Evolution of electrochemical education

Specialized electrochemical education is considered in the context of electrochemistry evolution. The ratio of various branches of electrochemical knowledge is changing systematically as affected by the needs of the society, and we are hardly in time with curriculum tuning. The educational scheme compatible with this situation is considered.

     

On the evolution and application of the concept of electrochemical polarization

This paper yields an overview on the evolution of the concept of polarization applied to electrochemical systems, ranging from electrodes to cells. The historical discussion starts at the early phase of the development of electrochemistry when current-controlled measurements were possible only, and when the early definitions of polarization, depolarization and depolarizer were created. A number of contemporary handbooks, recommendations and other reference resources are listed in which these concepts are represented in various ways, from conservative definitions to attempts of redefining them. The traditional definitions are confronted with the everyday use of professional language, drawing attention to the fact that the widespread application of potential-controlled electrochemical measurements led to new meanings. Some suggestions are made that open room for the application of the term of polarization in accord with the modern methodologies, without compromising the traditional introduction of the term. Polarization-related phenomena in biological membranes are not dealt with in the present work.

     

Transition metal-catalyzed organic reactions in undivided electrochemical cells

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation. This conversion mainly focuses on transition metal-catalyzed anodic oxidation and cathodic reduction and great progress has been achieved in both areas. Typically, only one of the half-cell reactions is involved in the organic reaction while a sacrificial reaction occurs at the counter electrode, which is inherently wasteful since one electrode is not being used productively. Recently, transition metal-catalyzed paired electrolysis that makes use of both anodic oxidation and cathodic reduction has attracted much attention. This perspective highlights the recent progress of each type of electrochemical reaction and relatively focuses on the transition metal-catalyzed paired electrolysis, showcasing that electrochemical reactions involving transition metal catalysis have advantages over conventional reactions in terms of controlling the reaction activity and selectivity and figuring out that transition metal-catalyzed paired electrolysis is an important direction of organic electrochemistry in the future and offers numerous opportunities for new and improved organic reaction methods.

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation.     

Reconstitution of supramolecular organization involved in energy metabolism at electrochemical interfaces for biosensing and bioenergy production

How the redox proteins and enzymes involved in bioenergetic pathways are organized is a relevant fundamental question, but our understanding of this is still incomplete. This review provides a critical examination of the electrochemical tools developed in recent years to obtain knowledge of the intramolecular and intermolecular electron transfer processes involved in metabolic pathways. Furthermore, better understanding of the electron transfer processes associated with energy metabolism will provide the basis for the rational design of biotechnological devices such as electrochemical biosensors, enzymatic and microbial fuel cells, and hydrogen production factories. Starting from the redox complexes involved in two relevant bacterial chains, i.e., from the hyperthermophile Aquifex aeolicus and the acidophile Acidithiobacillus ferrooxidans, examination of protein–protein interactions using electrochemistry is first reviewed, with a focus on the orientation of a protein on an electrochemical interface mimic of a physiological interaction between two partners. Special attention is paid to current research in the electrochemistry of essential membrane proteins, which is one mandatory step toward the understanding of energy metabolic pathways. The complex and challenging architectures built to reconstitute a membrane-like environment at an electrode are especially considered. The role played by electrochemistry in the attempt to consider full bacterial metabolism is finally emphasized through the study of whole cells immobilized at electrodes as suspensions or biofilms. Before the performances of biotechnological devices can be further improved to make them really attractive, questions remain to be addressed in this particular field of research. We discuss the bottlenecks that need to be overcome in the future.     

Synergistic microfluidic and electrochemical strategy to activate and pattern surfaces selectively with ligands and cells

We show a straightforward, flexible synergistic approach that combines microfluidics, electrochemistry, and a general immobilization strategy to activate regions of a substrate selectively for the precise immobilization of ligands and cells in patterns for a variety of cell-based assays and cell migration and cell adhesion studies. We develop microfluidic microchips to control the delivery of electrolyte solution to select regions of an electroactive hydroquinone SAM. Once an electrical potential is applied to the substrate, only the hydroquinone exposed to electrolyte solution within the microfluidic channels oxidizes to the corresponding quinone. The quinone form can then react chemoselectively with oxyamine-tethered ligands to pattern the surface. Therefore, this microfluidic/electrochemistry strategy selectively activates the surface for ligand patterning that exactly matches the channel design of the microfluidic channel. We demonstrate the ease of this system by first quantitatively characterizing the electrochemical activation and immobilization of ligands on the surface. Second, we immobilize a fluorescent dye to show the fidelity of the methodology, and third, we show the immobilization of biospecific cell adhesive peptide ligands to pattern cells. This is the first report that combines microfluidics/electrochemistry and a general electroactive immobilization strategy to pattern ligands and cells. We believe that this strategy will be of broad utility for applications ranging from fundamental studies of cell behavior to patterning molecules on a variety of materials for molecular electronic devices.     

