Search

Biofuel cells have recently gained popularity as a green and renewable energy source. Biofuel cells are unique devices of energy and are capable of converting the stored chemical energy from waste materials such as pollutants, organics and wastewater into reliable, renewable, pollution-free energy sources through the action of biocatalysts such as various microorganisms and enzymes. It is a promising technological device to treat waste to compensate for global warming and the energy crisis through the green energy production process. Due to their unique properties, various potential biocatalysts are attracting researchers to apply them to various microbial biofuel cells for improving electricity and power. Recent research in biofuel cells is focusing on the exploitation of different biocatalysts and how they are enhancing power generation for various applications in the field of environmental technology, and biomedical fields such as implantable devices, testing kits, and biosensors. This review focusing the importance of microbial fuel cells (MFCs) and enzymatic fuel cells (ECFs) and role of different types of biocatalysts and their mechanisms for improving biofuel cell efficiency gathered from recent reports. Finally, its multifaceted applications with special emphasis on environmental technology and biomedical field will be described, along with future perspectives.

Flap endonuclease 1 (FEN1) is a structure-specific endonuclease that plays a critical role in the maintenance of genome integrity. In this work, we demonstrate a novel self-powered electrochemical FEN1 biosensor for potential applications in molecular diagnosis. Porous Fe 3 O 4 nanoparticles are first prepared, and single-strand DNA probes are absorbed on the surface of the nanoparticles. Thus, electrochemical species of [Fe(CN) 6 ] 3- can be encapsulated inside the porous nanoparticles with the molecular gate of negatively charged DNA. On the other hand, a dumbbell structured DNA probe with 5' flap is designed. FEN1 is able to cleave the flap and activate the CRISPR/Cas system for the digestion of single-stranded DNA around Fe 3 O 4 nanoparticles. As a result, the leakage of [Fe(CN) 6 ] 3- contributes to an enhanced electrochemical response, which can be used to reveal the level of FEN1. The high sensitivity of this biosensor is due to the application of porous nanomaterials and Mn 2+ accelerated CRISPR/Cas cleavage. It succeeds in detection of biological samples and screening of FEN1 inhibitors. Therefore, this proposed method has potential applications in the early diagnosis of diseases and drug discovery.

Effective wound management has the potential to reduce both the duration and cost of wound healing. However, traditional methods often rely on direct observation or complex and expensive biological testing to monitor and evaluate the invasive damage caused by wound healing, which can be time-consuming. Biosensors offer the advantage of precise and real-time monitoring, but existing devices are not suitable for integration with sensitive wound tissue due to their external dimensions. Here, we have designed a self-powered biosensing suture (SPBS) based on biofuel cells to accurately monitor glucose concentration at the wound site and promote wound healing. The anode of the SPBS consists of carbon nanotubes-modified carbon fibers, tetrathiafulvalene (TTF), and glucose oxidase (GOx), while the cathode is composed of Ag 2 O and carbon nanotubes modified nanotubes modified carbon fibers. It was observed that SPBS exhibited excellent physical and chemical stability in vitro. Regardless of different bending degrees or pH values, the maximum power density of SPBS remained above 92%, which is conducive to long-term dynamic evaluation. Furthermore, the voltage generated by SPBS reflects blood glucose concentration, and measurements at wound sites are consistent with those obtained using a commercially available blood glucose meter. SPBS achieves the healing effect of traditional medical sutures after complete healing within 14 days. It offers valuable insights for intelligent devices dedicated to real-time wound monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

A novel biofuel cell (BFC)-based self-powered electrochemical immunosensing platform was developed by integrating the target-induced biofuel release and biogate immunoassay for ultrasensitive 17β-estradiol (E2) detection. The carbon nanocages/gold nanoparticle composite was employed in the BFCs device as the electrode material, through which bilirubin oxidase and glucose oxidase were wired to form the biocathode and bioanode, respectively. Positively charged mesoporous silica nanoparticles (PMSN) were encapsulated with glucose molecules as biofuel and subsequently coated by the negatively charged AuNPs-labelled anti-E2 antibody (AuNPs-Ab) serving as a biogate. The biogate could be opened efficiently and the trapped glucose released once the target E2 was recognized and captured by AuNPs-Ab due to the decreased adhesion between the antigen-antibody complex and PMSN. Then, glucose oxidase oxidized the glucose to produce a large number of electrons, resulting in significantly increased open-circuit voltage (E OCV ). Promisingly, the proposed BFC-based self-powered immunosensor demonstrated exceptional sensitivity for the detection of E2 in the concentration range from 1.0 pg mL -1 to 10.0 ng mL -1 , with a detection limit of 0.32 pg mL -1 (S/N = 3). Furthermore, the prepared BFC-based self-powered homogeneous immunosensor showed significant potential for implementation as a viable prototype for a mobile and an on-site bioassay system in food and environmental safety applications., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

As a reliable energy-supply platform for wearable electronics, biosupercapacitors combine the characteristics of biofuel cells and supercapacitors to harvest and store the energy from human's sweat. However, the bulky preparation process and deep embedding of enzyme active sites in bioelectrodes usually limit the energy-harvesting process, retarding the practical power-supply sceneries especially during the complicated in vivo motion. Herein, a MXene/single-walled carbon nanotube/lactate oxidase hierarchical structure as the dual-functional bioanode is designed, which can not only provide a superior 3D catalytic microenvironment for enzyme accommodation to harvest energy from sweat, but also offers sufficient capacitance to store energy via the electrical double-layer capacitor. A wearable biosupercapacitor is fabricated in the "island-bridge" structure with a composite bioanode, active carbon/Pt cathode, polyacrylamide hydrogel substrate, and liquid metal conductor. The device exhibits an open-circuit voltage of 0.48 V and the high power density of 220.9 µW cm -2 at 0.5 mA cm -2 . The compact conformal adhesion with skin is successfully maintained under stretching/bending conditions. After repeatedly stretching the devices, there is no significant power attenuation in pulsed output. The unique bioelectrode structure and attractive energy harvesting/storing properties demonstrate the promising potential of this biosupercapacitor as a micro self-powered platform of wearable electronics., (© 2023 Wiley-VCH GmbH.)

