. Bioelectrochemical systems in which O2 is replaced by an electrode as a terminal electron acceptor offer a promising solution to these problems. The aim of this study was to establish a mediated electron transfer between the anode and the metabolism of living cells, i.e. anodic respiration, using fructose as electron and carbon source. Since C. necator is not able to transfer electrons directly to an electrode, redox mediators are required for this process. Based on previous observations on the extracellular electron transfer enabled by a polymeric mediator, we tested 11 common biological and non-biological redox mediators for their functionality and inhibitory effect for anodic electron transfer in a C. necator-based bioelectrochemical system. The use of ferricyanide at a concentration of 15 mM resulted in the highest current density of 260.75µAcm−2 and a coulombic efficiency of 64.1 %.

Redox mediator interaction with Cupriavidus necator – spectroelectrochemical online analysis

Bioelectrochemical systems with Cupriavidus necator present a viable solution for harnessing H2/CO2 mixtures as substrates, employing mediated electron transfer to an infinite electron acceptor in the form of an anode instead of O2. Fourteen redox mediators were spectroelectrochemically characterized, and their efficiency was evaluated through screening with C. necator in common cuvettes with screen printed electrodes (e-Cuvettes). Key performance indicators, including total turnover number, reduction rate, and growth, were analyzed. Ferricyanide emerged as highly effective for anodic respiration, reaching a total turnover number of 8.38 over 120 h of cultivation. On the other hand, phenazine methosulfate exhibited the highest reduction rate at 2.49 mM h−1 with a total of 5.16 turnovers. Contrary, growth impairment is reported for menadione, possibly leading to deficient anodic electron transfer. The utilization of a broad spectrum of these shuttle molecules highlights the potential for optimizing bioelectrochemical applications involving C. necator.

A sustainable redox-active electrocatalyst utilizing natural quercetin-infused MWCNT for ultra-sensitive detection of environmental Cr(VI) contaminants

Hexavalent chromium (Cr(VI)), classified as a Group 1 carcinogen, is a widely acknowledged water pollutant, posing significant public health risks. The persisting challenge involves the development of sensitive and cost-effective methods for the detection and monitoring of Cr(VI) species at the concentration level recommended by the World Health Organization (WHO), which is 50 ppb (960 nM), in water sources. In the electrochemical detection of Cr(VI), modified electrodes utilizing precious metals (Au and Ag) and toxic organic redox mediators (Thionine, methylene blue, quionone, bisphenol and phenosafranine) have been employed. In this work, as an new platform, green electrochemical approach based on parsley-plant based natural quercetin (Qn-Redox) infused MWCNT modified glassy carbon electrode, designated as GCE/MWCNT@Qn-Redox, has been introduced for highly-effective electrocatalytic reduction and sensing of Cr(VI) species in pH 2 KCl-HCl solution. The as prepared GCE/MWCNT@Qn-Redox showed highly redox active surface confined peak at Eo = 0.550 V vs Ag/AgCl with surface excess value, 10.31 × 10−9 mol cm−2. Extensive physicochemical, spectroscopic, molecular characterization, and electrochemical control experiments confirm the identity of the entrapped molecular species in the green electrode as quercetin. By using scanning-electrochemical technique, the electroactive site of the green-electrode was imaged using Fe(CN)63−/Fe(CN)64− redox couple. The green-electrode showed excellent electrocatalytic Cr(VI) reduction signal where the Qn-Redox peak appears without any fouling problem. As a practical application, a portable batch-injection analysis coupled with three-in-one screen-printed electrode modified with MWCNT@Qn-Redox, which exhibitted a detection limit of 203 nM (S/N = 3), has been demonstrated for real time monitoring of toxic Cr(VI) species in tannery industries contaminated water samples. Given the electrochemical foundation of this approach, it holds promise for various sustainable electroanalytical assays in the future.

Reversible Carbon Dioxide/Lithium Oxalate Regulation toward Advanced Aprotic Lithium Carbon Dioxide Battery.

