Backside calibration potentiometry: ion activity measurements with selective supported liquid membranes by calibrating from the inner side of the membrane.

In direct potentiometry, the magnitude of the measured potentials is used to determine the composition of the sample. While this places rather formidable demands on the required reproducibility of the associated potential measurements, typically on the order of microvolts, in vitro clinical analyses of blood samples are today successfully performed with direct potentiometry using ion-selective electrodes (ISEs). Unfortunately, most other analytical situations do not permit the sensor to be recalibrated every few minutes, as in environmental monitoring or in vivo measurements, and direct potentiometry is often bound to fail as an accurate method in these circumstances. This paper introduces a novel direction for potentiometric sensing, termed backside calibration potentiometry. Chemical asymmetries across thin supported liquid ISE membranes are assessed by determining the direction of potential drift upon changing the stirring rate on either side of the membrane. Disappearance of this drift indicates the disappearance of concentration gradients across the membrane and is used to determine the sample composition if the solution composition at the backside of the membrane and the interfering ion concentration in the sample are known. For practical determinations, the concentration of either the primary or the interfering ion is varied in the reference solution until the stirring effect disappears. The procedure is demonstrated with a Ca2+-selective membrane using Ba2+ as the dominant interfering ion. Another example includes the determination of Pb2+ in environmental samples where the pH is adjusted to a known level. At pH 4.0, H+ turns out to be the dominant interfering ion. The practical applicability of the method is shown with different environmental water samples, for which the results obtained with the novel method are compared with those obtained by traditional calibration using standard additions. The limitations of the novel method in terms of accuracy and applicable concentration ranges are discussed.

Potentiometry at trace levels in confined samples: ion-selective electrodes with subfemtomole detection limits.

We explore here for the first time the direct potentiometric detectability of calcium, lead, and silver ions in amounts on the order of 300 attomoles at 100 picomolar concentrations without any preconcentration, analyte recycling, or electrocatalytic signal enhancement. The results presented here place zero-current potentiometry among the most sensitive electrochemical methods available.

Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits.

Ten Ag+-selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with pi-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 1 month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3 x 10(-11) M (potentiometrically) and 2 x 10(-11) M Ag+ (optically) are found with bridged thiacalixarenes.

Ion-selective supported liquid membranes placed under steady-state diffusion control.

Supported liquid membranes are used here to establish steady-state concentration profiles across ion-selective membranes rapidly and reproducibly. This opens up new avenues in the area of nonequilibrium potentiometry, where reproducible accumulation and depletion processes at ion-selective membranes may be used to gain valuable analytical information about the sample. Until today, drifting signals originating from a slowly developing concentration profile across the ion-selective membrane made such approaches impractical in zero current potentiometry. Here, calcium- and silver-selective membranes were placed between two identical aqueous electrolyte solutions, and the open circuit potential was monitored upon changing the composition of one solution. Steady state was reached in approximately 1 min with 25-microm porous polypropylene membranes filled with bis(2-ethylhexyl) sebacate doped with ionophore and lipophilic ion exchanger. Ion transport across the membrane resulted on the basis of nonsymmetric ion-exchange processes at both membrane sides. The steady-state potential was calculated as the sum of the two membrane phase boundary potentials, and good correspondence to experiment was observed. Concentration polarizations in the contacting aqueous phases were confirmed with stirring experiments. It was found that interferences (barium in the case of calcium electrodes and potassium with silver electrodes) induce a larger potential change than expected with the Nicolsky equation because they influence the level of polarization of the primary ion (calcium or silver) that remains potential determining.

Ionized magnesium in erythrocytes--the best magnesium parameter to observe hypo- or hypermagnesemia.

BACKGROUND: Almost 99% of the body magnesium is inside cells. The concentration of intracellular ionized magnesium (iMg) is physiologically relevant. iMg in erythrocytes is a new parameter that can help to establish reliable information on the functional magnesium status. METHODS: iMg concentration in erythrocytes and serum was measured by ion-selective electrode, in clinical analyzer Microlyte (KONE). Total magnesium (tMg) concentration was measured by atomic absorption spectrometry (AAS). Albumin and total protein concentration were measured colorimetrically. RESULTS: In critically ill postoperative patients, the mean of albumin, protein and hematocrit concentration was significantly lower compared to healthy individuals. Hypomagnesemia was found in 15.9% patients as tMgs, at 22.2% as iMgs and 36.5% as iMge. Significant correlations are between iMgs and tMgs or iMge and iMgs/tMgs. In dialyzed patients, the mean of hematocrit was significantly lower, iMge was significantly higher compared with healthy individuals. Significant negative correlations are between iMgs and tMge or iMge/tMge and tMge. CONCLUSIONS: iMge is the best magnesium parameter to observe hypo- or hypermagnesemia for both groups of patients. The function of magnesium is mainly intracellular and intracellular magnesium concentrations can be the method to evaluate the magnesium status.

Improving the detection limit of anion-selective electrodes: an iodide-selective membrane with a nanomolar detection limit.

The lower detection limit and the selectivity behavior of anion-selective electrodes (ISEs) are improved by using optimized inner solutions and membrane compositions. With a membrane based on the recently described ionophore [9]mercuracarborand-3, a detection limit of 2 x 10(-9) M has been achieved for iodide. Nevertheless, the improvements are less pronounced than in the case of cation ISEs. This is mainly due to the fact that so far no anion ISE is known with the extremely high selectivities of cation ISEs. If the membrane does not contain an ionophore, leaching of the ion exchanger from the membrane into the sample is also a relevant limiting factor except for ion exchangers of very high lipophilicity.

Comparison of the potentiometric, (31)P NMR, and zero-point titration methods of determining ionized magnesium in erythrocytes.

A simple and rapid method of determining ionized magnesium in erythrocytes using a potentiometric clinical analyzer, Microlyte 6 (Kone, Finland), was investigated. The erythrocyte cell membranes were destroyed using ultrasound. The results were compared with those obtained with the (31)P nuclear magnetic resonance spectroscopy method and the zero-point titration method using atomic absorption spectrometry. The results obtained from potentiometry and from the other methods did not differ significantly (Student t test, alpha = 0.01). Total magnesium concentration was determined using atomic absorption spectrometry.