Recent developments in wearable and implanted devices have resulted in numerous, unprecedented capabilities that generate increasingly detailed information about a user's health or provide targeted therapy. However, options for powering such systems remain limited to conventional batteries which are large and have toxic components and as such are not suitable for close integration with the human body. This work provides an in-depth overview of biofluid-activated electrochemical energy devices, an emerging class of energy sources judiciously designed for biomedical applications. These unconventional energy devices are composed of biocompatible materials that harness the inherent chemistries of various biofluids to produce useable electrical energy. This work covers examples of such biofluid-activated energy devices in the form of biofuel cells, batteries, and supercapacitors. Advances in materials, design engineering, and biotechnology that form the basis for high-performance, biofluid-activated energy devices are discussed. Innovations in hybrid manufacturing and heterogeneous integration of device components to maximize power output are also included. Finally, key challenges and future scopes of this nascent field are provided., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Quick and effective point-of-care (POC) devices have the chance to revolutionize healthcare in developed and developing countries since they can operate anywhere the patient is, with the possibility of obtaining and sending the results to the doctor without delay. In recent years, significant efforts have focused on developing new POC systems that can screen for biomarkers continuously and non-invasively in body fluids to prevent, diagnose, and manage diseases. However, one of the critical challenges left to address is how to power them effectively and sufficiently. In developing countries and rural and remote areas, where there are usually no well-established electricity grids or nearby medical facilities, and using batteries is unreliable or not cost-effective, alternative power sources are the most challenging issue for stand-alone and self-sustained POC devices. Here, we provide an overview of the techniques for used self-powering POC devices, where the sample is used to detect and simultaneously generate energy to power the system. Likewise, this paper introduced the state-of-the-art with a review of different research projects, patents, and commercial products for self-powered POCs from the mid-2010s until present day.

Chemical biomarkers in the central nervous system can provide valuable quantitative measures to gain insight into the etiology and pathogenesis of neurological diseases. Glutamate, one of the most important excitatory neurotransmitters in the brain, has been found to be upregulated in various neurological disorders, such as traumatic brain injury, Alzheimer's disease, stroke, epilepsy, chronic pain, and migraines. However, quantitatively monitoring glutamate release in situ has been challenging. This work presents a novel class of flexible, miniaturized probes inspired by biofuel cells for monitoring synaptically released glutamate in the nervous system. The resulting sensors, with dimensions as low as 50 by 50 μm, can detect real-time changes in glutamate within the biologically relevant concentration range. Experiments exploiting the hippocampal circuit in mice models demonstrate the capability of the sensors in monitoring glutamate release via electrical stimulation using acute brain slices. These advances could aid in basic neuroscience studies and translational engineering, as the sensors provide a diagnostic tool for neurological disorders. Additionally, adapting the biofuel cell design to other neurotransmitters can potentially enable the detailed study of the effect of neurotransmitter dysregulation on neuronal cell signaling pathways and revolutionize neuroscience., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Self-powered biofuel cells (BFCs) have evolved for highly sensitive detection of biomarkers such as noncodon micro ribonucleic acids (miRNAs) in the presence of interfering substrates. Self-charging supercapacitive BFCs for in vivo and in vitro cellular microenvironments represent the most prevalent sensing mechanism for diagnosis. Therefore, self-powered biosensing (SPB) with a capacitor and contact separation with a triboelectric nanogenerator (TENG) offers electrochemical and colorimetric dual-mode detection via improved electrical signal intensity. In this review, we discuss three major components: stretchable self-powered BFC design, miRNA sensing, and impedance spectroscopy. A specific focus is given to 1) assembling of sensors for biomarkers, 2) electrical output signal intensification, and 3) role of supercapacitors and nanogenerators in SPBs. We outline the key features of stretchable SPBs and the sequence of miRNA sensing by SPBs. We have emphasized the need of a supercapacitor and nanogenerator for SPBs in the context of advanced assembly of the sensing unit. Finally, we outline the role of impedance spectroscopy in the detection and estimation of biomarkers. We highlight key challenges in SPBs for biomarker sensing, which needs improved sensing accuracy, integration strategies of electrochemical biosensing for in vitro and in vivo microenvironments, and the impact of miRNA sensing on cancer diagnostics. This article attempts a specific focus on the accuracy and limitations of sensing unit for miRNA biomarkers and associated tool for boosting electrical signal intensity for a potential big step further.

The extraordinary potential of hydrogen as a clean and sustainable fuel has sparked the interest of the scientific community to find environmentally friendly methods for its production. Biological catalysts are the most attractive solution, as they usually operate under mild conditions and do not produce carbon-containing byproducts. Hydrogenases promote reversible proton reduction to hydrogen in a variety of anoxic bacteria and algae, displaying unparallel catalytic performances. Attempts to use these sophisticated enzymes in scalable hydrogen production have been hampered by limitations associated with their production and stability. Inspired by nature, significant efforts have been made in the development of artificial systems able to promote the hydrogen evolution reaction, via either electrochemical or light-driven catalysis. Starting from small-molecule coordination compounds, peptide- and protein-based architectures have been constructed around the catalytic center with the aim of reproducing hydrogenase function into robust, efficient, and cost-effective catalysts. In this review, we first provide an overview of the structural and functional properties of hydrogenases, along with their integration in devices for hydrogen and energy production. Then, we describe the most recent advances in the development of homogeneous hydrogen evolution catalysts envisioned to mimic hydrogenases.

Developing flexible bioelectronics is essential to the realization of artificial intelligence devices and biomedical applications, such as wearables, but their potential is limited by sustainable energy supply. An enzymatic biofuel cell (BFC) is promising for power supply, but its use is limited by the challenges of incorporating multiple enzymes and rigid platforms. This paper shows the first example of screen-printable nanocomposite inks engineered for a single-enzyme-based energy-harvesting device and a self-powered biosensor driven by glucose on bioanode and biocathode. The anode ink is modified with naphthoquinone and multiwalled carbon nanotubes (MWCNTs), whereas the cathode ink is modified with Prussian blue/MWCNT hybrid before immobilizing with glucose oxidase. The flexible bioanode and the biocathode consume glucose. This BFC yields an open circuit voltage of 0.45 V and a maximum power density of 266 μW cm -2 . The wearable device coupled with a wireless portable system can convert chemical energy into electric energy and detect glucose in artificial sweat. The self-powered sensor can detect glucose concentrations up to 10 mM. Common interfering substances, including lactate, uric acid, ascorbic acid, and creatinine, have no effect on this self-powered biosensor. Additionally, the device can endure multiple mechanical deformations. New advances in ink development and flexible platforms enable a wide range of applications, including on-body electronics, self-sustainable applications, and smart fabrics., (© 2023. The Author(s).)

