Mechanical pre-treatment (disc refining) of wheat straw, at both atmospheric and elevated pressure, is shown to be an efficient process to access fermentable monosaccharides, with the potential to integrate within the infrastructure of existing first-generation bioethanol plants. The mild, enzymatic degradation of this sustainable lignocellulosic biomass affords 0.10-0.13 g/g (dry weight) of d-glucose quantifiable voltammetrically in real time, over a two hundred-fold range in experimental laboratory scales (25 mL to 5.0 L), with pressure disc refining of the wheat straw enabling almost twice the amount of d-glucose to be generated during the hydrolysis stage than experiments using atmospheric refining (0.06-0.09 g/g dry weight). Fermentation of the resulting hydrolysate affords 0.08-0.10 g/g (dry weight) of ethanol over similar scales, with ethanol productivity at 37 mg/(L h). These results demonstrate that minimal cellulose decomposition occurs during pressure refining of wheat straw, in contrast to hemicellulose, and suggest that the development of green, mechanochemical processes for the scalable and cost-effective manufacture of second-generation bioethanol requires improved cellulose decomposition.

Efficient electrogeneration of hydrogen peroxide (HO) is critical for treatment of refractory pollutants by the electro-Fenton process. An effective strategy is developed by combining a flow-through reactor with a poly- tetrafluoroethylene (PTFE)-modified graphite felt cathode. In this design, anodic oxygen is directly used for efficient HO generation at the modified cathode. Experimental results show that the modified cathode with the optimum PTFE content can produce 29.6 mg/L of HO, which is 16 times higher than the unmodified graphite felt cathode for a flow rate of 3 mL/min. Maximum HO production, up to 30.7 mg/L, was obtained under the following conditions: 120 mA, 3 mL/min, initial pH 13, no external aeration.

Antimicrobial surfaces are ones that incapacitate or kill pathogens landing on them, which could allow for self-sanitising surfaces for hospitals or implants, ensuring healthier stays and procedures. Cuprous compounds such as CuO are especially effective at incapacitating both viruses and bacteria, and nanorod arrays have been shown to prevent the adhesion of pathogens and mechanically deform bacteria to the point that their cell walls rupture. A CuO nanorod array should therefore allow for the exploitation of both of these effects. In the present work, an electrochemical method is introduced, where CuO nanorods formed in a substrate-supported anodic aluminium oxide (AAO) template are held at a stable electrochemical potential throughout the removal of the AAO template. This avoids the partial reduction of the nanorods from CuO to Cu that was observed during chemical removal of the template, which was attributed to the presence of residual aluminium from the template fabrication process that reacts with the etchant and lowers the electrochemical potential of the nanorods to a value that favours reduction. Using the electrochemical removal method, the reliable production of phase-pure, free-standing, crystalline CuO nanorod arrays on ITO/glass substrates is demonstrated. This simple method is compatible with nanorod arrays of any size.

Near patient detection of viral infection represents a powerful approach for the control of emerging threats to global health. Moreover, the ability to identify individuals who have contracted the disease and developed antibodies that confer immunity is central to a return to normal daily activities. This review presents some of the recent advances in electrochemical sensors for the detection of viruses and their associated antibody profiles. Given the speed, portability, sensitivity and selectivity achieved using electrochemical detection, these sensor systems hold the promise of transformative change in clinical practice.

A low maintenance, "self-cleaning" electrochemical approach is evaluated for regeneration of dye-loaded granular activated carbon (GAC). To do so, batch experiments were conducted using a low-cost granular activated carbon/stainless steel mesh (GACSS) composite cathode and a stable Ti/mixed metal oxides (Ti/MMO) anode without the addition of oxidants or iron catalysts. The GACSS cathode supports simultaneous HO electrogeneration via the supplied O from Ti/MMO anode and the subsequent HO activation for ·OH generation, thus enabling the cracking of dye molecules adsorbed on GAC and regenerating the GAC's sorption capacity. Results show that a prolonged electrochemical processing for 12h will achieve up to 88.7% regeneration efficiency (RE). While RE decreases with multi-cycle application, up to 52.3% could still be achieved after 10 adsorption-regeneration cycles. To identify the mechanism, experiments were conducted to measure HO electrogeneration, HO activation, and ·OH generation by various GAC samples. The dye-loaded GAC and GAC treated after 10 adsorption-regeneration cycles were still capable of ·OH generation, which contributes to effective "self-cleaning" and regeneration over multi-cycles.

