Theoretical Framework and Guidelines for the Cyclic Voltammetry of Closed Bipolar Cells.

Closed bipolar cells (cBPCs) can offer valuable platforms for the development of electrochemical sensors. On the other hand, such systems are more intricate to model and interpret than conventional systems with a single polarizable interface, with the applied potential "splitting" into two polarized interfaces where two coupled charge transfers take place concomitantly. As a result, the voltammetry of cBPCs shows peculiarities that can be misleading if analyzed under the framework of classic electrochemical cells. In this work, rigorous mathematical solutions are deduced for the cyclic voltammetry (CV) of cBPCs, including the current-potential response, the interfacial potentials, and the interfacial redox concentrations. With such theoretical tools, a comprehensive view of the behavior of cBPCs can be gained, and adequate diagnosis criteria are established on the basis of the shape, magnitude, and position of the CV signal as a function of the scan rate and of the experimental conditions in the anodic and cathodic compartments.

Human Wharton's jelly-derived mesenchymal stromal cells promote bone formation in immunodeficient mice when administered into a bone microenvironment.

BACKGROUND: Wharton's Jelly (WJ) Mesenchymal Stromal Cells (MSC) have emerged as an attractive allogeneic therapy for a number of indications, except for bone-related conditions requiring new tissue formation. This may be explained by the apparent recalcitrance of MSC,WJ to differentiate into the osteogenic lineage in vitro, as opposed to permissive bone marrow (BM)-derived MSCs (MSC,BM) that readily commit to bone cells. Consequently, the actual osteogenic in vivo capacity of MSC,WJ is under discussion. METHODS: We investigated how physiological bone environments affect the osteogenic commitment of recalcitrant MSCs in vitro and in vivo. To this end, MSC of BM and WJ origin were co-cultured and induced for synchronous osteogenic differentiation in vitro using transwells. For in vivo experiments, immunodeficient mice were injected intratibially with a single dose of human MSC and bone formation was evaluated after six weeks. RESULTS: Co-culture of MSC,BM and MSC,WJ resulted in efficient osteogenesis in both cell types after three weeks. However, MSC,WJ failed to commit to bone cells in the absence of MSC,BM's osteogenic stimuli. In vivo studies showed successful bone formation within the medullar cavity of tibias in 62.5% of mice treated with MSC, WJ. By contrast, new formed trabeculae were only observed in 25% of MSC,BM-treated mice. Immunohistochemical staining of human COXIV revealed the persistence of the infused cells at the site of injection. Additionally, cells of human origin were also identified in the brain, heart, spleen, kidney and gonads in some animals treated with engineered MSC,WJ (eMSC,WJ). Importantly, no macroscopic histopathological alterations, ectopic bone formation or any other adverse events were detected in MSC-treated mice. CONCLUSIONS: Our findings demonstrate that in physiological bone microenvironment, osteogenic commitment of MSC,WJ is comparable to that of MSC,BM, and support the use of off-the-shelf allogeneic MSC,WJ products in bone repair and bone regeneration applications.

Voltammetric Kinetic Studies of Electrode Reactions: Guidelines for Detailed Understanding of Their Fundamentals.

Theoretical and practical foundations of basic electrochemical concepts of heterogeneous charge transfer reactions that underline electrochemical processes are presented for their detailed study by undergraduate and postgraduate students. Several simple methods for calculating key variables, such as the half-wave potential, limiting current, and those implied in the kinetics of the process, are explained, discussed, and put in practice through simulations making use of an Excel document. The current-potential response of electron transfer processes of any kinetics (i.e., any degree of reversibility) are deduced and compared for electrodes of different size, geometry, and dynamics, namely: static macroelectrodes in chronoamperometry and normal pulse voltammetry, and static ultramicroelectrodes and rotating disc electrodes in steady state voltammetry. In all cases, a universal, normalized current-potential response is obtained in the case of reversible (fast) electrode reactions, whereas this is not possible for nonreversible processes. For this last situation, different widely used protocols for the determination of the kinetic parameters (the mass-transport corrected Tafel analysis and the Koutecký-Levich plot) are deduced, proposing learning activities that highlight the foundations and limitations of such protocols, as well as the influence of the mass transport conditions. Discussions on the implementation of this framework and on the benefits and difficulties found are also presented.

Investigating Comproportionation in Multielectron Transfers via UV-Visible Spectroelectrochemistry: The Electroreduction of Anthraquinone-2-sulfonate in Aqueous Media.

