Scanning Gel Electrochemical Microscopy (SGECM): Lateral Physical Resolution by Current and Shear Force Feedback.

Scanning gel electrochemical microscopy (SGECM) is a novel technique measuring local electrochemistry based on a gel probe. The gel probe, which is fabricated by electrodeposition of hydrogel on a microdisk electrode, immobilizes the electrolyte, and constitutes a two-electrode system upon contact with the sample. The contact area determines the lateral physical resolution of the measurement, and considering the soft nature of the gel it is essential to be well analyzed. In this work, the lateral physical resolution of SGECM is quantitatively studied from two aspects: (1) marking single sampling points by locally oxidizing Ag to AgCl and measuring their size; (2) line scan over reference samples with periodic topography and composition. The gel probe is approached to the sample by either current or shear force feedback, and the physical resolution of them is compared. For the optimal gel probe based on 25 µm diameter Pt disk electrode of Rg ≈ 2, the lateral physical resolution of SGECM at contact position is ca. 50 µm for current feedback and ca. 63 µm for shear force feedback. More importantly, the lateral physical resolution of SGECM can be flexibly tuned in the range of 14-78 µm by pulling or pressing the gel probe after touching the sample. In general, current feedback is more sensitive to gel-sample contact than shear force feedback. But the latter is more versatile, which is also applicable to nonconductive samples.

Electrochemical Filter To Remove Oxygen Interference Locally, Rapidly, and Temporarily for Sensing Applications.

An electrochemical oxygen filter is described that removes efficiently dissolved oxygen from the surface of an electrochemical sensor. Simulations show that 99% of oxygen can be removed in less than 60 s if an electrochemical filter made of a porous electrode is positioned at less than 200 µm from the sensor surface. For an experimental demonstration, the metallic filter was made with either a stainless steel or a platinum grid separated from the sensor by a porous separator. It was combined with a sensor for analysis of paraquat, an herbicide widely used over the world. In aerated solutions, paraquat signal was not distinguished due to the strong interference of oxygen. When using the oxygen filter, paraquat was clearly detected with a better-defined response than the one obtained under a N2 atmosphere that requires a longer time period before analysis.

Real-Time Ozone Sensor Based on Selective Oxidation of Methylene Blue in Mesoporous Silica Films.

Sensitive and selective personal exposure monitors are needed to assess ozone (O3) concentrations in the workplace atmosphere in real time for the analysis and prevention of health risks. Here, a cumulative gas sensor using visible spectroscopy for real-time O3 determination is described. The sensing chip is a mesoporous silica thin film deposited on transparent glass and impregnated with methylene blue (MB). The sensor is reproducible, stable for at least 50 days, sensitive to 10 ppb O3 (one-tenth of the occupational exposure limit value in France, Swiss, Canada, U.K., Japan, and the USA) with a measurement range tested up to 500 ppb, and insensitive to NO2 and to large variation in relative humidity. A model and its derivative as a function of time are proposed to convert in real time the sensor response to concentrations, and an excellent correlation was obtained between those data and reference O3 concentrations. This sensor is based on a relatively cheap sensing material and a robust detection system, and its analytical performance makes it suitable for monitoring real-time O3 concentrations in workplaces to promote a safer environment for workers.

Scanning Gel Electrochemical Microscopy for Topography and Electrochemical Imaging.

Scanning electrochemical probe techniques have been widely applied for analyzing the local electrochemical activity of surfaces and interfaces. In this work, we develop a new concept of carrying out local electrochemical measurements by localizing both the electrode and the electrolyte. This is achieved through a gel probe, which is prepared by electrodepositing chitosan-gelatin gel on a microdisk electrode. It is positioned in contact with the sample surface by shear force feedback. The preliminary results indicate that the topography of the sample can be mapped by tapping the probe and recording the coordinates at a given normalized shear force signal, while the local electrochemical activity can be retrieved from local measurements with the probe touching the sample surface. The technique is denoted as scanning gel electrochemical microscopy. As compared with existing techniques, it has a major advantage of operating in air with the electrolyte immobilized in gel. This would prevent the spreading and leakage of solution on the sample surface and may lead to field applications.

