David Hickey

• PhD
• Professor (Assistant) at Michigan State University

Bacterial microcompartments (BMCs) are prokaryotic organelles that consist of a protein shell which sequesters metabolic reactions in its interior. While most of the substrates and products are relatively small and can permeate the shell, many of the encapsulated enzymes require cofactors that must be regenerated inside. We have analyzed the occurr...

Cell-free bioelectrocatalysis has drawn significant research attention as a Green approach for producing commodity and fine chemicals. Enzymatic bioelectrocatalysis utilizes electrodes to drive challenging enzymatic redox reactions, such as CO 2 reduction and selective oxidation of lignocellulosic biomass to generate value-added products. For many...

In the search for useful redox-active materials for redox flow batteries (RFBs), organic compounds offer a massive design space. Attractive anolyte candidates should be easily and inexpensively produced while exhibiting very low reduction potentials, rapid electrode kinetics, high solubility, low viscosity, and very high persistence of the reduced...

Lignins, abundant aromatic biopolymers and one of the major components of lignocellulosic biomass, remain the most underutilized renewable bioresources of aromatics and hydrocarbons on the Earth. Numerous physical and chemical processes have been developed for lignin valorization; however, they generally suffer from environmentally unfriendly, hars...

Bacterial microcompartments (BMCs) are prokaryotic organelles that consist of a protein shell which sequesters metabolic reactions in its interior. While most of the substrates and products are relatively small and can permeate the shell, many of the encapsulated enzymes require cofactors that must be regenerated inside. We have analyzed the occurr...

Point-of-care sensors, which are low-cost and user-friendly, play a crucial role in precision medicine by providing quick results for individuals. Here, we transform the conventional glucometer into a 4-hydroxytamoxifen therapeutic biosensor in which 4-hydroxytamoxifen modulates the electrical signal generated by glucose oxidation. To encode the 4-...

This chapter provides a comprehensive overview of microbial electrochemical biosensors, which are a unique class of biosensors that utilize the metabolic activity of microorganisms to convert chemical signals into electrical signals. The principles and mechanisms of these biosensors are discussed, including the different types of microorganisms tha...

Non-renewable and limited fossil resources (i.e. petroleum, coal, and natural gas) have been used over the last years for the production of energy, commodity chemicals, and polymer materials. Nonetheless, the extraction and consumption of these resources leads to deleterious and irreversible environmental impacts. As a sustainable alternative, lign...

The push to bring more renewable energy sources onto the grid has spawned a flurry of work to develop viable options for long duration energy storage. Redox flow batteries (RFBs) represent one of the most attractive possibilities, and research toward employing redox-active organic materials to improve or replace the incumbent commercially available...

Organic redox flow batteries (ORFBs) offer significant promise as a means of efficient grid-scale energy storage to compliment the intermittent power supply of renewable energy sources such as solar and wind power. ORFBs efficiently store energy in the form of redox-active organic molecules (ROMs) by passing them over two polarized electrodes to ge...

Enzyme-catalyzed redox transformations are an attractive approach for conversion of unactivated alkanes into value-added products under mild reaction conditions. This is especially true since advancements in the area of enzyme engineering has led to a dramatic expansion in the use of modified oxidoreductases for selective functionalization of commo...

Biomimetics of nicotinamide adenine dinucleotide (mNADH) are promising cost-effective alternatives to their natural counterpart for biosynthetic applications; however, attempts to recycle mNADH often rely on coenzymes or precious metal catalysts. Direct electrolysis is an attractive approach for recycling mNADH, but electrochemical reduction of the...

Successful application of emerging bioelectrocatalysis technologies depends upon an efficient electrochemical interaction between redox enzymes as biocatalysts and conductive electrode surfaces. One approach to establishing such enzyme-electrode interfaces utilizes small redox-active molecules to act as electron mediators between an enzyme-active s...

Grid-scale energy storage applications, such as redox flow batteries, rely on the solubility of redox-active organic molecules. Although redox-active pyridiniums exhibit exceptional persistence in multiple redox states at low potentials (desirable properties for energy storage applications), their solubility in non-aqueous media remains low, and fe...

Biomimetics of nicotinamide adenine dinucleotide (mNADH) are promising cost-effective alternatives to their natural counterpart for biosynthetic applications; however, attempts to recycle mNADH often rely on coenzymes or precious metal catalysts. Direct electrolysis is an attractive approach for recycling mNADH, but electrochemical reduction of the...

