Selectivity Enhancement for Chloride Ion by In(III)‐Porphyrin‐Based Polymeric Membrane Electrode Operated in Pulsed Chronopotentiometric Mode

A robust selectivity enhancement of an In(III)‐porphyrin ionophore‐based chloride‐selective electrode under pulsed chronopotentiometric measurement mode that enables the detection of chloride ions in the presence of a normally interfering concentration of salicylate ions is described. This enhancement is achieved by the rapid depletion of the surface concentration of the more dilute lipophilic anion during an initial anodic current pulse period due to extraction of this preferred anion into the membrane phase. Measurement of chloride with a detection limit of 8 mM and near Nernstian response slope in the presence of 1 mM salicylate is possible using the pulstrode method.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/90345/1/643_ftp.pd

Flash chronopotentiometric sensing of the polyions protamine and heparin at ion-selective membranes

We report here on a highly sensitive and rapid detection technique, multipulse flash chronopotentiometry, for the anticoagulant polyion heparin and its antidote protamine. The technique is based on a localized titration of the polyions at the surface of an appropriately formulated polymeric ion-selective membrane devoid of ion exchange properties to prohibit spontaneous extraction processes. A defined ion flux from the sample side to the membrane is induced electrochemically by applying a current pulse of appropriate amplitude and sign. The resulting depletion of the measured ions at the membrane surface gives rise to a characteristic limiting current or transition time and is observed as an inflection point in the resulting chronopotentiogram. The limiting current and the square root of the transition time are linear functions of the concentration of the polyion and yield sensitive and rapid analytical information attractive for clinical diagnostics applications. The polyion protamine is detected in 10-fold diluted blood samples in a matter of seconds via a cathodic current pulse. The utility of the technique for monitoring heparin/protamine titrations in physiological saline solutions is demonstrated

Beyond potentiometry: Robust electrochemical ion sensor concepts in view of remote chemical sensing

For about 100 years, potentiometry with ion-selective electrodes has been one of the dominating electroanalytical techniques. While great advances in terms of selective chemistries and materials have been achieved in recent years, the basic manner in which ion-selective membranes are used has not fundamentally changed. The potential readings are directly co-dependent on the potential at the reference electrode, which requires maintenance and for which very few accepted alternatives have been proposed. Fouling or clogging of the exposed electrode surfaces will lead to changes in the observed potential. At the same time, the Nernst equation predicts quite small potential changes, on the order of millivolts for concentration changes on the order of a factor two, making frequent recalibration, accurate temperature control and electrode maintenance keyrequirements of routine analytical measurements. While the relatively advanced selective materials developed for ion-selective sensors would be highly attractive for low power remote sensing application, one should consider solutions beyond classical potentiometry to make this technology practically feasible. This paper evaluates some recent examples that may be attractive solutions to the stated problems that face potentiometric measurements. These include high-amplitude sensing approaches, with sensitivities that are an order of magnitude larger than predicted by the Nernst equation; backside calibration potentiometry, where knowledge of the magnitude of the potential is irrelevant and the system is evaluated from the backside of the membrane; controlled current coulometry with ion-selective membranes, an attractive technique for calibration-free reagent delivery without the need for standards or volumetry; localized electrochemical titrations at ion-selective membranes, making it possible to design sensors that directly monitor parameters such as total acidity for which volumetric techniques were traditionally used; and controlled potential coulometry, where all ions of interest are selectively transferred into the ion-selective organic phase, forming a calibration-free technique that would be exquisitely suitable for remote sensing applications

Pulsed Chronopotentiometry with Polymer-Based Potassium-Selective Electrodes

This research aimed to develop ion-selective electrodes selective to potassium for use in measuring potassium concentration in blood. Potassium is an important electrolyte within the body, orchestrating nerve excitation, muscular function, and heart rate. Excessive or insufficient potassium levels can cause breakdowns in these systems difficult to differentiate from other potential causes. Isolating potassium concentration as the sole cause necessitates selective measurement. Pulsed Chronopotentiometry with polymer-based membrane electrodes offered a versatile route of interrogation: membrane composition and magnitude of applied current can be altered to assess selectivity in a fast and controlled manner. All potential measurements recorded corresponded to known concentrations of potassium. Known concentrations were first used to construct calibration curves, then to explore depletion of ions at the membrane surface. The latter offers a method of measurement not requiring calibration. Both methods saw success when measuring potassium alone, while depletion proved difficult in presence of sodium

Pulsed chronopotentiometric membrane electrodes based on plasticized poly(vinyl chloride) with covalently bound ferrocene functionalities as solid contact transducer

Ion-selective membrane materials based on poly(vinyl chloride) (PVC)-containing covalently attached redox-active ferrocene (Fc) groups are characterized here as all-solid-state pulsed voltammetric ion sensors. The redox capacity of the membrane increases 7-fold with a doubling of the Fc content and 3-fold with the addition of 10 wt % of the lipophilic electrolyte ETH 500, tetradodecylammonium tetrakis(4-chlorophenyl) borate. This salt improves the ionic conductivity of the membrane and appears to make the Fc groups electrochemically more accessible. A too high content of the two, on the other hand, was found to cause undesired sensitivity to redox-active species present in the sample solution. Dilution of the membrane with a plasticizer eliminated this redox sensitivity while preserving its high redox capacity. A practical application of the designed electrodes in electrochemical analysis was demonstrated with a multi-pulse protocol that includes a current-controlled ion uptake pulse, followed by an open-circuit potential (OCP) measurement and a regeneration pulse. Potentiometric calibration curves obtained with this protocol exhibited a linear response with near-Nernstian slopes for acetate, nitrate, chloride, and perchlorate ions with the selectivity expected for an ion-exchanging membrane

Polyion‐Sensitive Polymeric Membrane‐Based Pulstrode as a Potentiometric Detector in Liquid Chromatography

Potentiometric polyion‐sensitive polymeric membrane electrodes are capable of detecting a wide variety of polyionic macromolecules. Herein, we utilize this lack of selectivity to report the first application of this sensor technology as a detector in liquid chromatography (LC). A reversible polycation pulstrode based on tridodecylmethylammonium‐dinonylnaphthalene sulfonate doped within a polymeric membrane is employed as the LC detector. Poly‐arginines/protamine mixtures are separated by cation‐exchange/affinity chromatography on an immobilized heparin column, with eluted polycation peptide bands clearly observed via the pulstrode detector. The LC‐pulstrode system is further applied to follow the production of different polycation peptides derived from thermolysin catalyzed protamine digestion.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/113143/1/1823_ftp.pd