Combined Raman microspectrometer and shearforce regulated SECM for corrosion and self-healing analysis.

Shearforce regulated scanning electrochemical microscopy (SECM) has been associated with Raman microspectrometry in order to perform combined electrochemical and spectrochemical analysis on reactive interfaces. The interest of the method was evaluated by analyzing local corrosion phenomena in damaged Zn(Mg, Al) self-healing coatings deposited on steel. Despite the high aspect ratio of the analyzed sample displaying here more than a 50 µm depth profile, the optimized setup allowed (1) precise electrode positioning with the help of shearforce detection, (2) electrochemical measurement at a constant distance from the sample surface, and (3) local chemical analysis of the solid surface by confocal Raman microspectroscopy performed at a constant focal distance from the sample. All in all, this new setup allows one to approach the detailed reactivity involved in defective metal samples.

An L-glucitol oxidizing dehydrogenase from Bradyrhizobium japonicum USDA 110 for production of D-sorbose with enzymatic or electrochemical cofactor regeneration.

A gene in Bradyrhizobium japonicum USDA 110, annotated as a ribitol dehydrogenase (RDH), had 87 % sequence identity (97 % positives) to the N-terminal 31 amino acids of an L-glucitol dehydrogenase from Stenotrophomonas maltophilia DSMZ 14322. The 729-bp long RDH gene coded for a protein consisting of 242 amino acids with a molecular mass of 26.1 kDa. The heterologously expressed protein not only exhibited the main enantio selective activity with D-glucitol oxidation to D-fructose but also converted L-glucitol to D-sorbose with enzymatic cofactor regeneration and a yield of 90 %. The temperature stability and the apparent K m value for L-glucitol oxidation let the enzyme appear as a promising subject for further improvement by enzyme evolution. We propose to rename the enzyme from the annotated RDH gene (locus tag bll6662) from B. japonicum USDA as a D-sorbitol dehydrogenase (EC 1.1.1.14).

Evaluation of short-circuited electrodes in combination with dark fermentation for promoting biohydrogen production process.

Short-circuited electrodes, in combination with dark fermentation, were evaluated in a biohydrogen production process. The system is based on an innovative design of a non-compartmented electromicrobial bioreactor with a conductive tubular membrane as cathode and a graphite felt as anode. In particular, the electrode specialization occurred when the bioreactor was inoculated with manure as the whole medium and when a vacuum was applied in the tubular membrane, for allowing continuous extraction of gaseous species (H2, CH4, CO2) from the bioreactor. This specialization of the electrodes as anode and cathode was further confirmed by microbial ecology analysis of biofilms and by cyclic voltammetry measurements. In these experimental conditions, the potential of the electrochemical system (short-circuited electrodes) reached values as low as -320 mV vs. SHE, associated with a significant bioH2 production. Moreover, a higher bioH2 production occurred and a potential of the electrochemical system as low as -429 mV vs SHE was temporarily observed, when additional heat treatments of the whole manure were applied in order to remove methanogen microorganisms (i.e., hydrogen consumers). In the bioreactor, the higher production of bioH2 would be promoted by electrofermentation from the current flow observed between short-circuited anode and cathode.

Functionalized MXene Films with Substantially Improved Low-Voltage Actuation.