Glucose oxidase (GOx)-based electrodes are important for bioelectronics, such as glucose sensors. It is challenging to effectively link GOx with nanomaterial-modified electrodes while preserving enzyme activity in a biocompatible environment. To date, no reports have used biocompatible food-based materials, such as egg white proteins, combined with GOx, redox molecules, and nanoparticles to create the biorecognition layer for biosensors and biofuel cells. This article demonstrates the interface of GOx integrated with egg white proteins on a 5 nm gold nanoparticle (AuNP) functionalized with a 1,4-naphthoquinone (NQ) and conjugated with a screen-printed flexible conductive carbon nanotube (CNT)-modified electrode. Egg white proteins containing ovalbumin can form three-dimensional scaffolds to accommodate immobilized enzymes and adjust the analytical performance. The structure of this biointerface prevents the escape of enzymes and provides a suitable microenvironment for the effective reaction. The bioelectrode's performance and kinetics were evaluated. Using redox-mediated molecules with the AuNPs and the three-dimensional matrix made of egg white proteins improves the transfer of electrons between the electrode and the redox center. By engineering the layer of egg white proteins on the GOx-NQ-AuNPs-mediated CNT-functionalized electrodes, we can modulate analytical performances such as sensitivity and linear range. The bioelectrodes demonstrate high sensitivity and can prolong the stability by more than 85% after 6 h of continuous operation. The use of food-based proteins with redox molecule-modified AuNPs and printed electrodes demonstrates advantages for biosensors and energy devices due to their small size, large surface area, and ease of modification. This concept holds a promise for creating biocompatible electrodes for biosensors and self-sustaining energy devices.

Metal-organic frameworks (MOFs) are crystalline materials that are formed by self-assembling organic linkers and metal ions with large specific areas and pore volumes. Their chemical tunability, structural diversity, and tailor-ability make them adaptive to decorate many substrate materials, such as biomass-derived carbon materials, and competitive in many environmental biosystems, such as biofuel cells, bioelectrocatalysts, microbial metal reduction, and fermentation systems. In this review, we surmised the recent progress of MOFs and MOF-derived materials and their applications in environmental biosystems. The behavior of MOFs and MOF-derived materials in different environmental biosystems and their influences on performance are described. The inherent mechanisms will guide the rational design of MOF-related materials and lead to a better understanding of their interaction with biocomponents.

Many healthcare and environmental monitoring devices use electrochemical techniques to detect and quantify analytes. With sensors progressively becoming smaller-particularly in point-of-care (POC) devices and wearable platforms-it creates the opportunity to operate them using less energy than their predecessors. In fact, they may require so little power that can be extracted from the analyzed fluids themselves, for example, blood or sweat in case of physiological sensors and sources like river water in the case of environmental monitoring. Self-powered electrochemical sensors (SPES) can generate a response by utilizing the available chemical species in the analyzed liquid sample. Though SPESs generate relatively low power, capable devices can be engineered by combining suitable reactions, miniaturized cell designs, and effective sensing approaches for deciphering analyte information. This review details various such sensing and engineering approaches adopted in different categories of SPES systems that solely use the power available in liquid sample for their operation. Specifically, the categories discussed in this review cover enzyme-based systems, battery-based systems, and ion-selective electrode-based systems. The review details the benefits and drawbacks with these approaches, as well as prospects of and challenges to accomplishing them., (© 2022 The Authors. Advanced Science published by Wiley-VCH GmbH.)

Biofuel cell (BFC) that transfers chemical energy into electricity is a promising candidate as an energy-harvesting device for implantable electronics. However, there still remain major challenges for implantable BFCs, including bulky and rigid device structure mismatching with soft tissues such as the brain, and the power output decreases due to the fouling process in a biological environment. Here, a flexible and anti-biofouling fiber BFC working in the brain chronically is developed. The fiber BFC is based on a carbon nanotube fiber electrode to possess small size and flexibility. A hydrophilic zwitterionic anti-biofouling polydopamine-2-methacryloyloxyethyl phosphorylcholine layer is designed on the surface of fiber BFC to resist the nonspecific protein adsorption in a complex biological environment. After implantation, the fiber BFC can achieve a stable device/tissue interface, along with a negligible immune response. The fiber BFC has first realized power generation in the mouse brain for over a month, exhibiting its promising prospect as an energy-harvesting device in vivo., (© 2022 Wiley-VCH GmbH.)

Redox enzymes can work as efficient electrocatalysts. The coupling of redox enzymatic reactions with electrode reactions is called enzymatic bioelectrocatalysis, which imparts high reaction specificity to electrode reactions with nonspecific characteristics. The key factors required for bioelectrocatalysis are hydride ion/electron transfer characteristics and low specificity for either substrate in redox enzymes. Several theoretical features of steady-state responses are introduced to understand bioelectrocatalysis and to extend the performance of bioelectrocatalytic systems. Applications of the coupling concept to bioelectrochemical devices are also summarized with emphasis on the achievements recorded in the research group of the author., (© The Author(s) 2021. Published by Oxford University Press on behalf of Japan Society for Bioscience, Biotechnology, and Agrochemistry.)

Electrically conductive polymers are promising materials for charge transfer from living cells to the anodes of electrochemical biosensors and biofuel cells. The modification of living cells by polypyrrole (PPy) causes shortened cell lifespan, burdens the replication process, and diminishes renewability in the long term. In this paper, the viability and morphology non-modified, inactivated, and PPy-modified yeasts were evaluated. The results displayed a reduction in cell size, an incremental increase in roughness parameters, and the formation of small structural clusters of polymers on the yeast cells with the increase in the pyrrole concentration used for modification. Yeast modified with the lowest pyrrole concentration showed minimal change; thus, a microbial fuel cell (MFC) was designed using yeast modified by a solution containing 0.05 M pyrrole and compared with the characteristics of an MFC based on non-modified yeast. The maximal generated power of the modified system was 47.12 mW/m 2 , which is 8.32 mW/m 2 higher than that of the system based on non-modified yeast. The open-circuit potentials of the non-modified and PPy-modified yeast-based cells were 335 mV and 390 mV, respectively. Even though applying a PPy layer to yeast increases the charge-transfer efficiency towards the electrode, the damage done to the cells due to modification with a higher concentration of PPy diminishes the amount of charge transferred, as the current density drops by 846 μA/cm 2 . This decrease suggests that modification by PPy may have a cytotoxic effect that greatly hinders the metabolic activity of yeast.

