In Situ Recalibration of Ion Selective Electrodes

Reference electrode drift resulting from the exchange of ions at the solution/reference electrode chamber interface is the number one reason why ion selective electrodes and pH sensors in particular require recalibration, costing companies up to 70 % of the total lifetime cost of a pH probe. In this work, a novel and innovative methodology is proposed in which the reference potential is tracked, allowing for in-situ recalibration of the sensor without the need for end-user intervention

Multiphase Methods in Organic Electrosynthesis

© 2019 American Chemical Society. ConspectusWith water providing a highly favored solution environment for industrial processes (and in biological processes), it is interesting to develop water-based electrolysis processes for the synthesis and conversion of organic and biomass-based molecules. Molecules with low solubility in aqueous media can be dispersed/solubilized (i) by physical dispersion tools (e.g., milling, power ultrasound, or high-shear ultraturrax processing), (ii) in some cases by pressurization/supersaturation (e.g., for gases), (iii) by adding cosolvents or "carriers" such as chremophor EL, or (iv) by adding surfactants to generate micelles, microemulsions, and/or stabilized biphasic conditions. This Account examines and compares methodologies to bring the dispersed or multiphase system into contact with an electrode. Both the microscopic process based on individual particle impact and the overall electro-organic transformation are of interest. Distinct mechanistic cases for multiphase redox processes are considered.Most traditional electro-organic transformations are performed in homogeneous solution with reagents, products, electrolyte, and possibly mediators or redox catalysts all in the same (usually organic) solution phase. This may lead to challenges in the product separation step and in the reuse of solvents and electrolytes. When aqueous electrolyte media are used, reagents and products (or even the electrolyte) may be present as microdroplets or nanoparticles. Redox transformations then occur during interfacial "collisions" under multiphase conditions or within a reaction layer when a redox mediator is present. Benefits of this approach can be (i) the use of a highly conducting aqueous electrolyte, (ii) simple separation of products and reuse of the electrolyte, (iii) phase-transfer conditions in redox catalysis, (iv) new reaction pathways, and (v) improved sustainability. In some cases, a surface phase or phase boundary processes can lead to interesting changes in reaction pathways. Controlling the reaction zone within the multiphase redox system poses a challenge, and methods based on microchannel flow reactors have been developed to provide a higher degree of control. However, detrimental effects in microchannel systems are also observed, in particular for limited current densities (which can be very low in microchannel multiphase flow) or in the development of technical solutions for scale-up of multiphase redox transformations.This Account describes physical approaches (and reactor designs) to bring multiphase redox systems into effective contact with the electrode surface as well as cases of important electro-organic multiphase transformations. Mechanistic cases considered are "impacts" by microdroplets or particles at the electrode, effects of dissolved intermediates or redox mediators, and effects of dissolved redox catalysts. These mechanistic cases are discussed for important multiphase transformations for gaseous, liquid, and solid dispersed phases. Processes based on mesoporous membranes and hydrogen-permeable palladium membranes are discussed

Evaporative Mass Loss Measurement as a Quality Control Tool for Quality Assurance in the Manufacture of Inks Suitable for High Speed (≥60 m/min) Printing

In any manufacturing environment, it is always important to be able to embrace a culture of traceability of any non-conformed product. For the case of ink manufacture, operator confusion, leading to the mixing-up of solvents, or connecting the incorrect solvent drum to solvent lines, can lead to disastrous consequences that are not trivial for a quality control/quality assurance team to unravel. Accordingly, simple methods for assessing whether the correct solvents were added in the correct ratios to products empower this QA/QC requirement. In this paper, we examine the use of a trivial measurement of evaporative mass loss as a protocol for validating the conformance of manufactured ink to specification. Inspired by the transport-limit that occurs at ultramicroelectrodes in electrochemistry, we develop theory to analyse evaporation rate measurements, and illustrate how vaporisation at the liquid | gas interface is dominated by a diffusion anisotropy, owing to natural convection for organic solvents, manufactured resins and commercialised inks that have been used, inter alia, for the underground transport tickets in the cities of London and Paris. We further demonstrate that the use of incorrect solvents is readily seen through evaporation rate transients, thereby enabling this measurement for human factor mitigation during the ink manufacture process

Asymmetric and Anharmonic Electrode Kinetics: Evaluation of a Model for Electron Transfer with Concerted Rupture of Weak, Inner Shell Interactions

A surface-integrated form of the widely used (anharmonic) Lennard-Jones 12–6 interaction potential, the Lennard-Jones 9–3 potential, is used to develop a quadratic activation/driving force relationship that gives rise to asymmetric Tafel plots for electron transfer occurring with simultaneous interaction rupture. The Tafel plots are shown to exhibit linearity over a wide potential range, depending on the ratio of the Gibbs interaction well to the solvent reorganisation free energy. The fit of the model to experimental data for a ferrocene-based self-assembled monolayer (SAM) bathed by aqueous perchloric acid suggests ion pairing between ferricenium and perchlorate ions. This crude and primitive model readily enables experimentalists to obtain a parametric understanding of the physicochemical dynamics underpinning interaction rupture in concert with electron transfer, which may empower routes to improve the efficiency of a plethora of topical electrochemical technologies