The performance of the Electro-Fenton (EF) process for contaminant degradation depends on the rate of HO production at the cathode via 2-electron dissolved O reduction. However, the low solubility of O (≈1×10 mol dm) limits HO production. Herein, a novel and practical strategy that enables the synergistic utilization of O from the bulk electrolyte and ambient air for efficient HO production is proposed. Compared with a conventional "submerged" cathode, the HO concentration obtained using the "floating" cathode is 4.3 and 1.5 times higher using porous graphite felt (GF) and reticulated vitreous carbon (RVC) foam electrodes, respectively. This surprising enhancement results from the formation of a three-phase interface inside the porous cathode, where the O from ambient air is also utilized for HO production. The contribution of O from ambient air varies depending on the cathode material and is calculated to be 76.7% for the GF cathode and 35.6% for the RVC foam cathode. The effects of pH, current, and mixing on HO production are evaluated. Finally, the EF process enhanced by the "floating" cathode degraded 78.3% of the anti-inflammatory drug ibuprofen after 120 min compared to only 25.4% using a conventional "submerged" electrode, without any increase in the cost.

The in situ generation of hydrogen peroxide (HO) for water treatment is more practical than the use of liquid HO, which is costly to store and transport. Calcium peroxide (CaO), a solid carrier of HO, can release HO on dissolution in water. However, the constant HO release rate of CaO has been a bottleneck constraining its wider application. In this study, a practical electrochemical method using a divided cell is developed to control the rate of release of HO from CaO. The results show that the rate of HO release from CaO is enhanced in the anolyte. The increase in HO release is positively correlated with the current. Under a current of 100 mA, the HO concentration was 2.5 times higher after 30 min of electrolysis than in the control experiment in which no current was applied. Water electrolysis in the anodic compartment generates protons that not only: (i) en-hance dissolution of CaO and release of HO, but also (ii) neutralize the alkaline pH resulting from CaO dissolution, thus providing new advantages for the use of CaO. This effective technique may be suitable for the sophisticated control of HO release in environmental applications.

Pentameric ligand-gated ion channels (pLGICs) mediate fast neurotransmission in the nervous system. Their dysfunction is associated with psychiatric, neurological and neurodegenerative disorders such as schizophrenia, epilepsy and Alzheimer's disease. Understanding their biophysical and pharmacological properties, at both the functional and the structural level, thus holds many therapeutic promises. In addition to their agonist-elicited activation, most pLGICs display another key allosteric property, namely desensitization, in which they enter a shut state refractory to activation upon sustained agonist binding. While the activation mechanisms of several pLGICs have been revealed at near-atomic resolution, the structural foundation of desensitization has long remained elusive. Recent structural and functional data now suggest that the activation and desensitization gates are distinct, and are located at both sides of the ion channel. Such a 'dual gate mechanism' accounts for the marked allosteric effects of channel blockers, a feature illustrated herein by theoretical kinetics simulations. Comparison with other classes of ligand- and voltage-gated ion channels shows that this dual gate mechanism emerges as a common theme for the desensitization and inactivation properties of structurally unrelated ion channels.

Antimicrobial resistance is a leading patient safety issue. There is a need to develop novel mechanisms for monitoring and subsequently improving the precision of how we use antibiotics. A surface modified microneedle array was developed for monitoring beta-lactam antibiotic levels in human interstitial fluid. The sensor was fabricated by anodically electrodepositing iridium oxide (AEIROF) onto a platinum surface on the microneedle followed by fixation of beta-lactamase enzyme within a hydrogel. Calibration of the sensor was performed to penicillin-G in buffer solution (PBS) and artificial interstitial fluid (ISF). Further calibration of a platinum disc electrode was undertaken using amoxicillin and ceftriaxone. Open-circuit potentials were performed and data analysed using the Hill equation and log(concentration [M]) plots. The microneedle sensor demonstrated high reproducibility between penicillin-G runs in PBS with mean K (±1SD) = 0.0044 ± 0.0013 M and mean slope function of log(concentration plots) 29 ± 1.80 mV/decade (r=0.933). Response was reproducible after 28 days storage at 4°C. In artificial ISF, the sensors response was K (±1SD) = 0.0077 ± 0.0187 M and a slope function of 34 ± 1.85 mv/decade (r=0.995). Our results suggest that microneedle array based beta-lactam sensing may be a future application of this AEIROF based enzymatic sensor.