With the rapid decline of fossil fuels, various types of biofuel cells (BFCs) are being developed as an alternative energy source. BFCs based on multi-enzyme cascade reactions are utilized to extract more electrons from substrates. Thus, more power density is obtained from a single molucule of substrate. In the present study, a bioanode that could extract six electrons from a single molecule of L-proline via a three-enzyme cascade reaction was developed and investigated for its possible use in BFCs. These enzymes were immobilized on the electrode to ensure highly efficient electron transfer. Then, oriented immobilization of enzymes was achieved using two types of self-assembled monolayers (SAMs). In addition, a microfluidic system was incorporated to achieve efficient electron transfer. The microfluidic system, in which the electrodes were arranged in a tooth-shaped comb, allowed for substrates to be supplied continuously to the cascade, which resulted in smooth electron transfer. Finally, we developed a high-performance bioanode which resulted in the accumulation of higher current density compared to that of a gold disc electrode (205.8 μA cm -2 : approximately 187 times higher). This presents an opportunity for using the bioanode to develop high-performance BFCs in the future.

Enzymes have been incorporated into a wide variety of fields and industries as they catalyze many biochemical and chemical reactions. The immobilization of enzymes on carbon nanotubes (CNTs) for generating nano biocatalysts with high stability and reusability is gaining great attention among researchers. Functionalized CNTs act as excellent support for effective enzyme immobilization. Depending on the application, the enzymes can be tailored using the various surface functionalization techniques on the CNTs to extricate the desirable characteristics. Aiming at the preparation of efficient, stable, and recyclable nanobiocatalysts, this review provides an overview of the methods developed to immobilize the various enzymes. Various applications of carbon nanotube-based biocatalysts in water purification, bioremediation, biosensors, and biofuel cells have been comprehensively reviewed., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The continuous operation of wearable electronics demands reliable sources of energy, currently met through Li-ion batteries and various energy harvesters. These solutions are being used out of necessity despite potential safety issues and unsustainable environmental impact. Safe and sustainable energy sources can boost the use of wearables systems in diverse applications such as health monitoring, prosthetics, and sports. In this regard, sweat- and sweat-equivalent-based studies have attracted tremendous attention through the demonstration of energy-generating biofuel cells, promising power densities as high as 3.5 mW cm -2 , storage using sweat-electrolyte-based supercapacitors with energy and power densities of 1.36 Wh kg -1 and 329.70 W kg -1 , respectively, and sweat-activated batteries with an impressive energy density of 67 Ah kg -1 . A combination of these energy generating, and storage devices can lead to fully energy-autonomous wearables capable of providing sustainable power in the µW to mW range, which is sufficient to operate both sensing and communication devices. Here, a comprehensive review covering these advances, addressing future challenges and potential solutions related to fully energy-autonomous wearables is presented, with emphasis on sweat-based energy storage and energy generation elements along with sweat-based sensors as applications., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Potentiometric biosensors are incredibly versatile tools with budding uses in industry, security, environmental safety, and human health. This mini-review on recent (2018-2020) advances in the field of potentiometric biosensors is intended to give a general overview of the main types of potentiometric biosensors for novices while still providing a brief but thorough summary of the novel advances and trends for experienced practitioners. These trends include the incorporation of nanomaterials, graphene, and novel immobilization materials, as well as a strong push towards miniaturized, flexible, and self-powered devices for in-field or at-home use., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest.

Enzymes are promising electrocatalysts in many biological processes. We proposed two strategies, co-immobilization and three-dimensional (3D) space design, to strengthen electron transfer (ET). In this research, DNA base and CNT were mixed in an aqueous solution; then the mixture was dried and ground. Finally, the powder was annealed in N 2 to obtain DNA derived N-doped 3D conductive network (N-G@CNT). N-G@CNT immobilized mediators on itself through adsorption. Such 3D space structure shows high activity toward a set of critical electrochemical reactions and high-performance in enzymatic biofuel cells (EBFCs). It is found that N-G@CNT conductive network possesses an interconnected porous structure and well-developed porosity. As a result, the membrane-less EBFCs equipped with enzyme/mediator co-immobilization N-G@CNT bioelectrodes were measured in a model 5 mM glucose-containing aqueous solution, human serum, and rabbit whole blood, respectively, which can generate 0.34, 0.078, and 0.15 mW cm -2 power density, respectively. The constant-current discharge method carried out in a model 5 mM glucose-containing aqueous solution shows that the discharge time reached 19 h at a discharge current density of 0.01 mA cm -2 . The membrane EBFCs can deliver a high open circuit voltage of 0.68 V, a short-circuit current density of 2 mA cm -2 , and a maximum power density of 0.5 mW cm -2 ., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

