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Reduction and nanoparticle nucleation of Cu2+ by decamethylferrocene was studied with cyclic and square‐wave voltammetry at a microscale liquid–liquid interface established at the tip of a micropipette. With square‐wave voltammetry, two reduction steps could be distinguished as two separate current waves. Comparing the experimental results of cyclic voltammetry with finite element method simulations, particle growth could be observed as an increasing limiting current. Furthermore, kinetic parameters could be estimated with square‐wave voltammetry simulations following Butler‐Volmer kinetics. [ABSTRACT FROM AUTHOR]

Metal reduction at the interface between two immiscible electrolyte solutions (ITIES) has been studied with scanning electrochemical microscopy (SECM). Metal cations in the aqueous phase are reduced by 7,7,8,8‐tetracyanoquinodimethane anion (TCNQ−) residing in the oil phase, methyl isobutyl ketone (MIBK). TCNQ− is formed at the SECM tip by reducing TCNQ, which results in a positive feedback loop between the tip and the ITIES when an electron is donated to a metal cation. The effect of the Galvani potential difference on the rate of the interfacial electron transfer was investigated, establishing the potential difference either by an additional substrate electrode in the aqueous phase or by an a common ion in both phases. It is shown that the Galvani potential difference as a driving force does enable TCNQ− mediated Cu2+ reduction. Finite element method (FEM) simulations were run to provide information on the reaction kinetics and stoichiometry. [ABSTRACT FROM AUTHOR]

Aromatic Tb(III) chelates can be detected down to subnanomolar concentrations at polystyrene-carbon black composite electrodes on the basis of hot electron-induced electrochemiluminescence, and used as electrochemiluminescent labels in bioaffinity assays. The excitation mechanism is based on chemiluminescent reactions that are initiated by the field emission/tunnel emission of hot electrons from the composite electrode. The composition and the properties of the novel composite electrodes were studied in detail. Hot electron-induced electrochemiluminescence intensities obtainable with the present composite electrodes are comparable to the previously used metal/insulator-type electrodes without exhibiting considerable long-lived solid state electroluminescence background emission, unlike e.g. oxide-coated silicon and aluminum electrodes. C-reactive protein was finally determined in a heterogeneous sandwich-assay by using the present composite electrodes as a solid support material for the capture antibodies. The detection antibody was labeled with a commercially available Tb(II) chelate. Calibration curve for the determination of C-reactive protein was linear over two orders of magnitude and the detection limit was well below the clinical reference value, approx. 1 μg l −1 . Disposable polystyrene-carbon black composite electrodes are superior alternatives for e.g. silicon-based electrodes due to the low cost, easier manufacturing process and a very good performance e.g. in immunoassays. [ABSTRACT FROM AUTHOR]