Ti3 C2 Tx MXene film is promising for low-voltage electrochemical actuators (ECAs) due to its excellent electrical conductivity, volumetric capacitance, and mechanical properties. However, its in-plane actuation is limited to little intralayer strain of MXene sheets under polarization. Here it is demonstrated that a simple tetrabutylammonium (TBA) functionalization of MXene improves the in-plane actuation strain by 337% and also enhances the mechanical property and stability in air and the electrolyte. Various in situ characterizations reveal that the improved actuation is ascribed to the co-insertion/desertion of TBA and Li ions into/from MXene interlayer galleries and inter-edge gaps that causes a large in-plane sliding of MXene sheets under negative/positive polarizations. The assembled bending actuator has a high strength and modulus and generates a peak-to-peak strain difference of 0.771% and a blocking force up to 51.5 times its own weight under 1 V. The designed soft robotic tweezer can grasp an object under 1 V and hold it firmly under 0 V. The novel sheet sliding mechanism resembling the filament sliding theory in skeletal muscles may inspire the design of high-performance actuators with other nanomaterials.

Electrochemical approaches for the fabrication and/or characterization of pure and hybrid templated mesoporous oxide thin films: a review.

Electrochemistry can be used for fabrication and characterization of mesoporous oxide films. First, this review provides insight into the methods used to prepare templated mesoporous thin films on an electrode surface, i.e., evaporation-induced self-assembly (EISA) and electrochemically assisted self-assembly (EASA). Electrochemical characterization of mass transport processes in pure and organically functionalized mesoporous oxide films is then discussed. The electrochemical response can be basically restricted by the electron/mass transfer reaction at the electrode-film interface and diffusion through mesopore channels. The contributions of cyclic voltammetry, hydrodynamic voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy to the characterization of films with distinct mesostructures are finally described, with special emphasis on identification of conditions that can affect the electrochemical response recorded with such modified electrodes.

Reagentless D-sorbitol biosensor based on D-sorbitol dehydrogenase immobilized in a sol-gel carbon nanotubes-poly(methylene green) composite.

A reagentless D-sorbitol biosensor based on NAD-dependent D-sorbitol dehydrogenase (DSDH) immobilized in a sol-gel carbon nanotubes-poly(methylene green) composite has been developed. It was prepared by durably immobilizing the NAD(+) cofactor with DSDH in a sol-gel thin film on the surface of carbon nanotubes functionalized with poly(methylene green). This device enables selective determination of D-sorbitol at 0.2 V with a sensitivity of 8.7 µA mmol(-1) L cm(-2) and a detection limit of 0.11 mmol L(-1). Moreover, this biosensor has excellent operational stability upon continuous use in hydrodynamic conditions.

Challenges and applications of nitrate-reducing microbial biocathodes.

Bioelectrochemical systems which employ microbes as electrode catalysts to convert chemical energy into electrical energy (or conversely), have emerged in recent years for water sanitation and energy recovery. Microbial biocathodes, and especially those reducing nitrate are gaining more and more attention. The nitrate-reducing biocathodes can efficiently treat nitrate-polluted wastewater. However, they require specific conditions and they have not yet been applied on a large scale. In this review, the current knowledge on nitrate-reducing biocathodes will be summarized. The fundamentals of microbial biocathodes will be discussed, as well as the progress towards applications for nitrate reduction in the context of water treatment. Nitrate-reducing biocathodes will be compared with other nitrate-removal techniques and the challenges and opportunities of this approach will be identified.

Site selective generation of sol-gel deposits in layered bimetallic macroporous electrode architectures.

The elaboration of an original composite bimetallic macroporous electrode containing a site-selective sol-gel deposit is reported. Regular colloidal crystals, obtained by a modified Langmuir-Blodgett approach, are used as templates for the electrogeneration of the desired metals in the form of a well-defined layered bimetallic porous electrode. This porous matrix shows a spatially modulated electroactivity which is subsequently used as a strategy for targeted electrogeneration of a sol-gel deposit, exclusively in one predefined part of the porous electrode.

Amperometric Sensor for Selective On-Site Analysis of Free Sulfite in Wines.