We investigate gold, TiN, and platinum in combination with a chitosan-catechol-based redox-cycling system (RCS) for electrochemical detection of the antipsychotic clozapine. We have previously demonstrated the RCS for detection of clozapine in serum, but challenges remain regarding low signal-to-noise ratios. This can be mitigated by selection of electrode materials with beneficial surface morphologies and/or compositions. We employ cyclic voltammetry to assess the redox current generated by clozapine, and differentiate solely surface-area-based effects from clozapine-specific ones using a standard redox couple. We find that nano- and microstructured platinum greatly amplifies the clozapine signal compared to gold (up to 1490-fold for platinum black). However, the material performs poorly in the presence of chloride ions, and RCS modification provides no further amplification. The RCS combined with atomic-layer-deposited (ALD) TiN, on the other hand, increases the signal by 7.54 times, versus 2.86 times for RCS on gold, with a 9.2-fold lower variability, indicating that the homogenous and chemically inert properties of ALD-TiN may make it an ideal electrode material.

We report the first study of the electrochemical reactivity of a graphenated carbon nanotube (g-CNT) film. The electron transfer kinetics of the ferri-ferrocyanide couple were examined for a g-CNT film and compared to the kinetics to standard carbon nanotubes (CNTs). The g-CNT film exhibited much higher catalytic activity, with a heterogeneous electron-transfer rate constant, k, approximately two orders of magnitude higher than for standard CNTs. Scanning electron microscopy and Raman spectroscopy were used to correlate the higher electron transfer kinetics with the higher edge-density of the g-CNT film.

New membrane-protein based electrodes were prepared incorporating cytochrome bo(3) from E. coli and gold nanoparticles. Direct electron transfer between the electrode and the immobilized enzymes was achieved, resulting in an electrocatalytic activity in presence of O(2). The size of the gold nanoparticles was shown to be important and smaller particles were shown to reduce the overpotential of the process.

Electrochemical charge storage characteristics of vertically aligned multi-walled carbon nanotubes (MWCNTs) as a function of varying diameter and spacing are reported. It was observed that the specific capacitance of the MWCNTs increased as both diameter and inter-tube spacing decreased. The MWCNT films with 229 nm inter-MWCNT spacing exhibited specific capacitance of 228 F/g versus 70 F/g for 506 nm spacing, when tested in a non-aqueous electrolyte. Further, a trend in specific capacitance versus pore size is proposed. Coupled with previously reported trends observed in the sub-10 nm pore size regime, this is expected to offer better understanding of electrochemical behavior of porous carbon materials over a wide range of pore sizes.

A promising method for the elimination of undesired capacitive currents in view of realizing a potentially calibration free coulometric ion detection system is presented. The coulometric cell is composed of a porous polypropylene tube doped with a liquid calcium-selective membrane and a silver/silver chloride wire as an inner electrode, forming a thin layer sample between wire and tubing. The total charge passed through the system during potential controlled electrolysis of the thin layer sample is indeed found to be proportional to the amount of calcium present, but non-Faradaic processes do contribute to the obtained signal. We introduce here a multi-pulse procedure that allows one to perform a second excitation pulse at the same excitation potential after exhaustive ion transfer voltammetry of calcium has taken place. The intercept of the calibration curve after background subtraction is found as 20.6 +/- 0.6 muC, significantly lower than the value of 54.1 +/- 0.8 muC for the uncorrected curve. Changes in sample temperature (from 23 degrees C to 38 degrees C) did equally not affect the background corrected coulometric readings, supporting that the procedure renders the readout principle more robust.

An electrically controlled drug release (ECDR) system based on sponge-like nanostructured conducting polymer (CP) polypyrrole (PPy) film was developed. The nanostructured PPy film was composed of template-synthesized nanoporous PPy covered with a thin protective PPy layer. The proposed controlled release system can load drug molecules in the polymer backbones and inside the nanoholes respectively. Electrical stimulation can release drugs from both the polymer backbones and the nanoholes, which significantly improves the drug load and release efficiency. Furthermore, with one drug incorporated in the polymer backbone during electrochemical polymerization, the nanoholes inside the polymer can act as containers to store a different drug, and simultaneous electrically triggered release of different drugs can be realized with this system.

