Electrically Enhanced Sensitivity (EES) of Ion-Selective Membrane Electrodes and Membrane-Based Ion Sensors.

The use of external electronic enforcement in ion-sensor measurements is described. The objective is to improve the open-circuit (potentiometric) sensitivity of ion sensors. The sensitivity determines the precision of analyte determination and has been of interest since the beginning of ion-sensor technology. Owing to the theoretical interpretation founded by W.E. Nernst, the sensitivity is characterized by the slope and numerically predicted. It is empirically determined and validated during calibration by measuring an electromotive force between the ion sensor and the reference electrode. In practice, this measurement is made with commercial potentiometers that function as unaltered "black boxes". This report demonstrates that by gaining access to a meter's electrical systems and allowing for versatile signal summations, the empirical slope can be increased favorably. To prove the validity of the approach presented, flow-through ion-sensor blocks used in routine measurements of blood electrolytes (Na+, K+, Li+, Cl-) and multielectrode probes with flat surfaces, similar to those applied previously for monitoring transmembrane fluxes of Na+, K+, Cl- through living biological cells, are used. Several options to serve real-life electroanalytical challenges, including linear calibration for sensors with high-resistance membranes, responses with non-Nernstian slopes, non-linear calibration, and discrimination of nonfunctional sensors, are shown.

The Use of an Acylhydrazone-Based Metal-Organic Framework in Solid-Contact Potassium-Selective Electrode for Water Analysis.

A solid-contact ion-selective electrode was developed for detecting potassium in environmental water. Two versions of a stable cadmium acylhydrazone-based metal organic framework, i.e., JUK-13 and JUK-13_H2O, were used for the construction of the mediation layer. The potentiometric and electrochemical characterizations of the proposed electrodes were carried out. The implementation of the JUK-13_H2O interlayer is shown to improve the potentiometric response and stability of measured potential. The electrode exhibits a good Nernstian slope (56.30 mV/decade) in the concentration range from 10-5 to 10-1 mol L-1 with a detection limit of 2.1 µmol L-1. The long-term potential stability shows a small drift of 0.32 mV h-1 over 67 h. The electrode displays a good selectivity comparable to ion-selective electrodes with the same membrane. The K-JUK-13_H2O-ISE was successfully applied for the determination of potassium in three certified reference materials of environmental water with great precision (RSD < 3.00%) and accuracy (RE < 3.00%).

Solid-Contact Electrode with Composite PVC-Based 3D-Printed Membrane. Optimization of Fabrication and Performance.

Intense interest in reference electrode design and fabrication has recently been enriched with the application of 3D printing of electrodes with salt-loaded PVC membranes. This type of material is attractive in sensor technology and is challenging to implement in 3D. In this report, several improvements and simplifications in the technology were focused on and supported by a fundamental electrochemical characterization.

3D-printed manifold integrating solid contact ion-selective electrodes for multiplexed ion concentration measurements in urine.

Urinalysis is a simple and non-invasive approach for the diagnosis and monitoring of various health disorders. While urinalysis is predominantly confined to clinical laboratories the non-invasive sample collection makes it applicable in wide range of settings outside of central laboratory confinements. In this respect, 3D printed devices integrating sensors for measuring multiple parameters may be one of the most viable approaches to ensure cost-effectiveness for widespread use. Here we evaluated such a system for the multiplexed determination of sodium, potassium and calcium ions in urine samples with ion-selective electrodes based on state of the art octadecylamine-functionalized multi-walled carbon nanotube (OD-MWCNT) solid contacts. The electrodes were tested in the clinically relevant concentration range, i.e. ca. 10-4 - 10-1 mol L-1 and were proven to have Nernstian responses under flow injection conditions. The applicability of the 3D printed flow manifold was investigated through the analysis of synthetic samples and two certified reference materials. The obtained results confirm the suitability of the proposed system for multiplexed ion analysis in urine.

3D-printed flow manifold based on potentiometric measurements with solid-state ion-selective electrodes and dedicated to multicomponent water analysis.

A 3D-printed flow manifold dedicated to potentiometric simultaneous determination of potassium, sodium, calcium and chloride in water is presented. The method is based on application of miniature solid-contact ion selective electrodes with a special design obtained with the use of 3D printing. The electrodes offer many attractive advantages including short response time and miniaturization feasibility. The use of the proposed novel electrodes enables performance of rapid potentiometric measurements in flow-injection technique and registration of many injection peaks in a short time. One of the advantages of using a special 3D-printed flow vessel for potentiometric measurements was miniaturization of electrodes and the possibility of integrating several (from three up to six) ion selective electrodes in one module enabling realization of multi-component analyses in the same time. Thanks to that the volume of each solution and measurement time were significantly reduced during multi-component analysis. In order to find out if the proposed manifold works properly, three multi-component synthetic samples and four certified reference materials were analyzed. The presented study shows that the proposed 3D-printed flow manifold with solid-state ion-selective electrodes could be an effective tool in a modern multi-component analysis meeting the requirements of green analytical chemistry.

Reference Electrodes with Polymer-Based Membranes-Comprehensive Performance Characteristics.