Precision medicine is expected to revolutionize healthcare by prioritizing accuracy and efficacy over the traditional "one-fits-all" approach. Point-of-care (POC) sensors, which are low-cost and user-friendly, play a crucial role in driving this trend by providing quick results for individuals. Modeled after the 5G network, we conceptualized an inn...

For redox active organic molecules (ROMs) used in grid-scale energy storage applications, such as redox flow batteries, solubility is an essential physicochemical property. Specifically, solubility is directly proportional to the volumetric energy density of an energy storage device and thus affects its corresponding spatial footprint. Recently pyr...

Biomimetics of nicotinamide adenine dinucleotide (mNADH) are promising cost-effective alternatives to their natural counterpart for biosynthetic applications; however, attempts to recycle mNADH often rely on coenzymes or precious metal catalysts. Direct electrolysis is an attractive approach for recycling mNADH, but electrochemical reduction of the...

Successful application of emerging bioelectrocatalysis technologies depends upon an efficient electrochemical interaction between redox enzymes as biocatalysts and conductive electrode surfaces. One approach to establishing such enzyme-electrode interfaces utilizes small redox-active molecules to act as electron mediators between an enzyme active s...

Nitrates from agricultural wastewater are harmful to human health and result in eutrophication. Several emerging electrochemical technologies have been developed independently to enable efficient recovery and recycling of nitrate waste; however, it remains unclear whether the implementation of such combined technologies can be economically viable....

Enzymatic bioelectrocatalysis involves the application of enzymes to facilitate the conversion of chemical to electrical energy. This approach has been widely applied in the fields of biosensing, biofuel cells, and to a lesser degree the synthesis of fine chemicals. While direct electrochemical communication between the enzymes and electrodes is ge...

Nitrates from agricultural wastewater are harmful to human health and result in eutrophication. Several emerging electrochemical technologies have been developed independently to enable efficient recovery and recycling of nitrate waste; however, it remains unclear whether the implementation of such combined technologies can be economically viable....

Redox flow batteries (RFBs) are a strong candidate for grid-scale energy storage applications. Recent pursuits for chemical systems involve focus on organic species, due to their chemical abundance, and non-aqueous solvent systems, due to an expanded electrochemical stability window. Currently, RFBs suffer from limitations that prevent them from be...

While the use of nonaqueous solvents in redox flow batteries (RFBs) offers the promise of higher cell voltages than can typically be obtained in aqueous electrolytes, suitable compounds that are sufficiently soluble and stable to permit extended operation has proven challenging. Viologen anolytes have been successfully employed in aqueous systems,...

The chemical engineering industry relies increasingly on enzyme-catalyzed reactions in the production of fine chemicals, value-added compounds, and commodity chemicals. However, many attractive transformations, such as the selective reduction of ketones and alkenes, depend on cofactors that are prohibitively expensive for application on an industri...

A one-pot method for converting paraffinic hydrocarbons into versatile synthetic intermediates has been a long-standing goal in chemical catalysis research. In March’s issue of the Journal of the American Chemical Society, Minteer and co-workers report an electrochemically driven enzymatic cascade capable of producing imines from unactivated alkane...

Enzymatic biofuel cells are a promising and environmentally friendly technology for energy generation from renewable fuel sources. Glucose biofuel cells employ enzymatic catalysts at both the anode and cathode to oxidize glucose and reduce oxygen while producing electricity. Consequently, there is a need for materials capable of immobilizing enzyme...

Bipyridine complexes of Ni are used as catalysts in a variety of reductive transformations. Here, the electroreduction of [Ni(Mebpy) 3 ] 2+ (Mebpy = 4,4’‐dimethyl‐2,2’‐bipyridine) in dimethylformamide is reported, with the aim of determining the redox mechanism and oxidation states of products formed under well‐controlled electrochemical conditions...

A novel laccase-based amperometric biosensor was developed through the modification of carbon paper electrodes with layered two-dimensional molybdenum disulfide (MoS2) presented in two different morphologies, flowers (MoS2-F) and ribbons (MoS2-R). Two laccase isoforms from Pycnoporus sanguineus CS43 fungi (LacI and LacII) were evaluated for the fir...

p>Bipyridine complexes of Ni are used as catalysts in a variety of reductive transformations. Here, the electroreduction of [Ni(Mebpy)₃]²⁺ (Mebpy = 4,4’-dimethyl-2,2’-bipyridine) in dimethylformamide is reported, with the aim of determining the redox mechanism and oxidation states of products formed under well-controlled elect...

