Cyclic voltammetry in weakly supported media: The reduction of the cobaltocenium cation in acetonitrile – Comparison between theory and experiment

Limon-Petersen, Juan G.; Dickinson, Edmund J. F.; Belding, Stephen R.; Rees, Neil V.; Compton, Richard G.

doi:10.1016/j.jelechem.2010.08.011

Cited by 20 publications

(13 citation statements)

References 31 publications

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“…This is separate to the issues of solution conductivity and weakly supported voltammetry resulting in increased resistance and unscreened electric fields. 36 This triad of complications present significant barriers to electrochemical detection which must be addressed. Due to the aforementioned issues with the electrochemistry of glutathione and glutathione disulfide there have been a number of routes investigated to attempt to improve the voltammetric signals for these species.…”

Section: Detection Methodsmentioning

confidence: 99%

Electrochemical determination of glutathione: a review

Harfield

Batchelor‐McAuley

Compton

2012

Analyst

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198

136

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The physiological importance of glutathione and glutathione disulfide is evident from their implications in an array of medical conditions including diabetes, Parkinson's disease and cancer. As such the need for simple, rapid and cheap assays to aid clinical diagnostics and treatment is clear. These requirements are, in principle at least, ideally suited to electrochemical detection. Accordingly a large array of voltammetric methods ultimately aimed at making cheap and most likely disposable electrodes have been reported. This critical review analyses the context in which physiological glutathione measurement can be undertaken electrochemically and compares it to current assay approaches, while also covering the current literature for glutathione disulfide detection. The various characteristics and limitations of the methodologies are compared and contrasted, with the analytical parameters (matrix, pH, limit of detection, etc.) tabulated to aid comparison.

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Section: Detection Methodsmentioning

confidence: 99%

Electrochemical determination of glutathione: a review

Harfield

Batchelor‐McAuley

Compton

2012

Analyst

Self Cite

198

136

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“…However, the experimental electrical conductivity of "pure" acetonitrile (6.6 × 10 −10 Ω −1 cm −1 [52]) is much larger compared to a theoretical estimation based on the self-dissociation of the solvent (≈ 10 −17 Ω −1 cm −1 ). Moreover, a comparison between simulated cyclic voltammograms and experiments for the weakly-supported cobaltocenium-cobaltocene couple in acetonitrile at a microhemispherical mercury electrode suggests that ionic impurities are easily introduced when using "as received" chemicals without further purification [53]. Hence, sufficient ionic impurities are usually present so that the Debye length is indeed much smaller than the typical interelectrode distance of >100 µm.…”

Section: Model Equationsmentioning

confidence: 99%

Current and concentration distributions in electrochemical microreactors: Numerical calculations and asymptotic approximations for self-supported paired synthesis

Fransen

Fransaer

Kuhn

2018

Electrochimica Acta

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Weakly-supported electrolyses are frequently encountered in organic electrosynthesis in small scale flow reactors. Sometimes "self-supported" electrolyses are reported where no supporting electrolyte is deliberately added at all. To interpret the steady-state and transient behavior of these electrochemical micro-and millireactors, an orthogonal collocation method based on Chebyshev polynomials was developed for calculating the concentration and current distributions in parallel plate and annular geometries. This method takes into account diffusion, migration, and convection in unidirectional flow for an arbitrary number of dilute ionic species. In particular, the method is flexible with regard to the electrode and homogenous reactions so that intricate reaction schemes are conveniently simulated. As a case study, the effect of the supporting electrolyte concentration and the stability of the generated reactive intermediate ions on a generic paired electrosynthesis is investigated. The numerically calculated concentration profiles and current responses are then compared with asymptotic approximations. This reveals that fundamentally different operating regimes exist for a self-supported paired electrolysis compared to more conventional electrolyses where an excess of supporting electrolyte is added. The Matlab code and a detailed user guide is freely available via the Supplementary Information.

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“…This model has been extensively discussed by several authors to interpret different aspects of the electrical response of a medium containing ions submitted to an external excitation [8][9][10][11][12][13][14][15][16][17].…”

Section: Model Of Poisson-nernst-planckmentioning

confidence: 99%

“…It is based on the equation of continuity for the mobile ions, stating the conservation of the number of ions, and on the equation of Poisson, relating the actual electric potential to the bulk density of ions [7]. This model is also known as model of Poisson-NernstPlanck [8][9][10]. The predictions of this model for a symmetric sample in the shape of a slab limited by partially blocking electrodes are discussed in Section 3.…”

Section: Introductionmentioning

confidence: 99%