Electrochemistry at Krakowian research institutions

The electrochemistry research team activity from Poland is marked by significant increase in the last 20 years. The joining of European Community in 2004 gives an impulse for the development of Polish science. The development of electrochemistry has been stimulated by cooperation with industry and the establishment of technology transfer centers, technology parks, business incubators, etc. and the mostly by simplified international collaborations. Five research institutions from Krakow reports work in the field of electrochemistry. The achievements of all teams are briefly described.

     

Recent advances in the direct electrochemical detection of drugs of abuse

In the last decade, the trafficking and use of illicit drugs showed a continuous incremental trend, remaining worldwide a challenging problem for the consequences on society, health, criminality, and environment. The introduction on the market of new products and of illicit synthetic compounds represents a new challenging task for analytical chemistry, looking for rapid and accurate methods for the detection of illicit substances in seized street samples, biological fluids, and wastewater. In this context, electrochemical sensors have shown promising results as an alternative to standard chromatographic and spectroscopic methods. This review aims at highlighting the most recent progresses in the use of electrochemistry for the detection of drugs of abuse, mainly including well consolidated substances like cannabinoids, cocaine, opioids, ecstasy, and methamphetamine as well as new psychoactive molecules widely diffused at the present time. Different strategies have been described particularly consisting in the direct electrochemical oxidation of the target analyte. The implementation of tailor-made portable instruments with electrochemical detection methods constitutes an added value to improve the effectiveness of electrochemical sensors for the identification of psychoactive substances when performing large-scale sampling tests.

     

Food dyes screening using electrochemistry approach in solid state: the case of sunset yellow dye electrochemical behavior

Concerning the importance of the identification and characterization of food dyes in food science, this work presents a screening method using voltammetry of immobilized microparticles for identification in solid state of sunset yellow, tartrazine yellow, brilliant blue, indigotine, and erythrosine in food matrices. Different aqueous supporting electrolyte were investigated for screening purpose and NaCl 0.1 mol L⁻¹ showed to be suitable for evaluating dyes in solid state. By using square wave voltammetry as detection mode was possible to establish qualitative diagnostic criteria for identification of dyes in commercials powder of food dyes samples using both anodic and cathodic scan. Moreover, based on the solid-state electrochemistry profile and due to the lack of information about the electrochemical behavior of these compounds in solid state, some oxi/reduction pathways could be elucidated, and special attention was given to the case of sunset yellow dye.

     

Colorimetric and electrochemical phosphodiesterase inhibition assays for yessotoxin detection: development and comparison with LC-MS/MS

This work describes the development and applicability of two functional assays for the detection of yessotoxin (YTX), a polycyclic ether marine toxin produced by dinoflagellates. The assays are based on the interaction between this toxin and the phosphodiesterase (PDE) enzyme and the subsequent measurement of the enzyme activity by colorimetric and electrochemical methods. Firstly, several enzyme substrates were tested in order to select those able to be detected by colorimetry or electrochemistry after enzymatic hydrolysis. The substrates that provided the highest absorbance values and density currents were p-nitrophenyl phenylphosphonate and α-naphthyl phosphate, respectively. After optimisation of the experimental parameters, limits of detection of 0.8 and 0.6 μM were attained by colorimetry and electrochemistry, respectively. An inhibitory effect of YTX on the PDE activity was observed. The assays have been applied to the analysis of YTX production by Protoceratium reticulatum cultures, and results were compared with liquid chromatography–tandem mass spectrometry analysis.     

A recyclable electrochemical allylation in water

To develop environmentally benign processes for C-C bond formation, electrochemistry is applied in a tin-mediated allylation reaction in water. In this electrochemical process, the corresponding homoallylic alcohols are prepared in excellent yields, while both tin salt and water can be recycled and electrode materials are not consumed.     