Accurate and rapid on-site analysis of free SO2 content is crucial in the process of winemaking from a producer and consumer perspective. Herein, we present an amperometric sensor based on commercially available screen-printed electrodes coupled with an electrochemical oxygen filter. The developed amperometric method gave a linear response in a concentration range up to 200 mg L-1 with a limit of quantification of 7.5 mg L-1. The applicability of the developed sensor was successfully tested on 27 white and red wine samples and compared to the Ripper method (iodometry) that is a standard procedure for free SO2 determination. The sensor exhibits similar precision and accuracy but shows no interference from oxidizable species such as ascorbic acid, which is a major advantage over iodometric titration. The performance of the sensor was in addition positively evaluated during on-site analysis in a winery.

Accurate and simplified consideration of the probe geometrical defaults in scanning electrochemical microscopy: theoretical and experimental investigations.

Fabrication of scanning electrochemical microscopy (SECM) tips cannot always guarantee a perfect disk geometry. In the present work, the impact of these defaults is investigated both theoretically and experimentally. The situations where these defaults can accurately be taken into account by considering that the probe behaves like a microdisk with effective geometric parameters are determined. In these situations, the quantitative analysis of the experimental results is greatly simplified. The study also proposes expressions to evaluate the apparent microdisk parameters from a picture of the probe.

Controlled electrochemically-assisted deposition of sol-gel biocomposite on electrospun platinum nanofibers.

The modification of platinum nanofibers by silica using the electrochemically-assisted deposition is reported here. Pt nanofibers are obtained by electrospinning and deposited on a glass substrate. The electrochemically-assisted deposition of the sol-gel material then gives the unique possibility to finely tune the silica film thickness around these nanofibers. It also allows the successful encapsulation of a biomolecule (glucose oxidase was chosen here as a model) while retaining its biological activity, as pointed out via the electrochemical monitoring of H(2)O(2) produced upon addition of glucose in the medium. This silica-glucose oxidase composite offers the possibility of comparing systematically the influence of the deposition time on the bioelectrode response and to compare it with the particular features of the deposits. It was found that the film first grew uniformly around the nanofibers and then started to deposit between them, covering the whole sample (fibers and glass substrate), and tended to fully embed the nanofibers for prolonged deposition. The thickness of the silica film is critical for the electroactivity of the biocomposite, the best response being obtained for a silica layer thickness in the range of the fiber diameter (∼50 nm).

Multiscale-tailored bioelectrode surfaces for optimized catalytic conversion efficiency.

We describe the elaboration of a multiscale-tailored bioelectrocatalytic system. The combination of two enzymes, D-sorbitol dehydrogenase and diaphorase, is studied with respect to the oxidation of D-sorbitol as a model system. The biomolecules are immobilized in an electrodeposited paint (EDP) layer. Reproducible and efficient catalysis of D-sorbitol oxidation is recorded when this system is immobilized on a gold electrode modified by a self-assembled monolayer of 4-carboxy-(2,5,7-trinitro-9-fluorenylidene)malonitrile used as a mediator. The insertion of mediator-modified gold nanoparticles into the EDP film increases significantly the active surface area for the catalytic reaction, which can be further enhanced when the whole system is immobilized in macroporous gold electrodes. This multiscale architecture finally leads to a catalytic device with optimized efficiency for potential use in biosensors, bioelectrosynthesis, and biofuel cells.

Composite Anion Exchange Membranes Fabricated by Coating and UV Crosslinking of Low-Cost Precursors Tested in a Redox Flow Battery.

This paper presents a novel, cost-effective approach to the fabrication of composite anion exchange membranes (AEMs). Hierarchical AEMs have been fabricated by coating a porous substrate with an interpenetrating polymer network (IPN) layer where poly(vinylpyrrolidone) (PVP) is immobilized in a crosslinked matrix. The IPN matrix was formed by UV initiated radical crosslinking of a mixture of acrylamide-based monomers and acrylic resins. The fabricated membranes have been compared with a commercial material (Fumatech FAP 450) in terms of ionic transport properties and performance in a vanadium redox flow battery (VRFB). Measures of area-specific resistance (ASR) and vanadium permeability for the proposed membranes demonstrated properties approaching the commercial benchmark. These properties could be tuned by changing the content of PVP in the IPN coating. Higher PVP/matrix ratios facilitate a higher water uptake of the coating layer and thus lower ASR (as low as 0.58 Ω.cm2). On the contrary, lower PVP/matrix ratios allow to reduce the water uptake of the coating and hence decrease the vanadium permeability at the cost of a higher ASR (as high as 1.99 Ω.cm2). In VRFB testing the hierarchical membranes enabled to reach energy efficiency comparable with the commercial AEM (PVP_14-74.7%, FAP 450-72.7% at 80 mA.cm-2).