Li-CO2 batteries have received significant attention owing to their advantages of combining greenhouse gas utilization and energy storage. However, the high kinetic barrier between gaseous CO2 and the Li2CO3 product leads to a low operating voltage (<2.5 V) and poor energy efficiency. In addition, the reversibility of Li2CO3 has always been questioned owing to the introduction of more decomposition paths caused by its higher charging plateau. Here, a novel "trinity" Li-CO2 battery system was developed by synergizing CO2, soluble redox mediator (2,2,6,6-tetramethylpiperidoxyl, as TEM RM), and reduced graphene oxide electrode to enable selective conversion of CO2 to Li2C2O4. The designed Li-CO2 battery exhibited an output plateau reaching up to 2.97 V, higher than the equilibrium potential of 2.80 V for Li2CO3, and an ultrahigh round-trip efficiency of 97.1 %. The superior performance of Li-CO2 batteries is attributed to the TEM RM-mediated preferential growth mechanism of Li2C2O4, which enhances the reaction kinetics and rechargeability. Such a unique design enables batteries to cope with sudden CO2-deficient environments, which provides an avenue for the rationally design of CO2 conversion reactions and a feasible guide for next-generation Li-CO2 batteries.

Reversible Carbon Dioxide/Lithium Oxalate Regulation toward Advanced Aprotic Lithium Carbon Dioxide Battery

AbstractLi−CO2 batteries have received significant attention owing to their advantages of combining greenhouse gas utilization and energy storage. However, the high kinetic barrier between gaseous CO2 and the Li2CO3 product leads to a low operating voltage (&lt;2.5 V) and poor energy efficiency. In addition, the reversibility of Li2CO3 has always been questioned owing to the introduction of more decomposition paths caused by its higher charging plateau. Here, a novel “trinity” Li−CO2 battery system was developed by synergizing CO2, soluble redox mediator (2,2,6,6‐tetramethylpiperidoxyl, as TEM RM), and reduced graphene oxide electrode to enable selective conversion of CO2 to Li2C2O4. The designed Li−CO2 battery exhibited an output plateau reaching up to 2.97 V, higher than the equilibrium potential of 2.80 V for Li2CO3, and an ultrahigh round‐trip efficiency of 97.1 %. The superior performance of Li−CO2 batteries is attributed to the TEM RM‐mediated preferential growth mechanism of Li2C2O4, which enhances the reaction kinetics and rechargeability. Such a unique design enables batteries to cope with sudden CO2‐deficient environments, which provides an avenue for the rationally design of CO2 conversion reactions and a feasible guide for next‐generation Li−CO2 batteries.

Engineered Metal‐Loaded Biohybrids to Promote the Attachment and Electron‐Shuttling between Enzymes and Carbon Electrodes

AbstractThe inorganic content and the catalytic performance pose metal‐loaded enzyme nanoflowers as promising candidates for developing bioelectrodes capable of functioning without the external addition of a redox mediator. However, these protein‐inorganic hybrids have yet to be successfully applied in combination with electrode materials. Herein, the synthesis procedure of these bionanomaterials is reproposed to precisely control the morphology, composition, and performance of this particular protein‐mineral hybrid, formed by glucose oxidase and cobalt phosphate. This approach aims to enhance the adherence and electron mobility between the enzyme and a carbon electrode. The strategy relies on dressing the protein in a tailored thin nanogel with multivalent chemical motifs. The functional groups of the polymer facilitate the fast protein sequence‐independent biomineralization. Furthermore, the engineered enzymes enable the fabrication of robust cobalt‐loaded enzyme inorganic hybrids with exceptional protein loads, exceeding 90% immobilization yields. Notably, these engineered biohybrids can be readily deposited onto flat electrode surfaces without requiring chemical pre‐treatment. The resulting bioelectrodes are robust and exhibit electrochemical responses even without the addition of a redox mediator, suggesting that cobalt complexes promote electron wiring between the active site of the enzyme and the electrode.

A Hybrid Redox‐Mediated Zinc‐Air Fuel Cell for Scalable and Sustained Power Generation

AbstractZinc‐air batteries (ZABs) have attracted considerable attention for their high energy density, safety, low noise, and eco‐friendliness. However, the capacity of mechanically rechargeable ZABs was limited by the cumbersome procedure for replacing the zinc anode, while electrically rechargeable ZABs suffer from issues including low depth of discharge, zinc dendrite and dead zinc formation, and sluggish oxygen evolution reaction, etc. To address these issues, we report a hybrid redox‐mediated zinc‐air fuel cell (HRM‐ZAFC) utilizing 7,8‐dihydroxyphenazine‐2‐sulfonic acid (DHPS) as the anolyte redox mediator, which shifts the zinc oxidation reaction from the electrode surface to a separate fuel tank. This approach decouples fuel feeding and electricity generation, providing greater operation flexibility and scalability for large‐scale power generation applications. The DHPS‐mediated ZAFC exhibited a superior peak power density of 0.51 W/cm2 and a continuous discharge capacity of 48.82 Ah with ZnO as the discharge product in the tank, highlighting its potential for power generation.