In this research the molybdenum disulfide (MoS 2 )-based nano/microparticles and coatings were synthesized through a simple, one-step hydrothermal approach without any other additives. Composition, structure, and morphology of the synthesized MoS 2 -based materials were investigated using ultraviolet-visible spectroscopy (UV-Vis), inductively coupled plasma optical emission spectrometry (ICP-OES), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) techniques. The fabricated materials exhibited relatively small (Δθ = 18.7 ± 2.5⁰) contact angle and prominent hydrophilic properties, which are attributable to sulfur-enriched MoS 2 composite as evidenced by simultaneous thermal analysis (STA) coupled with mass spectrometric (MS) analysis of evolving gaseous species (TG/DTA-MS) analysis. Such nanostructures exhibit a better adhesion of biomolecules, thus facilitating the interaction between them, as confirmed by highly effective antimicrobial action. The present study examines antimicrobial properties of hydrophilic, sulfur-enriched MoS 2 nano/microparticles as well as MoS 2 -based coatings against various humans' pathogenic bacteria such as Salmonella enterica, Pseudomonas aeruginosa, Escherichia coli, methicillin-resistant Staphylococcus aureus (MRSA), Micrococcus luteus, and two Candida yeast strains (C. parapsilosis, C. krusei). The MoS 2 -ns (40 μg mL -1 ) showed over 90% killing efficiency against S. aureus MRSA bacteria and both Candida yeast when exposed for 24 h. Petal-like MoS 2 microstructures and heterostructured MoS 2 /Ti and Pd/MoS 2 /Ti coatings also possessed high antimicrobial potential and are considered as a promising antimicrobial agent. The MoS 2 -induced production of intracellular reactive oxygen species (ROS) was evidenced by measuring the standard DCF dye fluorescence., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Biofuel cells (BFCs)-based self-powered biosensors suffer from the limited stability of bioenzymes. Meanwhile, the poor performance of self-powered biosensors affects the sensitivity of biosensing, thus, it is significant and challenging to improve their stability and sensitivity. In our work, a BFC-based self-powered biosensor, with simultaneously enhanced stability and sensitivity, was constructed utilizing dual metal-organic frameworks (MOFs) as the carriers of the bioenzyme and the electroactive probe, respectively. Anodic enzyme, glucose dehydrogenase (GDH), was encapsulated in zeolitic imidazolate framework-8 (ZIF-8) to form GDH@ZIF-8 composites, enhancing the catalytic activity and stability of GDH. Meanwhile, another zirconium metal-organic frameworks (UiO-66-NH 2 ) loaded with electroactive molecules (K 3 [Fe(CN) 6 ]) served as nano-enrichment carriers and improved the capability of the cathode to accept electrons from the anode, further improving the sensitivity of the as-proposed biosensor. Herein, the "signal-on" BFC-based self-powered biosensing of exosomes, the model analyte, with excellent stability and outstanding sensitivity was realized with the assistance of dual MOFs, and the detection limit was down to 300 particles mL -1 (based on 3s/k), which was superior to those previously reported in literatures. Furthermore, the developed protocol was capable of detecting exosomes derived from cancer cells in complex biological samples. Overall, in this work the enhancement of both stability and sensitivity has been achieved by utilizing two types of MOFs, which laid the foundation for expanding the applications of BFC-based self-powered biosensors., (Copyright © 2020 Elsevier B.V. All rights reserved.)

We report on a photobioelectrochemical fuel cell consisting of a glucose-oxidase-modified BiFeO 3 photobiocathode and a quantum-dot-sensitized inverse opal TiO 2 photobioanode linked to FAD glucose dehydrogenase via a redox polymer. Both photobioelectrodes are driven by enzymatic glucose conversion. Whereas the photobioanode can collect electrons from sugar oxidation at rather low potential, the photobiocathode shows reduction currents at rather high potential. The electrodes can be arranged in a sandwich-like manner due to the semi-transparent nature of BiFeO 3 , which also guarantees a simultaneous excitation of the photobioanode when illuminated via the cathode side. This tandem cell can generate electricity under illumination and in the presence of glucose and provides an exceptionally high OCV of about 1 V. The developed semi-artificial system has significant implications for the integration of biocatalysts in photoactive entities for bioenergetic purposes, and it opens up a new path toward generation of electricity from sunlight and (bio)fuels., (© 2020 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The incorporation of highly active but also highly sensitive catalysts (e.g. the [FeFe] hydrogenase from Desulfovibrio desulfuricans) in biofuel cells is still one of the major challenges in sustainable energy conversion. We report the fabrication of a dual-gas diffusion electrode H 2 /O 2 biofuel cell equipped with a [FeFe] hydrogenase/redox polymer-based high-current-density H 2 -oxidation bioanode. The bioanodes show benchmark current densities of around 14 mA cm -2 and the corresponding fuel cell tests exhibit a benchmark for a hydrogenase/redox polymer-based biofuel cell with outstanding power densities of 5.4 mW cm -2 at 0.7 V cell voltage. Furthermore, the highly sensitive [FeFe] hydrogenase is protected against oxygen damage by the redox polymer and can function under 5 % O 2 ., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Variants of the highly active [NiFeSe] hydrogenase from D. vulgaris Hildenborough that exhibit enhanced O 2 tolerance were used as H 2 -oxidation catalysts in H 2 /O 2 biofuel cells. Two [NiFeSe] variants were electrically wired by means of low-potential viologen-modified redox polymers and evaluated with respect to H 2 -oxidation and stability against O 2 in the immobilized state. The two variants showed maximum current densities of (450±84) μA cm -2 for G491A and (476±172) μA cm -2 for variant G941S on glassy carbon electrodes and a higher O 2 tolerance than the wild type. In addition, the polymer protected the enzyme from O 2 damage and high-potential inactivation, establishing a triple protection for the bioanode. The use of gas-diffusion bioanodes provided current densities for H 2 -oxidation of up to 6.3 mA cm -2 . Combination of the gas-diffusion bioanode with a bilirubin oxidase-based gas-diffusion O 2 -reducing biocathode in a membrane-free biofuel cell under anode-limiting conditions showed unprecedented benchmark power densities of 4.4 mW cm -2 at 0.7 V and an open-circuit voltage of 1.14 V even at moderate catalyst loadings, outperforming the previously reported system obtained with the [NiFeSe] wild type and the [NiFe] hydrogenase from D. vulgaris Miyazaki F., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

Aliphatic synthetic intermediates with high added value are generally produced from alkane sources (e.g., petroleum) by inert carbon-hydrogen (C-H) bond activation using classical chemical methods (i.e. high temperature, rare metals). As an alternative approach for these reactions, alkane monooxygenase from Pseudomonas putida (alkB) is able to catalyze the difficult terminal oxyfunctionalization of alkanes selectively and under mild conditions. Herein, we report an electrosynthetic system using an alkB biocathode which produces alcohols, epoxides, and sulfoxides through bioelectrochemical hydroxylation, epoxidation, sulfoxidation, and demethylation. The capacity of the alkB binding pocket to protect internal functional groups is also demonstrated. By coupling our alkB biocathode with a hydrogenase bioanode and using H 2 as a clean fuel source, we have developed and characterized a series of enzymatic fuel cells capable of oxyfunctionalization while simultaneously producing electricity., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Electrochemistry belongs to an important branch of chemistry that deals with the chemical changes produced by electricity and the production of electricity by chemical changes. Therefore, it can not only act a powerful tool for materials synthesis, but also offer an effective platform for sensing and catalysis. As extraordinary zero-dimensional materials, carbon-based quantum dots (CQDs) have been attracting tremendous attention due to their excellent properties such as good chemical stability, environmental friendliness, nontoxicity and abundant resources. Compared with the traditional methods for the preparation of CQDs, electrochemical (EC) methods offer advantages of simple instrumentation, mild reaction conditions, low cost and mass production. In return, CQDs could provide cost-effective, environmentally friendly, biocompatible, stable and easily-functionalizable probes, modifiers and catalysts for EC sensing. However, no specific review has been presented to systematically summarize both aspects until now. In this review, the EC preparation methods of CQDs are critically discussed focusing on CQDs. We further emphasize the applications of CQDs in EC sensors, electrocatalysis, biofuel cells and EC flexible devices. This review will further the experimental and theoretical understanding of the challenges and future prospective in this field, open new directions on exploring new advanced CQDs in EC to meet the high demands in diverse applications., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work, nano-inspired nickel oxide nanoparticles (NiO) and polythiophene (Pth) modified bioanode was prepared for biofuel cell applications. The chemically prepared nickel oxide nanoparticles and its composite with polythiophene were characterized for elemental composition and microscopic characterization while using scanning electron microscopy. The electrochemical characterizations of polythiophene@NiO composite, biocompatible mediator ferritin (Frt) and glucose oxidase (GOx) catalyst modified glassy carbon (GC) electrode were carried out using cyclic voltammetry (CV), linear sweep voltammetry (LSV), and charge-discharge studies. The current density of Pth@NiO/Frt/GOx bioanode was found to be 5.4 mA/cm 2 . The bioanode exhibited a good bio-electrocatalytic activity towards the oxidation of the glucose. The experimental studies of the bioanode are justifying its employment in biofuel cells. This will cater a platform for the generation of sustainable energy for low temperature devices.