UV-vis spectroelectrochemistry is assessed as a tool for the diagnosis and quantitative in situ investigation of the incidence of comproportionation in multielectron transfer processes. Thus, the sensitivity of the limiting current chronoabsorptometric signals related to the different redox states to the comproportionation kinetics is studied theoretically for different working modes (normal and parallel light beam arrangements) and mass transport regimes (from semi-infinite to thin layer diffusion). The theoretical results are applied to the spectroelectrochemical study of the two-electron reduction of the anthraquinone-2-sulfonate in alkaline aqueous solution, tuning the thermodynamic favorability of the comproportionation reaction through the electrolyte cation. The quantitative analysis of the experimental results reveals the occurrence of comproportionation in the three media examined, showing different kinetics depending on the cationic species in solution.

General Explicit Mathematical Solution for the Voltammetry of Nonunity Stoichiometry Electrode Reactions: Diagnosis Criteria in Cyclic Voltammetry.

Electrochemical reactions can effectively follow nonunity stoichiometries as can be found in the electrochemistry of halides, hydrogen, and metal complexes. The voltammetric response of these systems shows peculiar deviations with respect to the well-described features of the 1:1 stoichiometry. With the aim of specifying such differences, a rigorous and manageable analytical theory is deduced for the complete characterization of reversible electrode processes with complex stoichiometry in cyclic voltammetry (CV) at macroelectrodes. Particularly, the main features of the CV of 2:1, 1:2, 3:1, and 1:3 processes (that is, the peak currents and potentials and the influence of the scan rate and of the species concentration and diffusion coefficients) are given and compared with the 1:1 case in order to propose unambiguous diagnostic criteria of the stoichiometry of the electrode reaction. Also, expressions for the concentration profiles and surface concentrations of the redox species are given.

Quantitative Analysis of Cyclic Voltammetry of Redox Monolayers Adsorbed on Semiconductors: Isolating Electrode Kinetics, Lateral Interactions, and Diode Currents.

The design of devices whose functions span from sensing their environments to converting light into electricity or guiding chemical reactivity at surfaces often hinges around a correct and complete understanding of the factors at play when charges are transferred across an electrified solid-liquid interface. For semiconductor electrodes in particular, published values for charge-transfer kinetic constants are scattered. Furthermore, received wisdom suggests slower charge-transfer kinetics for semiconductors than for metal electrodes. We have used cyclic voltammetry of ferrocene-modified silicon photoanodes and photocathodes as the experimental model system and described a systematic analysis to separate charge-transfer kinetics from diode effects and interactions between adsorbed species. Our results suggest that literature values of charge-transfer kinetic constants at semiconductor electrodes are likely to be underestimates of their actual values. This is revealed by experiments and analytical models showing that the description of the potential distribution across the semiconductor-monolayer-electrolyte interface has been largely oversimplified.

Guidelines for the Voltammetric Study of Electrode Reactions with Coupled Chemical Kinetics at an Arbitrary Electrode Geometry.

A powerful, unified, and simplifying mathematical approach for the theoretical treatment of first-order chemical kinetics coupled to interfacial charge transfers at electrodes of arbitrary geometry and size, both uniformly accessible and nonuniformly accessible to the electroactive species, is presented. The general CEC mechanism at spherical and disc electrodes is considered to test the validity and benefits of such an approach, based on the application of the so-called kinetic steady state, that enables the reduction of the multivariable problem of kinetic-diffusive differential equations to a single variable problem of a diffusion-only differential equation. This is solved both analytically and numerically, showing how this approach leads to general, simple, and efficient solutions for the study of the influence of coupled chemical kinetics on the voltammetric response. The voltammetry of the CEC mechanism is analyzed as a function of the kinetics and thermodynamics of the preceding and subsequent chemical reactions and of the electrode size (from macroelectrodes to ultramicroelectrodes) and shape (spherical and disc). Comparison with the responses of the CE, EC, and E mechanisms is included, proposing diagnosis criteria and procedures for quantitative analysis of experimental data.

Double Transfer Voltammetry in Two-Polarizable Interface Systems: Effects of the Lipophilicity and Charge of the Target and Compensating Ions.

Analytical expressions are obtained for the study of the net current and individual fluxes across macro- and micro-liquid/liquid interfaces in series as those found in ion sensing with solvent polymeric membranes and in ion-transfer batteries. The mathematical solutions deduced are applicable to any voltammetric technique, independently of the lipophilicity and charge number of the target and compensating ions. When supporting electrolytes of semihydrophilic ions are employed, the so-called double transfer voltammograms have a tendency to merge into a single signal, which complicates notably the modeling and analysis of the electrochemical response. The present theoretical results point out that the appearance of one or two voltammetric waves is highly dependent on the size of the interfaces and on the viscosity of the organic solution. Hence, the two latter can be adjusted experimentally in order to "split" the voltammograms and extract information about the ions involved. This has been illustrated in this work with the experimental study in water | 1,2-dichloroethane | water cells of the transfer of the monovalent tetraethylammonium cation compensated by anions of different lipophilicity, and also of the divalent hexachloroplatinate anion.

