Effect of lipophilic ion-exchanger leaching on the detection limit of carrier-based ion-selective electrodes

The equilibrium partitioning of lipophilic ion-exchanger salts from ion-selective polymeric membrane electrodes (ISEs) and its possible effect on the lower detection limit of these sensors is described. Predictions are made on the basis of various parameters, including the knowledge of tetraphenylborate potassium salt partitioning constants, the selectivity of ionophore-free ion-exchanger membranes, and ionophore stability constants in the membrane. Ion-exchanger lipophilicities are significantly increased if the membrane contains an ionophore that strongly binds the primary ion. Predicted detection limits are on the order of 10(-5)-10(-8) M for ionophore-free membranes, and may reach levels as low as 10(-18) M with adequate ionophores in the membrane. Experiments are performed for well-described lead-selective membranes containing different tetraphenylborate derivatives, and detection limits appear to be independent of the ion-exchanger used. However, they are much higher if a more hydrophilic carborane cation-exchanger is incorporated in the membrane. The first finding confirms recent theory, which states that transmembrane ion fluxes, given by a small level of ion-exchange at the sample side by interfering ions, normally dictate the detection limit of these sensing systems. Predicted detection limits on the basis of ion-exchanger leaching alone are here listed for a number of analytically relevant cases. For potassium-selective electrodes containing BME-44 and tetraphenylborate as ion-exchanger, the experimental detection limits are in agreement with predicted values. These results suggest that the detection limit of many current ISEs for ultratrace level analysis are, in optimal cases, dictated by transmembrane ion fluxes; however, because improved chemical solutions are being developed to reduce such effects, simple ion-exchanger partitioning may indeed become an important mechanism that can give higher detection limits than practically desired, and should not be ruled out.     

Thick membrane, solid contact ion selective electrode for the detection of lead at picomolar levels

A new approach for decreasing the lower detection limit of a lead ion selective electrode (ISE) is presented. The ISE is designed using nonfunctionalized porous glassy carbon loaded with ionophore/plasticizer/additive cocktail. This material acts both as the support for the liquid polymeric membrane and as the signal transducer of the ISE. The high purity of the glassy carbon, together with its high conductivity, allows for the development of a thick, low-resistance composite membrane. This sensor element enables the continuous measurement of lead down to picomolar levels, with very small detection limit deterioration due to the lead ion transport within the bulk of the thick membrane.     

Evaluation of the separate equilibrium processes that dictate the upper detection limit of neutral ionophore-based potentiometric sensors

The upper detection limit of polar ionophore-based ion-selective electrode membranes is predicted by utilizing the coextraction constant of dissociated electrolyte, the stability constant of the ionophore, and the membrane composition. The coextraction constant of dissociated electrolytes into the polar poly(vinyl chloride) membrane plasticized with o-nitrophenyl octyl ether (PVC-NPOE) is here measured by a novel approach. The sandwich membrane technique is utilized, with one membrane segment containing a lipophilic cation exchanger and the other containing an anion exchanger. This yields information about the coextraction constant and the free ion concentrations of the electrolyte in the two segments. Predictions correlate quantitatively with the upper detection limit observed for ion-selective electrodes based on the ionophores valinomycin, tert-butylcalix[4]arene tetraethyl ester, and calcimycin. The difficulties of the prediction of the upper detection limit for nonpolar poly(vinyl chloride) membranes plasticized with bis(2-ethylhexyl sebacate) (PVC-DOS) due to ion association are discussed in detail. A thermodynamic cycle experiment with a series of sandwich membranes shows that the principal processes governing the upper detection limit of PVC-DOS membranes are identical to those for the PVC-NPOE membranes. However, the stability of the ion pairs between the ionophore-metal ion complexes and the extracted anion are different from that of ion pairs formed between the same anion and the lipophilic anion exchanger. This makes it difficult to quantitatively predict the upper detection limit on the basis of simple apparent coextraction and complexation data alone. The approach reported herein is useful not only for mechanistic purposes but also to shed light onto the many cases where coextraction effects need to be understood but are not directly experimentally accessible.     