Development of electrochemistry in Serbia-challenges and perspectives

In this review, the development of electrochemistry in Serbia is presented, with an accent on historical moments from the beginning up to contemporary research directions. The pioneer in the establishment of electrochemical science was Professor Panta S. Tutundzic, who was elected Assistant Professor in Physical Chemistry and Electrochemistry in 1925, when the Department of Technology, previously integrated within the Technical Faculty in Belgrade, was established as a separate department. From the time of Professor Tutundzic′s group to today, a community of many eminent researchers has been involved in electrochemistry development, creating the world-renowned Belgrade School of Electrochemistry. It was not actually a formal school of electrochemistry but rather a variety of research directions, and first of all people doing excellent electrochemical science recognized at the international level. As one of the members of the contemporary active electrochemistry community from Serbia, and successors of the Belgrade School of Electrochemistry, I have both the special honor and the responsibility of presenting the historical contribution of such outstanding and internationally recognized scientists in the most appropriate way. Having in mind that any school and research area is predominantly determined by human resources, I will focus on the great contribution of the most prominent electrochemists, from the founders up to those active today. The main research directions were and still are electrodeposition, electrochemical reaction kinetics, electrocatalysis, energy production and storage, and corrosion and corrosion protection.

     

Determination of Phenolic Sympathetic Stimulants in Pharmaceuticals by Liquid Chromatography with Electrochemical Detection

Abstract

A highly sensitive and selective instrument system combining pellicular cation exchange chromatography with thin layer electrochemistry is applied to the analysis of pharmaceutical dosage forms. Procedures are described for phenolic sympathetic amines in solid and liquid preparations. Satisfactory quantitation is achieved on the nanogram level with minimum sample manipulation and without need for any chemical reagents. Great advantage is demonstrated over previously described colorimetric, fluorometric, and gas chromatographic procedures.     

Electrostatic and electrochemical nature of liquid-gated electric-double-layer transistors based on oxide semiconductors

The electric-double-layer (EDL) formed at liquid/solid interfaces provides a broad and interdisciplinary attraction in terms of electrochemistry, photochemistry, catalysts, energy storage, and electronics because of the large interfacial capacitance coupling and its ability for high-density charge accumulation. Much effort has recently been devoted to the fundamental understanding and practical applications of such highly charged EDL interfaces. However, the intrinsic nature of the EDL charging, whether it is electrostatics or electrochemistry, and how to distinguish them are far from clear. Here, by combining electrical transport measurements with electrochemical impedance spectroscopy (EIS), we studied the charging mechanisms of highly charged EDL interfaces between an ionic liquid and oxide semiconductor, ZnO. The direct measure for mobile carriers from the Hall effect agreed well with that from the capacitance-voltage integration at 1 Hz, implying that the pseudocapacitance does not contribute to carrier transport at EDL interfaces. The temperature-frequency mapping of EIS was further demonstrated as a "phase diagram" to distinguish the electrostatic or electrochemical nature of such highly charged EDL interfaces with densities of up to 8 × 10(14) cm(-2), providing a guideline for electric-field-induced electronic phenomena and a simple method for distinguishing electrostatic and electrochemical charging in EDLTs not only based on a specific oxide semiconductor, ZnO, but also commonly applicable to all types of EDL interfaces with extremely high-density carrier accumulation.     

Radical-scavenging capacity of phenol fractions in the brown seaweed Ascophyllum nodosum: an electrochemical approach

In this article, the radical-scavenging capacity of phenol fractions extracted from the brown seaweed Ascophyllum nodosum was assessed using in parallel colorimetric methods (ABTS and DPPH) and electrochemistry (cyclic voltammetry). Results obtained by the three methods correlated in the case of global fractions, whereas only ABTS and DPPH correlated when activities were expressed on a phenol basis. The successive fractions separated by both their average molecular size and their polarity exhibited activities largely dependant on their phenol content, suggesting that phlorotannins are the main anti-oxidant molecules in hydro-alcoholic extracts of A. nodosum. In addition, phenol fractions of relative low molecular weight were clearly more active than others. This work opens new opportunities to better evaluate the radical-scavenging potential of phenol pools in algae using both bi-parametric fractionating and electrochemistry.     