Theoretical Treatment of Ion Transfers in Two Polarizable Interface Systems When the Analyte Has Access to Both Interfaces.

A new theory is presented to tackle the study of transfer processes of hydrophilic ions in two polarizable interface systems when the analyte is initially present in both aqueous phases. The treatment is applied to macrointerfaces (linear diffusion) and microholes (highly convergent diffusion), obtaining analytical equations for the current response in any voltammetric technique. The novel equations predict two signals in the current-potential curves that are symmetric when the compositions of the aqueous phases are identical while asymmetries appear otherwise. The theoretical results show good agreement with the experimental behavior of the "double transfer voltammograms" reported by Dryfe et al. in cyclic voltammetry (CV) ( Anal. Chem. 2014 , 86 , 435 - 442 ) as well as with cyclic square wave voltammetry (cSWV) experiments performed in the current work. The theoretical treatment is also extended to the situation where the target ion is lipophilic and initially present in the organic phase. The theory predicts an opposite effect of the lipophilicity of the ion on the shape of the voltammograms, which is validated experimentally via both CV and cSWV. For the above two cases, simple and manageable expressions and diagnosis criteria are derived for the qualitative and quantitative study of ion lipophilicity. The ion-transfer potentials can be easily quantified from the separation between the two signals making use of explicit analytical equations.

Microelectrode voltammetry of multi-electron transfers complicated by coupled chemical equilibria: a general theory for the extended square scheme.

A very general and simple theoretical solution is presented for the current-potential-time response of reversible multi-electron transfer processes complicated by homogeneous chemical equilibria (the so-called extended square scheme). The expressions presented here are applicable regardless of the number of electrons transferred and coupled chemical processes, and they are particularized for a wide variety of microelectrode geometries. The voltammetric response of very different systems presenting multi-electron transfers is considered for the most widely-used techniques (namely, cyclic voltammetry, square wave voltammetry, differential pulse voltammetry and steady state voltammetry), studying the influence of the microelectrode geometry and the number and thermodynamics of the (electro)chemical steps. Most appropriate techniques and procedures for the determination of the 'interaction' between successive transfers are discussed. Special attention is paid to those situations where homogeneous chemical processes, such as protonation, complexation or ion association, affect the electrochemical behaviour of the system by different stabilization of the oxidation states.

Single Fusion Events at Polarized Liquid-Liquid Interfaces.

A new electrochemical framework for tracking individual soft particles in solution and monitoring their fusion with polarized liquid-liquid interfaces is reported. The physicochemical principle lies in the interfacial transfer of an ionic probe confined in the particles dispersed in solution and that is released upon their collision and fusion with the fluid interface. As a proof-of-concept, spike-like transients of a stochastic nature are reported in the current-time response of 1,2-dichloroethane(DCE)|water(W) submilli-interfaces after injection of DCE-in-W emulsions. The sign and potential dependence of the spikes reflect the charge and lipophilicity of the ionic load of the droplets. A comparison with dynamic light scattering measurements indicates that each spike is associated with the collision of a single sub-picoliter droplet. This opens a new framework for the study of single fusion events at the micro- and nanoscale and of ion transport across biomimetic soft interfaces.

Transfer of complexed and dissociated ionic species at soft interfaces: a voltammetric study of chemical kinetic and diffusional effects.

A new transfer mechanism is considered in which two different ionic species of the same charge can be transferred across a soft interface while they interconvert with each other in the original phase through a homogeneous chemical reaction: the aqueous complexation-dissociation coupled to transfer (ACDT) mechanism. This can correspond to a free ion in aqueous solution in the presence of a neutral ligand that complexes it leading to a species that can be more or less lipophilic than the free ion. As a result, the transfer to the organic phase can be facilitated or hindered by the aqueous-phase chemical reaction. Rigorous and approximate explicit analytical solutions are derived for the study of the above mechanism via normal pulse voltammetry, derivative voltammetry and chronoamperometry at macrointerfaces. The solutions enable us to examine the process whatever the species' lipophilicity and diffusivity in each medium and the kinetics and thermodynamics of the chemical reaction in solution. Moreover, when the chemical reaction is at equilibrium, explicit expressions for cyclic voltammetry and square wave voltammetry are obtained. With this set of equations, the influence of different physicochemical phenomena on the voltammetric response is studied as well as the most suitable strategies to characterize them.