In situ construction of a P-doped TiO2/Ti3C2Tx heterostructure with local site optimization to improve Li-O2 battery performance

The performance of Li-O2 batteries is seriously limited by the sluggish kinetics of the mass transition in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). To explore a useful strategy to overcome these limitations, herein, we constructed a P-doped TiO2/Ti3C2Tx heterostructure (PTT) with local active site optimization, in which the highly conductive substrate anchored the P-TiO2 nanoparticles with a selective adsorption and conversion of LiOx. In contrast to the TiO2/Ti3C2Tx heterostructure with a relatively uniform active site inducing typical toroidal Li2O2, the introduction of P-doping generates a unique nanosheet array Li2O2 on the PTT surface as a discharge product. This unique structure is endowed with a shorter Li+ diffusion path and benefits mass transfer in ORR and OER, facilitating the reaction kinetics. It presents obviously enhanced battery performance with a high specific capacity of 13,482 mAh g−1 and decreased discharge–charge overpotential, as well as superior cycling stability of 190 cycles. Furthermore, this novel and efficient electrocatalyst can stably operate for more than 650 cycles at 1000 mA g−1 with the addition of a LiI redox mediator. This study provides new insight into high-performance electrocatalyst design in Li2O2 related battery system.

A Hybrid Redox-Mediated Zinc-Air Fuel Cell for Scalable and Sustained Power Generation.

Zinc-air batteries (ZABs) have attracted considerable attention for their high energy density, safety, low noise, and eco-friendliness. However, the capacity of mechanically rechargeable ZABs was limited by the cumbersome procedure for replacing the zinc anode, while electrically rechargeable ZABs suffer from issues including low depth of discharge, zinc dendrite and dead zinc formation, and sluggish oxygen evolution reaction, etc. To address these issues, we report a hybrid redox-mediated zinc-air fuel cell (HRM-ZAFC) utilizing 7,8-dihydroxyphenazine-2-sulfonic acid (DHPS) as the anolyte redox mediator, which shifts the zinc oxidation reaction from the electrode surface to a separate fuel tank. This approach decouples fuel feeding and electricity generation, providing greater operation flexibility and scalability for large-scale power generation applications. The DHPS-mediated ZAFC exhibited a superior peak power density of 0.51 W/cm2 and a continuous discharge capacity of 48.82 Ah with ZnO as the discharge product in the tank, highlighting its potential for power generation.

The combined effect of carbon starvation and exogenous riboflavin accelerated the Pseudomonas aeruginosa-induced nickel corrosion

The primary objective of this study is to elucidate the synergistic effect of an exogenous redox mediator and carbon starvation on the microbiologically influenced corrosion (MIC) of metal nickel (Ni) by nitrate reducing Pseudomonas aeruginosa. Carbon source (CS) starvation markedly accelerates Ni MIC by P. aeruginosa. Moreover, the addition of exogenous riboflavin significantly decreases the corrosion resistance of Ni. The MIC rate of Ni (based on corrosion loss volume) is ranked as: 10 % CS level + riboflavin > 100 % CS level + riboflavin > 10 % CS level > 100 % CS level. Notably, starved P. aeruginosa biofilm demonstrates greater aggressiveness in contributing to the initiation of surface pitting on Ni. Under CS deficiency (10 % CS level) in the presence of riboflavin, the deepest Ni pits reach a maximum depth of 11.2 μm, and the corrosion current density (icorr) peak at approximately 1.35 × 10−5 A·cm−2, representing a 2.6-fold increase compared to the full-strength media (5.25 × 10−6 A·cm−2). For the 10 % CS and 100 % CS media, the addition of exogenous riboflavin increases the Ni MIC rate by 3.5-fold and 2.9-fold, respectively. Riboflavin has been found to significantly accelerate corrosion, with its augmentation effect on Ni MIC increasing as the CS level decreases. Overall, riboflavin promotes electron transfer from Ni to P. aeruginosa, thus accelerating Ni MIC.