Covalently linked layers of glucose oxidase, single-wall carbon nanotubes and poly-L-lysine on pyrolytic graphite resulted in a stable biofuel cell anode featuring direct electron transfer from the enzyme. Catalytic response observed upon addition of glucose was due to electrochemical oxidation of FADH(2) under aerobic conditions. The electrode potential depended on glucose concentration. This system has essential attributes of an anode in a mediator-free biocatalytic fuel cell.

This Communication demonstrates the ability of potentiometric ion-selective electrodes (ISE) to probe the growth dynamics of metal nanoparticles in real-time. The new monitoring capability is illustrated using a solid-contact silver ISE for monitoring the hydroquinone-induced precipitation of silver on gold nanoparticle seeds. Potential-time recordings obtained under different conditions are used to monitor the depletion of the silver ion during the nanoparticle formation and shed useful insights into the growth dynamics of the nanoparticles. Such potentiometric profiles correlate well with the analogous optical measurements. The new real-time electrochemical probing of the particle growth process reflects the direct, rapid and sensitive response of modern ISE to changes in the level of the precipitated metal ion from the bulk solution and holds considerable promise for probing the preparation of different nanoscale materials.

We illustrate how the use of heated electrodes enhances the performance of glucose biosensors based on amperometric detection of the glucose-oxidase generated hydrogen peroxide. Nafion is shown to be an excellent matrix to protect glucose oxidase from thermal inactivation during the heating pulses. The influence of the electrode temperature upon the amperometric response is examined. Temperature pulse amperometry (TPA) has been used to obtain convenient peak-shaped analytical signals. Surprisingly, up to 67.5 °C, the activity of Nafion-entrapped glucose oxidase is greatly enhanced (24 -fold) by accelerated kinetics rather than decreased by thermal inactivation. Amperometric signals even at elevated temperatures are stable upon prolonged operation involving repetitive measurements. The linear calibration range is significantly extended.

The separation of nanoparticles from micron size particles in high conductance buffers was achieved using an AC dielectrophoretic (DEP) microarray device with hydrogel over-coated microelectrodes. While nanoparticles could be selectively concentrated into high field regions directly over the platinum microelectrodes, micro-bubbling and electrode darkening was also observed. For similar experiments using un-coated microelectrodes, SEM analysis showed severe erosion of the platinum microelectrodes and fusion of nanoparticles due to the aggressive electrochemistry.

We report herein a simple device for rapid biosensing consisting of a single microfluidic channel made from poly(dimethylsiloxane) (PDMS) coupled to an injector, and incorporating a biocatalytic sensing electrode, reference and counter electrodes. The sensing electrode was a gold wire coated with 5 nm glutathione-decorated gold nanoparticles (AuNPs). Sensitive detection of H(2)O(2) based on direct bioelectrocatalysis by horseradish peroxidase (HRP) was used for evaluation. HRP was covalently linked the glutathione-AuNPs. This electrode presented quasi-reversible cyclic voltammetry peaks at -0.01 V vs Ag/AgCl at pH 6.5 for the HRP heme Fe(III)/Fe(II) couple. Direct electrochemical activity of HRP was used to detect H(2)O(2) at high sensitivity with a detection limit of 5 nM in an unmediated system.

Electrochemical immunosensors based on single wall nanotube (SWNT) forests and 5 nm glutathione-protected gold nanoparticles (GSH-AuNP) were developed and compared for the measurement of human cancer biomarker interleukin-6 (IL-6) in serum. Detection was based on sandwich immunoassays using multiple (14-16) horseradish peroxidase labels conjugated to a secondary antibody. Performance was optimized by effective blocking of non-specific binding (NSB) of the labels using bovine serum albumin. The GSH-AuNP immunosensor gave a detection limit (DL) of 10 pg mL(-1) IL-6 (500 amol mL(-1)) in 10 muL calf serum, which was 3-fold better than 30 pg mL(-1) found for the SWNT forest immunosensor for the same assay protocol. The GSH-AuNPs platform also gave a much larger linear dynamic range (20-4000 pg mL(-1)) than the SWNT system (40-150 pg mL(-1)), but the SWNTs had 2-fold better sensitivity in the low pg mL(-1) range.