In biological systems, the majority of chemistry occurs in enzymatic pathways. Pathways are essentially cascades of protein catalysts used for catabolism or metabolism. However, in cellular-free systems, catalytic cascades have been rarely studied until recently. This review will introduce the lessons that can be learned from in vivo enzymatic path...

Nitrogenase enzymes are the only biological catalysts able to convert N2 to NH3. Molybdenum-dependent nitrogenase con-sists of two proteins and three metallocofactors that sequentially shuttle eight electrons between three distinct metallocofac-tors during the turnover of one molecule of N2. While the kinetics of isolated nitrogenase has been exten...

Translating homogeneous electrocatalysts to surface-immobilized electrocatalysts, while maintaining catalytic activity, has long been a research challenge. In this issue of Joule, Le Goff and coworkers report a surface-confined dinuclear copper electrocatalyst for O2 reduction that mimics the active site of multi-copper oxidases.

Electrochemical ethanol oxidation was performed at an innovative hybrid architecture electrode containing TEMPO-modified linear poly(ethylenimine) (LPEI) and oxalate oxidase (OxOx) immobilized on carboxylated multi-walled carbon nanotubes (MWCNT-COOH). On the basis of chromatographic results, the catalytic hybrid electrode system completely oxidize...

Enzymatic bioelectrocatalysis often requires an artificial redox mediator to observe significant electron transfer rates. The use of such mediators can add a substantial overpotential and obfuscate the protein’s native kinetics, which limits the voltage of a biofuel cell and alters the analytical performance of biosensors. We have recently develope...

Enzymatic biofuel cells utilize enzymes to electrochemically catalyze the anodic oxidation of a fuel or the cathodic reduction of an oxidant due the high volumetric catalytic activity towards oxidation of biofuels, providing clean and renewable energy, besides presenting great potential as alternative power sources for low-power electronic devices....

Monitoring reactive intermediates can provide vital information in the study of synthetic reaction mechanisms, enabling the design of new catalysts and methods. Many synthetic transformations are centred on the alteration of oxidation states, but these redox processes frequently pass through intermediates with short life-times, making their study c...

Electrostatic channeling is a naturally-occurring approach to control the flux of charged intermediates in catalytic cascades. Computational techniques have enabled quantitative understanding of such mechanisms, augmenting experimental approaches by modeling molecular interactions in atomic detail. In this work, we report the first utilization of a...

The integration of different catalytic modalities to control precursors, intermediates, and products requires a method for understanding these complex systems. A modular analytical platform is presented here that allows for catalytic conversion reactions and the delivery of catalytically transformed analytes to subsequent surface enhanced Raman sca...

Predicting the thermochemistry of interfacial proton-coupled electron-transfer reactions.

With increasing demand for electronic devices and electric vehicles, there is a need for good performance of electrochemical energy storage materials while considering cost, safety, and environmental impact [1][2]. Organic electrodes based on stable organic radicals such as (2,2,6,6,-tetramethylpiperidin-1-yl)oxy (TEMPO) are a promising alternative...

C-N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driven, Ni-...

div> C–N cross-coupling is one of the most valuable and widespread transformations in organic synthesis. Largely dominated by Pd- and Cu-based catalytic systems, it has proven to be a staple transformation for those in both academia and industry. The current study presents the development and mechanistic understanding of an electrochemically driv...

Scaled-up sodium-free Birch reductions The so-called Birch reduction is frequently used by chemists despite its daunting conditions: Pyrophoric sodium is dissolved in pure liquified ammonia to achieve partial reduction of aromatics. Peters et al. surveyed and then optimized small-scale electrochemical alternatives to devise a safer protocol that ca...

Establishing an efficient extracellular electron transfer (EET) process between photo-electroactive microorganisms and an electrode surface is critical for the development of photo-bioelectrocatalysis. Soluble and immobilized redox mediators have been applied with purple bacteria Rhodobacter capsulatus for this purpose. However, detailed informatio...

Cobalt complexes have shown great promise as electrocatalysts in applications ranging from hydrogen evolution to C–H functionalization. However, the use of such complexes often requires polydentate, bulky ligands to stabilize the catalytically active Co(I) oxidation state from deleterious disproportionation reactions, to enable the desired reactivi...