Electrochemical potentials from first principles

The electrochemical potential is the fundamental parameter in the theory of electrochemistry. Not only does it determine the position of electrochemical equilibria but also it acts as the driving force for electron transfer reactions, diffusion-migration phenomena, and phase transformations of all kinds. In the present work, the electrochemical potential is defined as the total work done in transferring a single particle of a substance from a universal reference state to a specified location, at constant temperature and pressure. It is the sum of two scalar fields: the electrostatic potential energy and the chemical potential energy. The electrochemical potential is widely underutilized within the fields of solid-state science and electrochemical engineering. For historical reasons, many authors prefer to analyze driving forces in terms of electrode potentials, concentration gradients, or Gibbs free energies. In this paper, the author provides a short introduction to the electrochemical potential and then shows how some of the major branches of electrochemistry can benefit from using it. Topics examined include the Volta potential difference, the membrane potential difference, the scanning Kelvin probe microscope, the electromotive force, the proton motive force, and the activation of electron transfer.

     

Abrasive stripping voltammetry — an electrochemical solid state spectroscopy of wide applicability

Abrasive stripping voltammetry is a new electroanalytical technique designed for the qualitative and quantitative analysis of solid materials. It is based upon a preliminary mechanical transfer of trace amounts of a solid sample onto the surface of an electrode. All conventional electrochemical measuring methods can be used. The technique is applicable in many fields of solid state analysis and for fundamental studies of the electrochemistry of solid compounds.     

Ternary molybdenum cluster sulfides: electrochemical and chemical behavior of in situ pulsed laser deposited thin films

The electrochemical deinsertions and insertions in recently synthesised PLD molybdenum cluster sulfide films are presented. We prove that Cu_xMo₆S₈ can be electrochemically converted to Mo₆S₈. The copper, cadmium, zinc and lead intercalation performed by electrochemistry on deintercalated films has succeeded. During this study, we also report that the use of a chemical process allows the formation of PbMo₆S₈ and SnMo₆S₈ thin films, that means that the intercalation of large cations is effective like the one of small cations.     

Adsorption and electrochemical activity: an in situ electrochemical scanning tunneling microscopy study of electrode reactions and potential-induced adsorption of porphyrins

The effect of adsorption on molecular properties and reactivity is a central topic in interfacial physical chemistry. At electrochemical interfaces, adsorbed molecules may lose their electrochemical activity. The absence of in situ probes has hindered our understanding of this phenomenon and electrode reactions in general. In this work, classical electrochemistry and electrochemical scanning tunneling microscopy (EC-STM) were combined to provide molecular level insight into electrochemical reactions and the molecular adsorption state at the electrolyte-electrode interface. The metal-free porphyrin 5,10,15,20-tetra(4-pyridyl)-21H,23H-porphine (TPyP) adsorbed on Au(111) in 0.1 M H(2)SO(4) solution was chosen as a model system. TPyP is found to irreversibly adsorb on Au(111) over a wide range of potentials, from -0.25 to 0.6 V(SCE). The adsorption state of TPyP has a dramatic effect on its electrochemistry. Preadsorbed, oxidized TPyP displays no well-defined cathodic peaks in cyclic voltammograms in sharp contrast to solution-phase TPyP. Our present work provides direct, molecular level evidence of the electrochemically "invisible" species. Electrochemical activity of absorbed species is recovered by allowing the oxidized molecule sufficient time (tens of minutes) to reduce. The redox state of adsorbed TPyP also affects the nature of the adsorption. Oxidized species can apparently only form monolayers. However, multilayers, stable enough to be imaged by STM, can form when the adsorbed TPyP is in the reduced state. This suggests that by controlling the electrochemistry one can either promote or suppress the formation of multilayers.     

Transfer Mechanism of Ionic Drugs: Piroxicam as an agent facilitating proton transfer

Facilitated proton transfer may be of potential significance in pharmacokinetic and pharmacodynamic processes. Here, we show that the NSAID piroxicam and its N-and O-methylated derivatives act as ionophores for proton transfer across the H₂O/1,2-dichloroethane interface. Investigations by cyclic voltammetry showed that the proton transfer occurs by interfacial protonation of the ionophore. The dissociation constants of the three compounds in the organic phase were calculated by Matsuda's theory. With this particular transfer mechanism, the present study exemplifies how electrochemistry at a liquid/liquid interface can be applied to calculate the fundamental thermodynamic parameters related to the pharmacokinetic behavior of ionic drugs.     

The potentials of additive manufacturing for mass production of electrochemical energy systems

Additive manufacturing has established itself as a popular and powerful tool in electrochemistry research and development. In this short review, we focus on the latest results in both 3D printing and electrochemistry communities that could potentially benefit manufacturing in the electrochemical industry. We provide insights from recent and relevant research works and conclude that the likely scenario in the industry is the deployment of a combination of subtractive and additive technologies in order to manufacture high quality and cost-effective electrochemical reactors within reasonable timeframes.