Advanced electrochemical techniques for investigating electron transfer kinetics

Heterogenous interfacial electron transfer processes are of fundamental and applied importance to electrochemists and are extensively studied by a wide range of electrochemical techniques. This thesis focuses on the development of analysis strategies and electrochemical methodologies for more detailed quantitative investigations of electron transfer kinetics at a plethora of electrode materials, with an emphasis on carbon-based materials. Of interest are the techniques of Fourier-transformed large amplitude alternating current voltammetry (FTACV) and scanning electrochemical microscopy (SECM). The complementary electrochemical techniques of FTACV and SECM are used for measurements of fast electron transfer to reveal the impact of the complex heterogeneous surface of degenerately-doped polycrystalline boron-doped diamond electrode surfaces compared to conventional electrode materials such as platinum and gold. This part of the work highlights the importance of understanding the influence of measurement technique and further demonstrates how electron transfer at semi-metallic electrodes differ from conventional metallic electrodes. The oxidation of a ferrocene-derivative at highly oriented pyrolytic graphite is used to demonstrate the effects of reversible reactant adsorption on the SECM response. The high surface area-to-solution volume ratio of nanogap SECM measurements depicts the importance of understanding the impact of such surface effects. Precise quantitative kinetic analysis requires understanding of the mass transport between the SECM probe and electrode surface. Finite element method modelling was used to extensively investigate the effects of electrode reactant processes and the results of the models shed light on important factors that need to be accounted for in quantitative analysis of nanogap voltammetric measurements. FTACV is further developed as a tool for kinetic selectivity at heterogeneous electrode surfaces. This is achieved by taking advantage of the harmonic-dependent measurement timescale of FTACV to deconvolute a dual-heterogeneity electrochemical response into its individual components. Protocols are developed for this application and demonstrated experimentally using the ruthenium hexamine and ferrocene methanol redox couples

Double layer effects in voltammetric measurements with scanning electrochemical microscopy (SECM)

Scanning electrochemical microscopy (SECM) operating as a variable gap ultra-thin layer twin-working electrode cell, has long been recognised as a powerful technique for investigating fast kinetics (heterogeneous electron transfer and homogeneous reactions coupled to electron transfer) as a consequence of high mass transport rates between the working electrodes when biased to promote redox shuttling. Recently, SECM has advanced technically and nanogap cells with dimensions on the 10s of nm scale have been reported. In this paper, we consider double layer effects on voltammetric measurements in this configuration, outlining a comprehensive model that solves the Nernst-Planck equation and Poisson equation with charged interfaces. For supporting electrolyte concentrations that have been used for such measurements (50 mM and 100 mM), it is shown that for typical electrode charges and charge on the glass insulator that encases the ultramicroelectrode (UME) tip used in SECM, there are profound effects on the voltammetric wave-shapes for redox reactions of charged redox couples, in the common modes used to study electron transfer kinetics, namely the tip-voltammetry (feedback) mode and substrate-voltammetry (substrate-generation/tip-collection and competition) modes. Using the reduction and oxidation of a singly charged redox species to a neutral and doubly charged species, respectively, as exemplar systems, it is shown that the charge on the electrodes can greatly distort the voltammetric wave-shape, while charge on the glass that surrounds the UME tip can affect the limiting current. Analysis of SECM voltammograms using methods that do not account for double layer effects will thus result in significant error in the kinetic values derived and tip-substrate distances that have to be estimated from limiting currents in SECM. The model herein provides a framework that could be developed for further studies with nanogap-SECM (e.g. consideration of alternative models for the electrical double layer, other supporting electrolyte concentrations, potential of zero charge on the electrodes and charges on the redox couples). The model results presented are shown to qualitatively match to SECM voltammetric features from experimental data in the literature, and are further supported by experimental data for redox processes of tetrathiafulvalene (TTF), namely the TTF/TTF+ and TTF+/TTF2+ redox couples. This serves to demonstrate the immediate practical application of some of the ideas presented herein. For future applications of SECM, the use of different supporting electrolyte concentrations and a range of tip-substrate separations may allow the determination of both electron transfer kinetics and double layer properties

