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.

Time-dependent phenomena in the potential response of ion-selective electrodes treated by the Nernst-Planck-Poisson model. 1. Intramembrane processes and selectivity.

The variability of selectivity coefficients, resulting from potential changes over time and the concentration ratio of primary to interfering ions, impedes many practical applications of ion-selective electrodes (ISEs). Existing theoretical interpretations of ISE selectivity are restricted by severe assumptions, such as steady state and electroneutrality, which hinder theorizing on this problem. For this reason, for the first time, the Nernst-Planck-Poisson equations are used to predict and visualize the selectivity variability over time and the concentration ratio. Special emphasis is placed on the non-Nernstian response in the measurements with liquid-ion-exchanger- and neutral-carrier-based ISEs. The conditions under which measured selectivity coefficients are true (unbiased) are demonstrated.

Ion-selective electrode for measuring low Ca2+ concentrations in the presence of high K+, Na+ and Mg2+ background.

In this work, ion-selective electrodes for calcium ion were investigated. Two ionophores were used in the membranes: ETH 1001 and ETH 129. An internal filling solution buffered for primary ion was used that allowed the lower detection limit to be decreased down to 10(-8.8) M. Theoretical and experimental electrode characteristics pertaining to both primary and interfering ions are discussed. Better behavior was obtained with the electrode prepared with ETH 129 in the membrane. This electrode would be the most likely candidate for obtaining a low Ca(2+) detection limit in measurements performed with high K(+), Na(+), Mg(2+) background, which is found inside the cells of living organisms, for example. The potentiometric response of the electrode in solutions containing main and interfering ions is in good agreement with simulated curves obtained using the Nernst-Planck-Poisson (NPP) model.

Vibrational spectroscopy of 3,4-difluorocyclobutenes: cis-d0, trans-d0 and trans-d4 species.

Infrared and Raman spectra were recorded for cis-3,4-difluorocyclobutene (cDFCB) and trans-3,4-difluorocyclobutene-d4. Unscaled density functional theory (DFT) calculations of frequencies and intensities at the B3LYP/6-311++G(d,p) level supported the complete assignment of the vibrational fundamentals. The previous assignment of fundamentals of trans-3,4-difluorocyclobutene was revised. An unusual blue shift occurs for the methylenic CH-stretching frequencies of cis-3,4-difluorocyclobutene in going from the gas phase to the liquid phase. This hydrogen bond effect is related to similar observations recently reported and interpreted. The blue shift does not occur for the vinylic CH bonds of the cis isomer and does not occur for either type of CH bond in the trans isomer.