In biological systems, the majority of chemistry occurs in enzymatic pathways. Pathways are essentially cascades of protein catalysts used for catabolism or metabolism. However, in cellular-free systems, catalytic cascades have been rarely studied until recently. This review will introduce the lessons that can be learned from in vivo enzymatic path...

Infrared microscopy was applied in the study of laccase biofuel cell electrodes that demonstrated high current and power densities traceable to the use of a low equivalent weight (EW), short side chain (Aquivion) ionomer in the catalyst layer. The electrodes were prepared from a biocatalyst ink composed of orientation‐directing anthracene‐modified...

Enzymes are promising catalysts for bioprocessing. For instance, the enzymatic capture of CO 2 using carbonic anhydrase (CA) is a carbon capture approach that allows obtaining bicarbonate (HCO 3 −) with no high-energy input required. However, application in a commercially viable biotechnology requires sufficient enzymatic lifetime. Although enzyme...

MWCNT-COOH, TEMPO-modified linear poly(ethylenimine), and alcohol (ADH) and aldehyde (AldDH) dehydrogenase immobilization on electrode surfaces yields a hybrid, tri-catalytic architecture that can catalyze complete ethanol electro-oxidation. The chromatographic results obtained for the tri-catalytic hybrid electrode system show that ethanol is tota...

Benefits of utilizing cascade reactions for chemical synthesis include minimizing waste and decreasing experimentation times. However, these complex systems lack an efficient screening platform for evaluating their progression. A paper‐based microfluidic platform was developed to monitor cascade systems without the need for off‐line product verific...

Natural enzyme cascades are able to employ electrostatic channeling as an efficient mechanism for shuttling charged intermediates between sequential active sites. Application of channeling mechanisms to artificial cascades has drawn increasing attention for its potential to improve cascade design. We report a quantitative model of a two-step artifi...

Enzymatic bioelectrocatalysis often requires an artificial redox mediator to observe significant electron transfer rates. The use of such mediators can add a substantial overpotential and obfuscate the protein’s native kinetics, which limits the voltage of a biofuel cell and alters the analytical peformance of biosensors. Herein, we describe a mate...

Increasing greenhouse gas emissions has resulted in greater motivation to find novel carbon dioxide (CO2) reduction technologies, where the reduction of CO2 to valuable chemical commodities is desirable. Molybdenum‐dependent formate dehydrogenase (Mo‐FDH) from Escherichia coli is a metalloenzyme that is able to interconvert formate and CO2. We desc...

Increasing greenhouse gas emissions has resulted in greater motivation to find novel carbon dioxide (CO2) reduction technologies, where the reduction of CO2 to valuable chemical commodities is desirable. Molybdenum‐dependent formate dehydrogenase (Mo‐FDH) from Escherichia coli is a metalloenzyme that is able to interconvert formate and CO2. We desc...

Fundamental understanding of the ways organic and/or inorganic catalysts can be incorporated with enzymes to enhance the efficiency of multi-step reactions can lead to knowledge that is crucial for any further improvements in the development of multi-component multi-step catalytic cascades. This knowledge can provide essential clues to the novel de...

Recently there has been an increased interest in the development of small molecule electrooxidation catalysts such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), for multistep electrochemical alcohol oxidation. Several TEMPO derivatives have long been used to electrochemically oxidize short chain alcohols and various sugars to the correspondin...

Enzyme-based catalytic systems are common bioelectrocatalysts employed in biofuel cells, as a consequence of the inherently high volumetric catalytic activity towards oxidation of biofuels. Integration of these bioelectrocatalysts with organic oxidation catalysts extends their utility by enabling significant amplification of the electrocatalytic ac...

The on-line, self-powered monitoring of the organic carbon content in hypersaline solutions (e.g. chemical oxygen demand, COD) based on a microbial biosensor would avoid the generation of toxic waste, originated by common COD analytical methods, and reduce the release of pollutants into the environment. Herein, a disposable cathode was applied to m...

This work combines the thermostable alcohol dehydrogenase D (AdhD) from Pyrococcus furiosus and the organic electrocatalyst TEMPO to create a bifunctional catalyst that selectively oxidizes primary and secondary alcohols. The active sites function independently, can be switched on by changing reaction conditions, and can selectively oxidize a mixtu...