Oxidative Dissolution of Lithium and Manganese from Lithium Manganospinel (LiMn 2 O 4 ): Towards Climate-Smart Processes for Critical Metal Recycling

This work reports the oxidative breakdown of the LiMn2O4 structure using alkaline hypochlorite, as a method for recovering both lithium and manganese species. The heterogeneous dissolution rate for this process is monitored through the formation of the permanganate ion. It is found that reaction occurs under activation control, with a barrier that matches that for electron hopping within the spinel. Moreover, this activation barrier is smaller than those observed for typical conventional methods of recovery of lithium or manganese from LiMn2O4; accordingly, the new process is suggested to be climate-smart, despite the low, single-pass, recovery efficiency that results from slow surface kinetics

Electrochemical immunoassay for the detection of stress biomarkers

A rapid electrochemical immunoassay method was developed to detect and measure stress biomarkers (cortisol and cortisone) in two biological samples (Zebrafish whole-body and artificial saliva). This methodology utilizes an immunoassay approach taking advantage of the lock and key mechanism that is related to the antibody-antigen interaction depending on the reliable immobilization of the antibody labelled with ferrocene tags (Ab-Fc) on a modified tin-doped indium oxide (ITO) electrode using electrochemical instrumentation to build a POC platform. The limit of detection (LOD) obtained for this biosensor was 1.03 pg ml−1 for cortisol and 0.68 pg ml−1 for cortisone, respectively. The correlation coefficient was 0.9852 and 0.9841 for cortisol and cortisone, respectively with a linear concentration from (0-50 ng ml−1) which covers the standard levels of stress hormones in both selected biological samples. The incubation time was investigated and 30 min was found to be the optimum incubation time. This time would be acceptable for the POC system as total process time can be determined within 35 min

A mechanistic study of the EC′ mechanism – the split wave in cyclic voltammetry and square wave voltammetry

In this paper, a detailed investigation of electrochemical reactions coupled with homogenous chemical steps using cyclic voltammetry (CV) and square wave voltammetry (SWV) was carried out to study the electrocatalytic (EC’) mechanism. In CV, parameters including scan rate, electrode material and redox reactant were investigated while in SWV, parameters including substrate concentrations and frequencies were altered to demonstrate EC’ mechanism. Mechanistic studies focused on the EC’ mechanism using L-cysteine with ferrocenecarboxylic acid and 1,1 ′-ferrocenedicarboxylic acid respectively. Voltammetric responses were recorded and under conditions of high chemical rate constant and low substrate concentration, a split wave was observed in both CV and SWV studies

Synthesis and antibacterial effects of cobalt–cellulose magnetic nanocomposites

© The Royal Society of Chemistry. Green synthesis is employed to prepare cobalt/cellulose nanocomposites with cubic (α-cobalt) cobalt as a main component with antibacterial and magnetic properties. An in situ reduction of aqueous solutions of cobalt ions on a model cellulose substrate surface using hydrogen gas affords spherical, cellulose-stabilised cobalt nanoclusters with magnetic properties and an average diameter of 7 nm that are distributed evenly over the surface of the cellulose fibres. These cobalt/cellulose nanocomposites exhibit good antibacterial action against opportunistic pathogens both Gram-positive (S. aureus) and Gram-negative (E. coli, A. baumannii and P. aeruginosa), with zones of inhibition up to 15 mm, thereby encouraging the deployment of these advanced materials for the treatment of wastewater or within medical dressings. This method of preparation is compared with the analogous in situ reduction of cobalt ions on a cellulose surface using sodium borohydride as reducing agent

Interaction of temperature, salinity and extracellular polymeric substances controls trace element incorporation into tufa calcite

The influence of extracellular polymeric substances on carbonate mineral growth in natural settings remains one of the most poorly understood contributors to the growth of non-marine carbonate sediments. The influences of these materials are complicated by their association with living cells creating local microenvironments via metabolism and enzyme production, and by our uncertainty about the extracellular polymeric substances materials themselves. Different mixtures of extracellular polymeric substance molecules may behave in different ways, and differences in the local physical environment may alter how the mixtures influence mineral formation, and even result in different patterns of polymerization. Here, the influence of extracellular polymeric substances on calcite precipitation rate and Mg/Cacalcite in the absence of cells is investigated using extracts of extracellular polymeric substances from temperate fluvial tufa biofilm. The influence is complex, with the concentration of extracellular polymeric substances in solution altering deposition rate and trace element incorporation. Moreover, the results show interaction of the presence/absence of extracellular polymeric substances and both temperature and salinity. However, despite extracting extracellular polymeric substances from the same parent sample, a uniform influence was not found in these experiments, implying that the mixture is sufficiently variable within a sample for microenvironments within the biofilm to either promote or inhibit mineralization. As sedimentologists, we can no longer take the view that extracellular polymeric substances are a bystander material, or that they have a single set of coherent and predictable or intuitive influences. Rather, the emphasis must be on investigating the specific mixtures present in nature, and their complex and dynamic interaction with both mineral surfaces and hydrochemical conditions