Voltammetry of the aqueous complexation-dissociation coupled to transfer (ACDT) mechanism with charged ligands.

The study of the so-called aqueous complexation-dissociation coupled to transfer (ACDT) mechanism is extended to systems where the ligand species is not neutral and so the charge of the two transferable ions is different (z1 ≠ z2). This has a profound effect on the voltammetric response of the system, which shows a complex behaviour depending on the chemical kinetics, the difference between the lipophilicity of the two ions and the applied potential. Such response is modelled making use of the diffusive-kinetic steady state (dkss) approach, obtaining analytical expressions for the current-potential-time curves in normal pulse, derivative and differential multipulse voltammetries. In addition, manageable expressions for the concentration profiles, interfacial fluxes and interfacial concentrations of all the species either side of the liquid|liquid interface are derived. From them, the effect on the voltammograms of the characteristics of the chemical reaction and the lipophilicity of the ions is thoroughly studied, comparing the cases where the ions carry the same and a different charge. The last case shows some striking behaviours that can be understood from the analysis of the concentration profiles.

Application of voltammetric techniques at microelectrodes to the study of the chemical stability of highly reactive species.

The application of voltammetric techniques to the study of chemical speciation and stability is addressed both theoretically and experimentally in this work. In such systems, electrode reactions are coupled to homogeneous chemical equilibria (complexations, protonations, ion associations, ...) that can be studied in a simple, economical, and accurate way by means of electrochemical methods. These are of particular interest when some of the participating species are unstable given that the generation and characterization of the species are performed in situ and on a short time scale. With the above aim, simple explicit solutions are presented in this article for quantitative characterization with any voltammetric technique and with the most common electrode geometries. From the theoretical results obtained, it is pointed out that the use of square-wave voltammetry in combination with microelectrodes is very suitable. Finally, the theory is applied to the investigation of the ion association between the anthraquinone radical monoanion and the tetrabutylammonium cation in acetonitrile medium.

Reversible surface two-electron transfer reactions in square wave voltcoulommetry: application to the study of the reduction of polyoxometalate [PMo12O40]3- immobilized at a boron doped diamond electrode.

Reversible surface two-electrons transfer reactions (stepwise processes) are analyzed using square wave voltcoulommetry (SWVC), which is a variety of square wave techniques based on the measurement of the transferred charge. Such reversible surface redox processes are exhibited by many two-redox center and multicenter biomolecules (proteins, enzymes, ...) and inorganic molecules like polyoxometalates (POMs), which have very interesting applications, mainly as electrocatalysts. Because of the stationary character of the response obtained, the key parameters that govern the cooperativity degree of the two reversible electron transfers (ETs) are the difference between their formal potentials, ΔE(0), and the square wave amplitude, |E(SW)|, whose combined effect sets the two peaks → one peak transition in the response. Working curves based on the variation of the peak parameters (peak potentials, half-peak widths, and peak heights) with ΔE(0) and |E(SW)| are given, from which the formal potentials and the total surface excess can be accurately determined. SWVC has been applied to the study of the reduction of polyoxometalate [PMo12O40](3-) adsorbed at a boron doped diamond electrode (BDD), for which three stable and well-defined reversible charge peaks, corresponding to three cooperative EE processes, are obtained in the interval (0.6, -0.2) V by using low square wave frequencies. From the analysis of these peaks, the values of the total surface excess and the formal potentials of the six ETs have been obtained in aqueous media for two electrolytes: HClO4 and LiClO4.

Integrating the United Nations sustainable development goals into higher education globally: a scoping review.