Composite Anion-Exchange Membrane Fabricated by UV Cross-Linking Vinyl Imidazolium Poly(Phenylene Oxide) with Polyacrylamides and Their Testing for Use in Redox Flow Batteries.

Composite anion-exchange membranes (AEMs) consisting of a porous substrate and a vinyl imidazolium poly(phenylene oxide) (VIMPPO)/acrylamide copolymer layer were fabricated in a straightforward process, for use in redox flow batteries. The porous substrate was coated with a mixture of VIMPPO and acrylamide monomers, then subsequently exposed to UV irradiation, in order to obtain a radically cured ion-exchange coating. Combining VIMPPO with low-value reagents allowed to significantly reduce the amount of synthesized ionomer used to fabricate the mem- brane down to 15%. Varying the VIMPPO content also allowed tuning the ionic transport properties of the resulting AEM. A series of membranes with different VIMPPO/acrylamides ratios were prepared to assess the optimal composition by studying the changes of membranes properties-water uptake, area resistivity, permeability, and chemical stability. Characterization of the membranes was followed by cycling experiments in a vanadium RFB (VRFB) cell. Among three composite membranes, the one with VIMPPO 15% w/w-reached the highest energy efficiency (75.1%) matching the performance of commercial ion-exchange membranes (IEMs) used in VRFBs (Nafion® N 115: 75.0% and Fumasep® FAP 450: 73.0%). These results showed that the proposed composite AEM, fabricated in an industrially oriented process, could be considered to be a lower-cost alternative to the benchmarked IEMs.

Electroanalytical metal sensor with built-in oxygen filter.

A rapid and reliable oxygen elimination system was evaluated here for the electroanalytical study of metals. Dissolved oxygen was removed locally in the vicinity of a sensor by the means of electrochemical oxygen filter constructed from platinum grids. Three metals (Cd, Pb, and Zn) were determined by stripping chronopotentiometry (SCP) at a mercury film screen-printed electrode. Limits of detection of metals were in the nanomolar range under optimized experimental conditions. The electrochemical device was also tested for metal quantification in simple electrolyte solutions and in a natural water matrix. The proposed combination of oxygen elimination system with the metal sensor completely removes the need to purge the sample before SCP measurement. This makes the determination of metals by SCP faster, portable and more suited for on-field applications.

Molecularly imprinted polymer as a synthetic receptor mimic for capacitive impedimetric selective recognition of Escherichia coli K-12.

We fabricated an electrochemical molecularly imprinted polymer (MIP) chemosensor for rapid identification and quantification of E. coli strain using 2-aminophenyl boronic acid as the functional monomer. This strain is a modified Gram-negative strain of Escherichia coli bacterium, an ordinary human gut component. The E. coli strongly interacts with a boronic acid because of porous and flexible polymers of the cell wall. The SEM imaging showed that the bacteria template was partially entrapped within the polymeric matrix in a single step. Moreover, this imaging confirmed E. coli K-12 cell template extraction effectiveness. The prepared MIP determined the E. coli K-12 strain up to 2.9 × 104 cells mL-1. The interference study performed in the presence of E. coli variants expressing different surface appendages (type 1 fimbriae or Antigen 43 protein) or Shewanella oneidensis MR1, another Gram-negative bacteria, demonstrated that the bacterial surface composition notably impacts sensing properties of the bacteria imprinted polymer.