A maximization of a direct electron transfer (DET) between redox enzymes and electrodes can be obtained through the oriented immobilization of enzymes onto an electroactive surface. Here, a strategy for obtaining carbon nanotube (CNTs) based electrodes covalently modified with perfectly control-oriented fungal laccases is presented. Modelizations of the laccase-CNT interaction and of electron conduction pathways serve as a guide in choosing grafting positions. Homogeneous populations of alkyne-modified laccases are obtained through the reductive amination of a unique surface-accessible lysine residue selectively engineered near either one or the other of the two copper centers in enzyme variants. Immobilization of the site-specific alkynated enzymes is achieved by copper-catalyzed click reaction on azido-modified CNTs. A highly efficient reduction of O 2 at low overpotential and catalytic current densities over -3 mA cm -2 are obtained by minimizing the distance from the electrode surface to the trinuclear cluster., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The amalgamation of flexible electronics in biological systems has shaped the way health and medicine are administered. The growing field of flexible electrochemical bioelectronics enables the in situ quantification of a variety of chemical constituents present in the human body and holds great promise for personalized health monitoring owing to its unique advantages such as inherent wearability, high sensitivity, high selectivity, and low cost. It represents a promising alternative to probe biomarkers in the human body in a simpler method compared to conventional instrumental analytical techniques. Various bioanalytical technologies are employed in flexible electrochemical bioelectronics, including ion-selective potentiometry, enzymatic amperometry, potential sweep voltammetry, field-effect transistors, affinity-based biosensing, as well as biofuel cells. Recent key innovations in flexible electrochemical bioelectronics from electrochemical sensing modalities, materials, systems, fabrication, to applications are summarized and highlighted. The challenges and opportunities in this field moving forward toward future preventive and personalized medicine devices are also discussed., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Pyranose oxidase (POx) catalyzes the oxidation of d-glucose to 2-ketoglucose with concurrent reduction of oxygen to H 2 O 2 . POx from Trametes ochracea (ToPOx) is known to react with alternative electron acceptors including 1,4-benzoquinone (1,4-BQ), 2,6-dichlorophenol indophenol (DCPIP), and the ferrocenium ion. In this study, enzyme variants with improved electron acceptor turnover and reduced oxygen turnover were characterized as potential anode biocatalysts. Pre-steady-state kinetics of the oxidative half-reaction of ToPOx variants T166R, Q448H, L545C, and L547R with these alternative electron acceptors were evaluated using stopped-flow spectrophotometry. Higher kinetic constants were observed as compared to the wild-type ToPOx for some of the variants. Subsequently, the variants were immobilized on glassy carbon electrodes. Cyclic voltammetry measurements were performed to measure the electrochemical responses of these variants with glucose as substrate in the presence of 1,4-BQ, DCPIP, or ferrocene methanol as redox mediators. High catalytic efficiencies (I max app ) compared to the wild-type POx proved the potential of these variants for future bioelectrocatalytic applications, in biosensors or biofuel cells. Among the variants, L545C showed the most desirable properties as determined kinetically and electrochemically.M app ) compared to the wild-type POx proved the potential of these variants for future bioelectrocatalytic applications, in biosensors or biofuel cells. Among the variants, L545C showed the most desirable properties as determined kinetically and electrochemically., (Copyright © 2019 The Author(s). Published by Elsevier B.V. All rights reserved.)

Cellobiose dehydrogenase (CDH) is an extracellular hemoflavoenzyme secreted by fungi to assist lignocellulolytic enzymes in biomass degradation. Its catalytic flavodehydrogenase (DH) domain is a member of the glucose-methanol-choline oxidoreductase family similar to glucose oxidase. The catalytic domain is linked to an N-terminal electron transferring cytochrome (CYT) domain which interacts with lytic polysaccharide monooxygenase (LPMO) in oxidative cellulose and hemicellulose depolymerization. Based on CDH sequence analysis, four phylogenetic classes were defined. CDHs in these classes exhibit different structural and catalytic properties in regard to cellulose binding, substrate specificity, and the pH optima of their catalytic reaction or the interdomain electron transfer between the DH and CYT domain. The structure, reaction mechanism and kinetics of CDHs from Class-I and Class-II have been characterized in detail and recombinant expression allows the application in many areas, such as biosensors, biofuel cells biomass hydrolysis, biosynthetic processes, and the antimicrobial functionalization of surfaces., (© 2020 Elsevier Inc. All rights reserved.)