Electrochemistry of Fe3+/2+ at highly oriented pyrolytic graphite (HOPG) electrodes : kinetics, identification of major electroactive sites and time effects on the response

The electrochemistry of the Fe3+/2+ redox couple has been studied on highly oriented pyrolytic graphite (HOPG) samples that differ in step edge density by 2 orders of magnitude to elucidate the effect of surface structure on the electron transfer (ET) kinetics. Macroscopic cyclic voltammetry measurements in a droplet-cell arrangement, highlight that the Fe3+/2+ process is characterised by slow ET kinetics on HOPG and that step edge coverage has little effect on the electrochemistry of Fe3+/2+. A standard heterogeneous ET rate constant of ~5 × 10-5 cm s-1 for freshly cleaved HOPG was derived from simulation of the experimental results, which fell into the range of the values reported for metal eletrodes, e.g. platinum and gold, despite the remarkable difference in density of electronic states (DOS) between HOPG and metal electrodes. This provides further evidence that outer-sphere redox processes on metal and sp2 carbon electrodes appear to be adiabatic. Complementary surface electroactivity mapping of HOPG, using scanning electrochemical cell microscopy, reveal the basal plane to be the predominant site for the Fe3+/2+ redox process. It is found that time after cleavage of the HOPG surface has an impact on the surface wettability (and surface contamination), as determined by contact angle measurements, and that this leads to a slow deterioration of the kinetics. These studies further confirm the importance of understanding and evaluating surface structure and history effects in HOPG electrochemistry, and how high resolution measurements, coupled with macroscopic studies provide a holistic view of electrochemical processes

Impact of adsorption on scanning electrochemical microscopy voltammetry and implications for nanogap measurements

Scanning electrochemical microscopy (SECM) is a powerful tool that enables quantitative measurements of fast electron transfer (ET) kinetics when coupled with modeling predictions from finite-element simulations. However, the advent of nanoscale and nanogap electrode geometries that have an intrinsically high surface area-to-solution volume ratio realizes the need for more rigorous data analysis procedures, as surface effects such as adsorption may play an important role. The oxidation of ferrocenylmethyl trimethylammonium (FcTMA+) at highly oriented pyrolytic graphite (HOPG) is used as a model system to demonstrate the effects of reversible reactant adsorption on the SECM response. Furthermore, the adsorption of FcTMA2+ species onto glass, which is often used to encapsulate ultramicroelectrodes employed in SECM, is also found to be important and affects the voltammetric tip response in a nanogap geometry. If a researcher is unaware of such effects (which may not be readily apparent in slow to moderate scan voltammetry) and analyzes SECM data assuming simple ET kinetics at the substrate and an inert insulator support around the tip, the result is the incorrect assignment of tip–substrate heights, kinetics, and thermodynamic parameters. Thus, SECM kinetic measurements, particularly in a nanogap configuration where the ET kinetics are often very fast (only just distinguishable from reversible), require that such effects are fully characterized. This is possible by expanding the number of experimental variables, including the voltammetric scan rate and concentration of redox species, among others

Consumer personality, privacy concerns and usage of location-based services (LBS)

This paper examines the effects of the Big Five personality traits on concern for information privacy (CFIP) and the effects of the formulated concern for information privacy towards perceived risk, which in turn determine location-based services (LBS) usage intention. Data for this research was collected from 291 users and non-users of LBS. Result from Pearson correlation analysis indicated significant relationships exist between: (1) extraversion, and openness with collection; (2) extraversion, conscientiousness, and openness with improper access; (3) extraversion, conscientiousness, and openness with errors; (4) agreeableness, neuroticism, and openness with secondary use. All four dimensions of CFIP are found to have a significant direct relationship with perceived risk of using LBS. Implications for research and practice for location-based service providers are discussed