BACKGROUND: In 2015, the United Nations adopted the 2030 Agenda for Sustainable Development, including the 17 Sustainable Development Goals (SDGs). Higher education institutions have a role in raising awareness and building skills among future professionals for implementing the SDGs. This review describes how the SDGs have been integrated into higher education globally. OBJECTIVES: Determine how have the SDGs been integrated into higher education globally. Describe the differences in the integration of the SDGs in higher education across high-income countries (HICs) and low- and middle-income countries (LMICs). METHODS: Following a scoping review methodology, we searched Medline, Web of Science, Global Health, and Educational Resources Information Center, as well as websites of key institutions including universities, identifying peer-reviewed articles and grey literature published between September 2015 and December 2021. RESULTS: We identified 20 articles and 38 grey literature sources. Since 2018, the number of publications about the topic has been increasing. The SDGs were most frequently included in bachelor-level education and disciplines such as engineering and technology; humanities and social sciences; business, administration, and economics. Methods of integrating the SDGs into higher education included workshops, courses, lectures, and other means. Workshops and courses were the most frequent. The methods of integration varied in high-income countries compared to low- and middle-income countries. High-income countries seemed to follow a more academic approach to the SDGs while low- and middle-income countries integrate the SDGs with the aim to solve real-world problems. CONCLUSION: This study provides examples of progress in integrating the SDGs into higher education. Such progress has been skewed to high-income countries, bachelor-level initiatives, and certain disciplines. To advance the integration of the SDGs, lessons learned from universities globally should be shared broadly, equitable partnerships formed, and students engaged, while simultaneously increasing funding for these processes.

Data Processing and Analysis in Mass Spectrometry-Based Metabolomics.

Metabolomics is the latest of the omics sciences. It attempts to measure and characterize metabolites-small chemical compounds <1500 Da-on cells, tissue, or biofluids, which are usually products of biological reactions. As metabolic reactions are closer to the phenotype, metabolomics has emerged as an attractive science for various areas of research, including personalized medicine. However, due to the complexity of data obtained and the absence of curated databases for metabolite identification, data processing is the major bottleneck in this area since most technicians lack the required bioinformatics expertise to process datasets in a reliable and fast manner. The aim of this chapter is to describe the available tools for data processing that makes an inexperienced researcher capable of obtaining reliable results without having to undergo through huge parametrization steps.

Some insights into the facilitated ion transfer voltammetric responses at ITIES exhibiting interfacial and bulk membrane kinetic effects.

General analytical equations corresponding to the Facilitated Ion Transfer (FIT) at ITIES (Interface between Two Immiscible Electrolyte Solutions) are presented for the most frequent case in which the complexing agent is present only in the organic phase, and considering both the ion transfer and the chemical complexation kinetic effects. Under these conditions, the FIT process can be regarded as an EC mechanism. This study is of great interest to elucidate the origin of the kinetic effects which affect the electrochemical signal. Normal Pulse Voltammetry and Derivative Normal Pulse Voltammetry are chosen as representative and easy understandable voltammetric techniques. From the general equations, the expressions corresponding to some interesting particular situations in which one or the two kinetic processes (ion transfer and organic complexation) are in equilibrium are derived. Moreover, working curves of the characteristic peak parameters of the derivative voltammetric response are given, from which it is possible to determine the kinetic constants. The results obtained here are applicable to a wide range of liquid membrane systems, from traditional liquid-liquid interfaces to plasticized polymeric membranes and supported liquid-liquid interfaces.

Kinetic effects of the complexation reaction in the facilitated ion transfer at liquid membrane systems of one and two polarized interfaces. Theoretical insights.

An in-depth study of the ion transfer facilitated by complexation in the organic phase (TOC mechanism) in liquid membrane systems of one and two polarized interfaces is carried out by taking into account the kinetic effects associated with the complexation reaction. Explicit analytical equations for the normal pulse voltammetric (I/E) and chronoamperometric (I/t) responses with an explicit dependence on the kinetic parameters of the chemical complexation are presented for both kinds of membrane system, which could be useful for modeling artificial and biological membranes. The equations are compared with those obtained by using the widely used approximation of total equilibrium conditions that leads to the transfer by interfacial complexation mechanism (TIC), which only depends on thermodynamic parameters. Simple methods are proposed that allow quantitative determination of the equilibrium and kinetic constants of the complexation reaction in the organic phase for both kinds of membrane system.

Analytical theory of the catalytic mechanism in square wave voltammetry at disc electrodes.

A simple analytical expression is presented for the study of the first-order catalytic mechanism using Square Wave Voltammetry (SWV) at disc electrodes. These electrodes are extensively used in electrochemical studies but modelling the electrochemical response at this geometry is complex and usually requires the use of sophisticated numerical methods. By contrast, the analytical solution presented in this work is easy to compute and it is applicable to any size of the disc and for arbitrary kinetics of the catalytic reaction. The effects of the electrode size, the homogeneous rate constants, the frequency and the square wave amplitude on the SWV response are analyzed. Criteria are given for the detection of the steady-state response as well as procedures for the extraction of the catalytic rate constant from the value of the peak current. The theory is applied to obtain the kinetics of the reduction of the anion nitrite by an electrogenerated heteropolyanion [P(W(3)O(10))(4)](4-) at gold microdiscs.