Several types of liquid membrane and solid-state reference electrodes based on different plastics were fabricated. In the membranes studied, equitransferent organic (QB) and inorganic salts (KCl) are dispersed in polyvinyl chloride (PVC), polyurethane (PU), urea-formaldehyde resin (UF), polyvinyl acetate (PVA), as well as remelted KCl in order to show the matrix impact on the reference membranes' behavior. The comparison of potentiometic performance was made using specially designed standardized testing protocols. A problem in the reference electrode research and literature has been a lack of standardized testing, which leads to difficulties in comparing different types, qualities, and properties of reference electrodes. Herein, several protocols were developed to test the electrodes' performance with respect to stability over time, pH sensitivity, ionic strength, and various ionic species. All of the prepared reference electrodes performed well in at least some respect and would be suitable for certain applications as described in the text. Most of the reference types, however, demonstrated some weakness that had not been previously highlighted in the literature, due in large part to the lack of exhaustive and/or consistent testing protocols.

A Breakthrough Application of a Cross-Linked Polystyrene Anion-Exchange Membrane for a Hydrogencarbonate Ion-Selective Electrode.

Polystyrene cross-linked with divinylbenzene and functionalized by a quaternary ammonium cation anion site is used as the membrane of a hydrogencarbonate (i.e., bicarbonate) ion-selective electrode. The polystyrene matrix membrane improves the selectivity towards interfering lipophilic ions in comparison to previously described polyvinyl chloride membranes. The reason for this behaviour is sought in coupled ion-exchange and pore-diffusion processes in the membrane and the resulting kinetic discrimination of interfering ions. The electrode is successfully used for determination of bicarbonates in mineral drinking waters. The simplex method is employed to refine the analytical outcome.

All-Solid-State Reference Electrode with Heterogeneous Membrane.

Novel reference electrodes with a solid contact coated by a heterogeneous polymer membrane are described. The electrodes are obtained using Ag nanoparticles, AgBr, KBr suspended in tetrahydrofuran solution of PVC and DOS and deposited on Ag substrate, or another substrate covered with Ag, by drop casting. After a short period of soaking in a KBr solution, stable and reproducible formal potentials of -157 ± 2 mV (vs Ag/AgCl/3 M KCl) were observed, and the solid-contact reference electrodes were ready to use. It is shown that the described reference electrodes are relatively insensitive to the changes in the sample matrix, the concentrations of ions, the pH and the redox potential. These electrodes can also be fabricated in miniaturized form, and thus used to produce miniaturized multielectrode probes.

Galvanic cell without liquid junction for potentiometric determination of copper.

This paper describes potentiometric measurements in an integrated galvanic cell with both indicator and reference electrodes. Both electrodes are conducting polymer-based. The copper-sensitive indicator electrode is made by using poly(3,4-ethylenedioxythiophene) (PEDOT) doped with 2-(o-arsenophenylazo)-1,8-dihydroxynaphthalene-3,6-disulphonic sodium salt (Arsenazo-I) as the electroactive substance in the film, while the reference electrode is based on PEDOT doped by 2-morpholineoethanesulfonic acid (MES). It is shown that the galvanic cell can be used for determination of copper both in non-aqueous media (where all PVC-based membranes failed) and in the presence of chloride ions, which disturb the signal of conventional copper ion-selective electrodes with solid-state membranes. It is further shown that the titration of copper ions can be successfully monitored using the described electrochemical cell.

Conducting polymers in modelling transient potential of biological membranes.

The possibility of using conducting polymer (CP) films doped with biological ligands as artificial biological membranes to study potential formation mechanisms is presented. Calcium and magnesium ion-binding anionic sites--asparagine, glutamine, adenosinotriphosphate and heparin are incorporated into the poly(pyrrole) film during electrochemical polymerization. This approach allows the competitive calcium-magnesium ion-exchange to be inspected by open circuit measurements. After a close-to-Nernstian sensitivity of the CP membranes was induced by soaking in alkaline solutions of calcium or magnesium, dynamic experiments were performed by a change in the bulk concentration of magnesium or calcium ions. A characteristic transitory potential response, though distinctively different for the calcium and magnesium ions, was observed and explained using the diffusion layer model (DML).

Junction-less reference electrode for potentiometric measurements obtained by buffering pH in a conducting polymer matrix.

A reference electrode for potentiometric measurements based on conducting polymers (CP) doped with pH buffering ligands is described. Both the CPs and doping ligands are selected and adjusted in such a way that possible ionic and redox sensitivity is hampered, while the pH buffering property of the CP film is exposed. In this way, the electric potential drop at the conducting polymer|solution interface is stabilized and close to constant over a certain pH range. The electrode behaves as a pseudo-reference electrode in amphiprotic solvents or their mixtures, e.g. water-alcohol mixtures. For the first time titration of sulfates with lead(ii) in water-methanol solution using two "plastic" electrodes, CP-based Pb(2+)-sensitive indicator and CP-based reference electrode, is shown. Because the electrode is junction-less it may easily be miniaturized and maintained and thus may serve in frontier applications of sensors.