Recent Progress in Modular Electrochemical Synthesis of Hydrogen and High-Value-added Chemicals based on Solid Redox Mediator.

Electrochemical synthesis of H2 and high-value-added chemicals is an efficient and cost-effective approach that can be powered using renewable electricity. Compared to a conventional electrochemical production system, the modular electrochemical production system (MEPS) based on a solid redox mediator (SRM) can separate the anodic and cathodic reactions in time and space. The MEPS can avoid the use of membranes and formation of useless products, as well as eliminate the mutual dependence of production rates at anode and cathode. The SRM can temporarily store or release electrons and ions to pair with cathodic and anodic reactions, respectively, in MEPS. Designing of SRMs with large charge capacity and good cyclability is of great significance for constructing a high-performance MEPS. This work summarizes the design principles, recent advances in MEPS based on SRM, and application in redox flow cells. Moreover, structure design strategies as well as in situ characterization techniques and theoretical calculations for SRM is also proposed. It is expected to promote the vigorous development of MEPS based on SRM. Finally, the challenges and perspectives of MEPS based on SRM are discussed.

Catalytic Effect of Ammonium Thiosulfate as a Bifunctional Electrolyte Additive for Regulating Redox Kinetics in Lithium-Sulfur Batteries by Altering the Reaction Pathway.

Sluggish sulfur redox kinetics and incessant shuttling of lithium polysulfides (LiPSs) greatly influence the electrochemical properties of lithium-sulfur (Li-S) batteries and their practical applications. For this reason, ammonium thiosulfate (AMTS) with effective redox regulation capability has been proposed as a functional electrolyte additive to promote the bidirectional conversion of sulfur species and inhibit the shuttle effect of soluble LiPSs. During discharging, the S2O32- in AMTS can trigger the rapid reduction of LiPSs from long chains to short chains by a spontaneous chemical reaction with sulfur species, thereby decreasing the accumulation of LiPSs in the electrolyte. During charging, the NH4+ in the AMTS enhances the dissociation/dissolution of Li2S2/Li2S by hydrogen-binding interactions, which alleviates the electrode surface passivation and facilitates the reversible oxidation of short-chain sulfides back to long chains. The enhanced bidirectional redox kinetics brought about by AMTS endows Li-S cells with high reversible capacity, excellent cycle stability, and rate capability even under lean electrolyte conditions. This work not only illustrates an effective redox regulation strategy by an electrolyte additive but also investigates its catalytic reaction mechanism and Li corrosion behavior. The crucial criteria for screening additives that enable bidirectional redox mediation analogous to AMTS are summarized, and its application perspectives/challenges are further discussed.

One-step construction of multiplexed enzymatic biosensors using light-addressable electrochemistry on a single silicon photoelectrode

The multiplexed detection of metabolites in parallel within a single biosensor plate is sufficiently valuable but also challenging. Herein, we combine the inherent light addressability of silicon with the high selectivity of enzymes, for the construction of multiplexed photoelectrochemical enzymatic biosensors. To conduct a stable electrochemistry and reagentless biosensing on silicon, a new strategy involving the immobilization of both redox mediators and enzymes using an amide bond-based hydrogel membrane was proposed. The membrane characterization results demonstrated a covalent coupling of ferrocene mediator to hydrogel, in which the mediator acted as not only a signal generator but also a renewable sacrifice agent. By adding corresponding enzymes on different spots of hydrogel membrane modified silicon and recording local photocurrents with a moveable light pointer, this biosensor setup was used successfully to detect multiple metabolites, such as lactate, glucose, and sarcosine, with good analytical performances. The limits of detection of glucose, sarcosine and lactate were found to be 179 μM, 16 μM, and 780 μM with the linear ranges of 0.5–2.5 mM, 0.3–1.5 mM, and 1.0–3.0 mM, respectively. We believe this proof-of-concept study provides a simple and rapid one-step immobilization approach for the fabrication of reagentless enzymatic assays with silicon-based light-addressable electrochemistry.