Scanning electrochemical microscopy (SECM) supplemented with potentiometric measurements was used to follow the time-dependent buildup of a steady-state diffusion layer at the aqueous-phase boundary of lead ion-selective electrodes (ISEs). Differential pulse voltammetry is adapted to SECM for probing the local concentration profiles at the sample side of solvent polymeric membranes. Major factors affecting the membrane transport-related surface concentrations were identified from SECM data and the potentiometric transients obtained under different experimental conditions (inner filling solution composition, membrane thickness, surface pretreatment). The amperometrically determined surface concentrations correlated well with the lower detection limits of the lead ion-selective electrodes.

The fabrication of a solid-contact, micropipette-based magnesium ion-selective micro-tipped electrode (ISME) suitable for scanning electrochemical microscopy is reported and compared against a conventional micro-tipped ISME having a conventional aqueous internal reference electrode. Measurements showed that the solid-contact ISME had a lower internal resistance and a faster response time than the one with a liquid-contact. These advantages increased the spatial distribution and improved 2D images depicting concentration distributions of Mg 2+ . The ability of the microelectrode to image local ionic concentration has been tested over magnesium surfaces freely corroding or galvanically coupled to iron in aqueous chloride-containing solution. Scans of magnesium ion distribution, in the absence of corrosion currents, were also made over a micro-pipette source containing a concentrated magnesium chloride gel as a source of Mg 2+ and over a current source in the absence of Mg 2+ . From these measurements it was concluded that the potentiometric measurements over corroding surfaces were dominated by the changes in Mg 2+ distributions with small electric potential contributions due to corrosion current.

Pretty choosy: The selectivity filters of biological ion channels serve as inspiration for the development of ionophore‐modified solid‐state nanopores exhibiting extraordinary ion selectivity (see picture). Potentiometric transduction is introduced as a simple means to demonstrate the ion‐sensing capability of such nanopores.

Ten Ag + -selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with π-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag + sensors can be maintained in the subnanomolar range for at least one month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3× 10 −11 M (potentiometrically) and 2 × 10 −11 M Ag + (optically) are found with bridged thiacalixarenes.

The applicability of scanning electrochemical microscopy for the local detection and quantification of relevant species participating in the corrosion of magnesium-based materials is presented. The ironmagnesium galvanic pair exposed to aqueous NaCl solution was adopted as model system for this purpose. Mg 2+ ion concentration and pH profiles were investigated using ion selective electrodes, containing a liquid membrane and Sb/Sb 2 O 3 as sensor elements, respectively. Oxygen consumption at the substrate related to the cathodic reaction was also monitored with the antimony-based electrode though operated amperometrically. Data show a major production of hydroxyl anions at the cathodic sites as result of the oxygen reduction half-reaction, whereas in the vicinity of the magnesium surface pH is greatly affected by the anodic dissolution process instead. The later produces the release of metal cations accompanied by hydrogen evolution.

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