The effects of intravenous infusion of autologous mesenchymal stromal cells in patients with subacute middle cerebral artery infarct: a phase 2 randomized controlled trial on safety, tolerability and efficacy

Background aims Mesenchymal stromal cells (MSCs) are characterized by paracrine and immunomodulatory functions capable of changing the microenvironment of damaged brain tissue toward a more regenerative and less inflammatory milieu. The authors conducted a phase 2, single-center, assessor-blinded randomized controlled trial to investigate the safety and efficacy of intravenous autologous bone marrow-derived MSCs (BMMSCs) in patients with subacute middle cerebral artery (MCA) infarct. Methods Patients aged 30-75 years who had severe ischemic stroke (National Institutes of Health Stroke Scale [NIHSS] score of 10-35) involving the MCA territory were recruited within 2 months of stroke onset. Using permuted block randomization, patients were assigned to receive 2 million BMMSCs per kilogram of body weight (treatment group) or standard medical care (control group). The primary outcomes were the NIHSS, modified Rankin Scale (mRS), Barthel Index (BI) and total infarct volume on brain magnetic resonance imaging (MRI) at 12 months. All outcome assessments were performed by blinded assessors. Per protocol, analyses were performed for between-group comparisons. Results Seventeen patients were recruited. Nine were assigned to the treatment group, and eight were controls. All patients were severely disabled following their MCA infarct (median mRS = 4.0 [4.0-5.0], BI = 5.0 [5.0-25.0], NIHSS = 16.0 [11.5-21.0]). The baseline infarct volume on the MRI was larger in the treatment group (median, 71.7 [30.5-101.7] mL versus 26.7 [12.9-75.3] mL, P = 0.10). There were no between-group differences in median NIHSS score (7.0 versus 6.0, P = 0.96), mRS (2.0 versus 3.0, P = 0.38) or BI (95.0 versus 67.5, P = 0.33) at 12 months. At 12 months, there was significant improvement in absolute change in median infarct volume, but not in total infarct volume, from baseline in the treatment group (P = 0.027). No treatment-related adverse effects occurred in the BMMSC group. Conclusions Intravenous infusion of BMMSCs in patients with subacute MCA infarct was safe and well tolerated. Although there was no neurological recovery or functional outcome improvement at 12 months, there was improvement in absolute change in median infarct volume in the treatment group. Larger, well-designed studies are warranted to confirm this and the efficacy of BMMSCs in ischemic stroke

Real-Time Observation of Iodide Ion Migration in Methylammonium Lead Halide Perovskites

Organic-inorganic metal-halide perovskites (e.g. CH3NH3PbI3-xClx) emerged as a promising opto-electronic material. However, the Shockley–Queisser Limit for the power conversion efficiency (PCE) of perovskite-based photovoltaic devices has still not been reached, which was attributed to non-radiative recombination pathways, as suggested by photoluminescence (PL) inactive (or dark) areas on perovskite films. Although these observations have been related to the presence of ions/defects, the underlying fundamental physics and detailed microscopic processes, concerning trap/defect status, ion migration, etc., still remain poorly understood. Here we utilize correlated wide-field PL microscopy and impedance spectroscopy (IS) on perovskite films to in-situ investigate both the spatial and temporal evolution of these PL inactive areas under external electrical fields. We attribute the formation of PL inactive domains to the migration and accumulation of iodine ions under external fields. Hence we are able to characterize the kinetic processes and determine the drift velocities of these ions. In addition, we show that I2 vapor directly affects the PL quenching of a perovskite film, which provides evidence that the migration/segregation of iodide ions plays an important role in the PL quenching and consequently limits the PCE of organometal halide based perovskite photovoltaic devices

Risk factors for long-term cardiovascular post-acute sequelae of COVID-19 infection: A nested case-control study in Hong Kong