Enzymatic glucose biosensors and biofuel cells make use of the electrochemical transduction between an oxidoreductase enzyme, such as glucose oxidase (GOx), and an electrode to either quantify the amount of glucose in a solution or generate electrical energy. However, many enzymes including GOx are not able to electrochemically interact with an ele...

The development of a hybrid, tri-catalytic architecture is demonstrated by immobilizing MWCNTs, TEMPO-modified linear poly(ethylenimine) and oxalate decarboxylase on an electrode to enable enhanced electrochemical oxidation of glycerol. This immobilized,...

Kinetic and mechanistic studies of the desymmetrization of benzhydrylamine using Pd/monoprotected amino acid ligands (Pd/MPAA) via C-H functionalization with molecular iodine provide mechanistic insight into the rate-determining step and the oxidation state of Pd in the C-H functionalization step. Intriguingly, C-H bond breaking does not occur prio...

Natural enzyme cascades utilize electrostatic guidance as an effective technique to control the diffusion of charged reaction intermediates between catalytic active sites in a process known as substrate channeling. However, limited understanding of channeling mechanisms has abated the application of this technique in artificial catalytic cascades....

The deployment of nonaqueous redox flow batteries for grid-scale energy storage has been impeded by a lack of electrolytes that undergo redox events at as low (anolyte) or high (catholyte) potentials as possible while exhibiting the stability and cycling lifetimes necessary for a battery device. Herein, we report a new approach to electrolyte desig...

Enzymatic biobatteries can be implanted in living organisms to exploit the chemical energy stored in physiological fluids. Generally, commonly-used electron donors (such as sugars) are ubiquitous in physiological environments, while electron acceptors such as oxygen are limited due to many factors including solubility, temperature, and pressure. Th...

Enzymatic fuel cells (EFCs) utilize enzymatic catalysts to convert chemical energy to electrical energy, typically by performing a 2e − oxidation of saccharides. In the case of sugars, a single 2e − oxidation does not fully exploit this energy-dense fuel that is capable of producing 24e − from its complete oxidation to CO 2. Here, we propose an eff...

Enzymatic fuel cells (EFCs) utilize enzymatic catalysts to convert chemical energy to electrical energy, typically by performing a 2e⁻ oxidation of saccharides. In the case of sugars, a single 2e⁻ oxidation does not fully exploit this energy-dense fuel that is capable of producing 24e⁻ from its complete oxidation to CO2. Here, we propose an efficie...

Cholesterol is an essential structural component of mammalian cells, although elevated concentrations of cholesterol in the human body are linked to atherosclerotic disease. In this context, monitoring physiological cholesterol concentrations is of great interest in medical fields and the concept of producing electrical energy from cholesterol is i...

Direct growth of hierarchical micro/nanostructured metal arrays on a 3D substrate is a powerful tool to enhance the catalytic efficiency of metal particles towards a wide range of substrates. In this contribution, we demonstrate a novel and versatile method for growing anisotropic microstructures directly onto a 3D carbon paper electrode, using Au,...

Here, we demonstrate the use of phospholipid micelles to enhance O2 concentrations by two-fold at the surface of a bilirubin oxidase biocathode. Specifically, 1,2-diarachidoyl-sn-glycero-3- phosphocholine was used in a glucose enzymatic fuel cell to limit power losses due to O2 transport, even in a quiescent solution.

Small implantable electronic devices require biologically compatible energy sources that are capable of delivering quick high-energy pulses. Combining batteries and supercapacitors allows for high power and energy density while providing both small size and biocompatibility. Here, we report a hybrid supercapacitor/biobattery whereby an oxygen-reduc...

Small implantable electronic devices require biologically compatible energy sources that are capable of delivering quick high-energy pulses. Combining batteries and supercapacitors allows for high power and energy density while providing both small size and biocompatibility. Here, we report a hybrid supercapacitor/biobattery whereby an oxygen-reduc...

Among the various alternative technologies for efficient energy conversion, the use of enzymes immobilized onto the surface of electrodes as the main catalyst in biological fuel cells has been extensively reported. The biofuel cell provide a means to obtain clean, renewable energy and have great potential for maybe in the future be used as alternat...

The mechanistic foundation behind the identity of a phosphine ligand that best promotes a desired reaction outcome is often non-intuitive, and thus has been addressed in numerous experimental and theoretical studies. In this work, multivariate correlations of reaction outcomes using 38 different phosphine ligands were combined with classic potentio...