This review summarizes the bioelectrocatalytic properties of d-fructose dehydrogenase (FDH), while taking into consideration its enzymatic characteristics. FDH is a membrane-bound flavohemo-protein with a molecular mass of 138 kDa, and it catalyzes the oxidation of d-fructose to 5-keto-d-fructose. The characteristic feature of FDH is its strong direct-electron-transfer (DET)-type bioelectrocatalytic activity. The pathway of the DET-type reaction is discussed. An overview of the application of FDH-based bioelectrocatalysis to biosensors and biofuel cells is also presented, and the benefits and problems associated with it are extensively discussed., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Biofuel cell (BFC) electrodes are typically manufactured by combining enzymes that act as catalysts with conductive carbon nanomaterials in a form of enzyme-nanocomposite. However, a little attention has been paid to effects of the carbon nanomaterials' structural properties on the electrochemical performances of the enzyme-nanocomposites. This work aims at studying the effects of surface and bulk properties of carbon nanomaterials with different degrees of graphitization on the electrochemical performances of glucose oxidase (GOx)-nanocomposites produced by immobilizing GOx within a network of carbon nanopaticles. Two types of carbon nanomaterials were used: graphitized mesoporous carbon (GMC) and purified mesoporous carbon (PMC). Graphitization index, surface functional groups, hydrophobic properties, and rate of aggregation were measured for as-received and acid-treated GMC and PMC samples by using Raman spectrometry, X-ray photoelectron spectroscopy ( XPS), contact angle measurement, and dynamic light scattering (DLS), respectively. In addition to these physical property characterizations, the enzyme loading and electrochemical performances of the GOx-nanocomposites were studied via elemental analysis and cyclic voltammetry tests, respectively. We also fabricated BFCs using our GOx-nanocomposite materials as the enzyme anodes, and tested their performances by obtaining current-voltage (IV) plots. Our findings suggest that the electrochemical performance of GOx-nanocomposite material is determined by the combined effects of graphitization index, electrical conductivity and surface chemistry of carbon nanomaterials.

A glucose/oxygen biofuel cell (BFC) that can operate continuously under oxygen-free conditions is described. The oxygen-deficit limitations of metabolite/oxygen enzymatic BFCs have been addressed by using an oxygen-rich cathode binder material, polychlorotrifluoroethylene (PCTFE), which provides an internal oxygen supply for the BFC reduction reaction. This oxygen-rich cathode component mitigates the potential power loss in oxygen-free medium or during external oxygen fluctuations through internal supply of oxygen, while the bioanode employs glucose oxidase-mediated reactions. The internal oxygen supply leads to a prolonged energy-harvesting in oxygen-free solutions, e.g., maintaining over 90% and 70% of its initial power during 10- and 24-h operations, respectively, in the absence of oxygen. The new strategy holds considerable promise for energy-harvesting and self-powered biosensing applications in oxygen-deficient conditions., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Herein, we have developed an ultrasensitive self-powered biosensor for miRNA assay based on biofuel cells. The system is composed of indium tin oxide cathode and graphene oxide/gold nanoparticle/glucose oxidase anode. Redox probe of [Fe(CN) 6 ] 3- is entrapped inside porous Fe 3 O 4 nanoparticles by DNA. However, in the presence of target miRNA, hybridization reaction occurs between miRNA and DNA, which initiates the release of [Fe(CN) 6 ] 3- . Moreover, duplex specific nuclease is further employed to trigger target recycling amplification. As a result, much more redox probes are released and the open circuit voltage is significantly increased. A "signal-on" self-powered biosensor for miRNA quantification is thus developed. The detection range is from 10 aM to 10 fM; meanwhile, the limit of detection is as low as 1.4 aM, which is superior to that in most reported methods. Therefore, the proposed biosensor is expected to be a powerful point-of-care tool for miRNA diagnostics, which may have wide applications in the future.

In the development of biofuel cells great effort is dedicated to achieving outstanding figures of merit, such as high stability, maximum power output, and a large open circuit voltage. Biofuel cells with immobilized redox mediators, such as redox polymers with integrated enzymes, show experimentally a substantially higher open circuit voltage than the thermodynamically expected value. Although this phenomenon is widely reported in the literature, there is no comprehensive understanding of the potential shift, the high open circuit voltages have not been discussed in detail, and hence they are only accepted as an inherent property of the investigated systems. We demonstrate that this effect is the result of a Nernstian shift of the electrode potential when catalytic conversion takes place in the absence or at very low current flow. Experimental evidence confirms that the immobilization of redox centers on the electrode surface results in the assembled biofuel cell delivering a higher power output because of charge storage upon catalytic conversion. Our findings have direct implications for the design and evaluation of (bio)fuel cells with pseudocapacitive elements., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, the direct electrochemistry of bilirubin oxidase from Magnaporthe orizae (MoBOD) was studied on CNTs functionalized by electrografting several types of diazonium salts. The functionalization induces favorable or unfavorable orientation of MoBOD, the latter being compared to the well-known BOD from Myrothecium verrucaria (MvBOD). On the same nanostructured electrodes, MoBOD can surpass MvBOD in terms of both current densities and minimal overpotentials. Added to the fact that MoBOD is also highly active at the gas-diffusion electrode (GDE), these findings make MoBOD one of the MCOs with the highest catalytic activity towards the oxygen reduction reaction (ORR)., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Dehydrogenase based bioelectrocatalysis has been increasingly exploited in recent years in order to develop new bioelectrochemical devices, such as biosensors and biofuel cells, with improved performances. In some cases, dehydrogeases are able to directly exchange electrons with an appropriately designed electrode surface, without the need for an added redox mediator, allowing bioelectrocatalysis based on a direct electron transfer process. In this review we briefly describe the electron transfer mechanism of dehydrogenase enzymes and some of the characteristics required for bioelectrocatalysis reactions via a direct electron transfer mechanism. Special attention is given to cellobiose dehydrogenase and fructose dehydrogenase, which showed efficient direct electron transfer reactions. An overview of the most recent biosensors and biofuel cells based on the two dehydrogenases will be presented. The various strategies to prepare modified electrodes in order to improve the electron transfer properties of the device will be carefully investigated and all analytical parameters will be presented, discussed and compared., Competing Interests: The authors declare no conflict of interest.