People with COVID-19 can experience post-acute sequelae of SARS-CoV-2 (PASC). Studies on risk factors of PASC outcomes are ongoing, especially for endocrine system-related diseases that may impact the cardiovascular system. Cardiac-related PASC is one of the burdens after COVID-19 infection. This study aimed to examine the risk factors of cardiac-related PASC. In this nested case-control study, we obtained electronic health records (EHRs) database from the Hong Kong Hospital Authority. We defined cases as patients with at least one cardiac-related PASC and controls as patients without any cardiac-related PASC. We applied the incidence density sampling and matched controls to cases on age and sex at a 1:10 ratio. Multivariable conditional logistic regression was used to determine the associations between risk factors and cardiac-related PASC. A total of 455 individuals with cardiac-related PASC and matched 3,423 controls were obtained in the underlying cohort. COVID-19-associated hospitalisation (aOR: 1.41, 95% CI: 1.03–1.93) and peripheral vascular disease (aOR: 2.98, 95% CI: 1.31–6.79) were associated with an increased likelihood of cardiac-related PASC. Higher doses of the COVID-19 vaccine (2 doses: 0.68 [0.52–0.89]; ≥3 doses: 0.56 [0.40–0.78]) and more frequent healthcare utilization visits (aOR: 0.95, 95% CI: 0.92–0.97) were associated with a lower likelihood of cardiac-related PASC. This is the first study to examine risk factors of cardiac-related PASC among the Chinese population. We identified peripheral vascular disease and COVID-19-associated hospitalisation as the risk factors for cardiac-related PASC. COVID-19 vaccination was protective against cardiac-related PASC, which should be prioritized for high-risk patients

Long-term effects of coronavirus disease 2019 on diabetes complications and mortality in people with diabetes:Two cohorts in the UK and Hong Kong

AIM: To evaluate the long-term associations between coronavirus disease 2019 (COVID-19) and diabetes complications and mortality, in patients with diabetes. MATERIALS AND METHODS: People with diabetes diagnosed with COVID-19 infection (exposed group), from 16 March 2020 to 31 May 2021 from the UK Biobank (UKB cohort; n = 2456), and from 1 April 2020 to 31 May 2022 from the electronic health records in Hong Kong (HK cohort; n = 80 546), were recruited. Each patient was randomly matched with participants with diabetes but without COVID-19 (unexposed group), based on age and sex (UKB, n = 41 801; HK, n = 391 849). Patients were followed for up to 18 months until 31 August 2021 for UKB, and up to 28 months until 15 August 2022 for HK. Characteristics between cohorts were further adjusted with Inverse Probability Treatment Weighting. Long-term association of COVID-19 with multi-organ disease complications and all-cause mortality after 21 days of diagnosis was evaluated by Cox regression. RESULTS: Compared with uninfected participants, patients with COVID-19 infection with diabetes were consistently associated with higher risks of cardiovascular diseases (coronary heart disease [CHD]: hazard ratio [HR] [UKB]: 1.6 [95% confidence interval {CI}: 1.0, 2.4], HR [HK]: 1.2 [95% CI: 1.0, 1.5]; and stroke: HR [UKB]: 2.0 [95% CI: 1.1, 3.6], HR [HK]: 1.5 [95% CI: 1.3, 1.8]), microvascular disease (end stage renal disease: HR [UKB]: 2.1 [95% CI: 1.1, 4.0], HR [HK]: 1.2 [95% CI: 1.1, 1.4]) and all-cause mortality (HR [UKB]: 4.6 [95% CI: 3.8, 5.5], HR [HK]: 2.6 [95% CI: 2.5, 2.8]), in both cohorts. CONCLUSIONS: COVID-19 infection is associated with long-term increased risks of diabetes complications (especially cardiovascular complications, and mortality) in people with diabetes. Monitoring for signs/symptoms of developing these long-term complications post-COVID-19 infection in the infected patient population of people with diabetes may be beneficial in minimizing their morbidity and mortality