The bioelectrooxidation of ethanol was investigated in a fully enzymatic membraneless ethanol/O2 biofuel cell assembly using hybrid bioanodes containing multi-walled carbon nanotube (MWCNT)-decorated gold metallic nanoparticles with either a pyrroloquinoline quinone (PQQ)-dependent alcohol dehydrogenase (ADH) enzyme or a nicotinamide adenine dinucl...

Biofuel cells are often limited by the current density produced by the cathode; this is especially true when such fuel cells are scaled down to fit a desired application. Herein, we created a computational model to examine the effects of carbon nanotube (CNT) connectivity and surface activity on the current density of a biofuel cell cathode. The mo...

Laccase is a multi-copper center enzyme that is able to oxidize phenolic substrates and undergo a four electron reduction of O 2 to H 2 O. The interaction of laccase with different environmental toxins has been reported, whereby laccase can either oxidize pollutants (polyphenols, polyamines and paradiphenols) as fuels or be inhibited by the toxin (...

Recently there has been an increased interest in the development of small molecule electrooxidation catalysts such as (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), for use in the anodic compartment of a biofuel cell. Some TEMPO derivatives are capable of electrochemically oxidizing short chain alcohols and various sugars to the corresponding ald...

Enzymatic fuel cells (EFCs) are capable of utilizing a wide range of sugars and short-chain alcohols as fuel sources. Using an enzymatic catalyst at either the anode or cathode, EFCs are able to operate under physiological pH and temperature. Recent advancements in bioanodic materials have allowed for generation of current densities in excess of 2...

Introduction Among the various alternative technologies for efficient energy conversion, the use of enzymes immobilized onto the surface of electrodes as the main catalyst in biological fuel cells has been extensively reported [1]. The biofuel cell provide a means to obtain clean, renewable energy and have great potential for maybe in the future be...

As perhaps the most commonly utilized fuel for enzymatic fuel cells (EFCs), glucose oxidation is largely under-exploited. Theoretically, the oxidation of glucose and its downstream metabolites is able to deliver a maximum of 24e ⁻ to a bioanode, however the vast majority of EFCs reported to date only perform a single 2e ⁻ oxidation of glucose. Comm...

Lactate is an important biomarker due to its excessive production by the body during anerobic metabolism. Existing methods for electrochemical lactate detection require the use of an external power source. This work present a light air-breathing bio-microfluidic fuel cell (BµFC) operated with 20 mM lactate in phosphate buffer pH 6.5 as fuel and the...

Laccase is a multi-copper center enzyme that is able to oxidize phenolic substrates and undergo a four electron reduction of O 2 to H 2 O. The interaction of laccase with different environmental toxins has been reported, whereby laccase can either oxidize pollutants (polyphenols, polyamines and paradiphenols) as fuels or be inhibited by the toxin (...

The reversible inhibition of laccase by arsenite (As3+) and arsenate (As5+) is reported for the first time. Oxygen-reducing lac-case bioelectrodes were found to be inhibited by both arsenic species for direct electron transfer bioelectrodes (using anthra-cene functionalities for enzymatic orientation) and for mediated electron transfer bioelectrode...

A number of bioelectronic applications work with oxidase enzymes and many of them can operate with small molecule or polymer redox mediators. However, for some oxidases, there are no known redox mediators able to mediate electron transfer. Therefore, electron transfer must occur through peroxide production and oxidation at the electrode surface. Or...

This book chapter will detail the fundamentals of direct and mediated bioelectrocatalysis, as well as the applications of bioelectrocatalysis. Applications discussed include environmental, biomedical, and food and drink biosensors, self-powered sensors, biofuel cells, biosolar cells, and bioelectrosynthesis of value added products.

Stable nitroxyl radical-containing compounds, such as 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) and its derivatives, are capable of electrocatalytically oxidizing a wide range of alcohols under mild and environmentally friendly conditions. Herein, we examine the structure-function relationships that determine the catalytic activity of a diverse...

Enzymatic biofuel cells (EFCs) are devices that are capable of producing electrical energy from the enzymatic oxidation of simple, energy-dense fuels (such as sugars and alcohols). Glucose oxidase (GOx) is perhaps the most widely used enzyme at the bioanode of EFCs, affording devices that can be fueled by glucose. Due to its high substrate specific...