In this work, high-performance non-enzymatic catalysts based on 3D hierarchical hollow porous Co 3 O 4 nanododecahedras in situ decorated on carbon nanotubes (3D Co 3 O 4 -HPND/CNTs) were successfully prepared via direct carbonizing metal-organic framework-67 in situ grown on carbon nanotubes. The morphology, microstructure, and composite of 3D Co 3 O 4 -HPND/CNTs were characterized by scanning electron microscopy, transmission electron microscopy, micropore and chemisorption analyzer, and X-ray diffraction. The electrochemical characterizations indicated that 3D Co 3 O 4 -HPND/CNTs present considerably catalytic activity toward glucose oxidation and could be promising for constructing high-performance electrochemical non-enzymatic glucose sensors and glucose/O 2 biofuel cell. When used for non-enzymatic glucose detection, the 3D Co 3 O 4 -HPND/CNTs modified glassy carbon electrode (3D Co 3 O 4 -HPND/CNTs/GCE) exhibited excellent analytical performance with high sensitivity (22.21 mA mM -1  cm -2 ), low detection limit of 0.35 μM (S/N = 3), fast response (less than 5 s) and good stability. On the other hand, when the 3D Co 3 O 4 -HPND/CNTs/GCE worked as an anode of a biofuel cell, a maximum power density of 210 μW cm -2 at 0.15 V could be obtained, and the open circuit potential was 0.68 V. The attractive 3D hierarchical porous structural features, the large surface area, and the excellent conductivity based on the continuous and effective electron transport network in 3D Co 3 O 4 -HPND/CNTs endow 3D Co 3 O 4 -HPND/CNTs with the enhanced electrochemical performance and promising applications in electrochemical sensing, biofuel cell, and other energy storage and conversion devices such as supercapacitor. Graphical abstract High-performance non-enzymatic catalysts for enzymeless glucose sensing and biofuel cell based on 3D hierarchical hollow porous Co 3 O 4 nanododecahedras anchored on carbon nanotubes were successfully prepared via direct carbonizing metal-organic framework-67 in situ grown on carbon nanotubes.

Self-powered electrochemical biosensors utilize biofuel cells as a simultaneous power source and biosensor, which simplifies the biosensor system, because it no longer requires a potentiostat, power for the potentiostat, and/or power for the signaling device. This review article is focused on detailing the advances in the field of self-powered biosensors and discussing their advantages and limitations compared to other types of electrochemical biosensors. The review will discuss self-powered biosensors formed from enzymatic biofuel cells, organelle-based biofuel cells, and microbial fuel cells. It also discusses the different mechanisms of sensing, including utilizing the analyte being the substrate/fuel for the biocatalyst, the analyte binding the biocatalyst to the electrode surface, the analyte being an inhibitor of the biocatalyst, the analyte resulting in the blocking of the bioelectrocatalytic response, the analyte reactivating the biocatalyst, Boolean logic gates, and combining affinity-based biorecognition elements with bioelectrocatalytic power generation. The final section of this review details areas of future investigation that are needed in the field, as well as problems that still need to be addressed by the field.

Environmental and sustainable economical concerns are generating a growing interest in biofuels predominantly produced from biomass. It would be ideal if an energy conversion device could directly extract energy from a sustainable energy resource such as biomass. Unfortunately, up to now, such a direct conversion device produces insufficient power to meet the demand of practical applications. To realize the future of biofuel-fed fuel cells as a green energy conversion device, efforts have been devoted to the development of carbon-based nanomaterials with tunable electronic and surface characteristics to act as efficient metal-free electrocatalysts and/or as supporting matrix for metal-based electrocatalysts. We present here a mini review on the recent advances in carbon-based catalysts for each type of biofuel-fed/biofuel cells that directly/indirectly extract energy from biomass resources, and discuss the challenges and perspectives in this developing field., Competing Interests: The authors declare no conflict of interest.

A novel paper-based biofuel cell with a series/parallel array structure has been fabricated, in which the cell voltage and output power can easily be adjusted as required by printing. The output of the fabricated 4-series/4-parallel biofuel cell reached 0.97±0.02 mW at 1.4 V, which is the highest output power reported to date for a paper-based biofuel cell. This work contributes to the development of flexible, wearable energy storage device., Competing Interests: The authors declare no conflict of interest.

In this study, the fabrication of a graphene-based bioanode utilizing ferrocenemethanol as mediator and glucose oxidase as enzyme catalyst through centrifugation was demonstrated. The enhanced in catalytic activity for glucose oxidation was achieved via centrifuge compressing respective components within the mixture. The glucose/O 2 biofuel cell (GBFC) was assembled by having the bioanode integrated with Pt wire as cathode. The GBFC produced maximum power density and open circuit voltage of approximately 70 μW cm -2 and 0.38 V., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Self-assembled redox protein nanowires have been exploited as efficient electron shuttles for an oxygen-tolerant hydrogenase. An intra/inter-protein electron transfer chain has been achieved between the iron-sulfur centers of rubredoxin and the FeS cluster of [NiFe] hydrogenases. [NiFe] Hydrogenases entrapped in the intricated matrix of metalloprotein nanowires achieve a stable, mediated bioelectrocatalytic oxidation of H 2 at low-overpotential., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Nanoporous gold (NPG) electrodes were prepared by dealloying sputtered gold:silver alloys. Electrodes of different thicknesses and pore sizes areas were prepared by varying the temperature and duration of the dealloying procedure; these were then used as supports for FAD-dependent glucose dehydrogenase (GDH) (Glomorella cingulata) and bilirubin oxidase (BOx) (Myrothecium verrucaria). Glucose dehydrogenase was immobilized by drop-casting a solution of the enzyme with an osmium redox polymer together with a crosslinked polymer, whereas bilirubin oxidase was attached covalently through carbodiimide coupling to a diazonium-modified NPG electrode. The stability of the bilirubin-oxidase-modified NPG electrode was significantly improved in comparison with that of a planar gold electrode. Enzyme fuel cells were also prepared; the optimal response was obtained with a BOx-modified NPG cathode (500 nm thickness) and a GDH-modified anode (300 nm), which generated power densities of 17.5 and 7.0 μW cm -2 in phosphate-buffered saline and artificial serum, respectively., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Graphene shows great potential in biosensing and bioelectronics. To facilitate graphene's applications and enhance its performance, recently, three-dimensional (3D) graphene-based materials especially free-standing porous graphene with tunable pore size and void space, have attracted increasing attention for bio-related applications owing to their special features. 3D graphene usually shows the following merits such as an interconnected porous network, a high electronic conductivity, a large active surface area, good chemical/thermal stability and can be more easily handled compared with dispersed graphene sheets. With modified surface properties, graphene can also be bio-friendly. These properties make 3D graphene a perfect candidate as high-performance electrode materials in bioelectronics devices. In this review, we discuss recent advance in fabricating monolithic 3D graphene and their applications in biosensing and biofuel cells., (Copyright © 2015 Elsevier B.V. All rights reserved.)