Improved detection limits and unbiased selectivity coefficients obtained by using ion-exchange resins in the inner reference solution of ion-selective polymeric membrane electrodes

By using a high concentration of an interfering ion and a low one of the primary ion in the inner reference solution of polymeric membrane ion-selective electrodes (ISEs), the lower detection limit may be improved and unbiased thermodynamic selectivity coefficients may be obtained. To this purpose, a cation-exchange resin is used here to keep the low concentration of the primary cation constant. Different compositions of the internal solution are required for obtaining optimal lower detection limits and unbiased selectivity coefficients. All ISEs studied here, i.e., for K+, Ca2+, and NH4+, based on valinomycin, ETH 5234, and nonactin/monactin, respectively, show improved lower detection limits in the range of 10(-7.6) (NH4+) to 10(-8.8) M (Ca2+). Nernstian responses and, therefore, unbiased selectivity coefficients are obtained with the K+-ISE for the discriminated ions, Na+, Mg2+, and Ca2+.     

Rotating disk potentiometry for inner solution optimization of low-detection-limit ion-selective electrodes

The extent of optimization of the lower detection limit of ion-selective electrodes (ISEs) can be assessed with an elegant new method. At the detection limit (i.e., in the absence of primary ions in the sample), one can observe a reproducible change in the membrane potential upon alteration of the aqueous diffusion layer thickness. This stir effect is predicted to depend on the composition of the inner solution, which is known to influence the lower detection limit of the potentiometric sensor dramatically. For an optimized electrode, the stir effect is calculated to be exactly one-half the value of the case when substantial coextraction occurs at the inner membrane side. In contrast, there is no stir effect when substantial ion exchange occurs at the inner membrane side. Consequently, this experimental method can be used to determine how well the inner filling solution has been optimized. A rotating disk electrode was used in this study because it provides adequate control of the aqueous diffusion layer thickness. Various ion-selective membranes with a variety of inner solutions that gave different calculated concentrations of the complex at the inner membrane side were studied to evaluate this principle. They contained the well-examined silver ionophore O,O' '-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene, the potassium ionophore valinomycin, or the iodide carrier [9]mercuracarborand-3. Stir effects were determined in different background solutions and compared to theoretical expectations. Correlations were good, and the results encourage the use of such stir-effect measurements to optimize ISE compositions for real-world applications. The technique was also found to be useful in estimating the level of primary ion impurities in the sample. For an iodide-selective electrode measured in phosphoric acid, for example, apparent iodide impurity levels were calculated as 5 x 10(-10) M.     

Discrimination between Butylammonium Isomers by Calix[5]arene-Based ISEs

Penta-O-alkylated p-tert-butylcalix[5]arenes 1-5 (R = benzyl, isohexyl, isopropoxyethyl, isopropoxycarbonylmethyl, and tert-butoxycarbonylmethyl, respectively) in a fixed C(5)(v) cone conformation have been studied as ionophores in liquid membrane ion-selective electrodes (ISEs) for n-butylammonium against the other branched butylammonium isomers, alkali metals, and ammonium ions, in terms of detection limits, sensitivity, and selectivity. The highest levels of potentiometric selectivity and detection limits up to 3 × 10(-)(6) M are observed with ISEs based on ionophore 2, where selectivity follows the order n-BuNH(3)(+) ? i-BuNH(3)(+) > s-BuNH(3)(+) > t-BuNH(3)(+). The lower potentiometric selectivity displayed by ISEs based on ionophores 3-5 is ascribed to their affinity for the Na(+) ion of the lipophilic salt present in the membrane, as evidenced by appropriate (1)H NMR competition experiments with Na(+) and n-BuNH(3)(+) ions. Further investigation on the selectivity mechanism of ionophore 2 by means of frequency response analysis shows that the interaction of the linear butylammonium ion with membranes containing 2 involves a lower resistance process than that occurring with the other branched isomers, thus suggesting the presence of a favorable kinetic-controlled mechanism.     

Monolithic capillary-based ion-selective electrodes

Poly(styrene-co-divinylbenzene)-based monolithic capillaries of an inner diameter of 200 mum and a length of 2-5 mm have been used to construct Ca2+-, Ag+-, and Na+-selective electrodes. The membranes consist of a solution of ionophore and ion exchanger in bis(2-ethylhexyl) sebacate or 2-nitrophenyl octyl ether, which are used as plasticizers in conventional PVC-based membranes. With capillaries of low porosity, the potentiometric responses down to 10(-8)-10(-9) M solutions do not depend on the composition of the internal solution, which indicates a strong suppression of transmembrane ion fluxes. Thus, no tedious optimization of the inner solution is required with monolith ISEs. The lower detection limits of Ag+- and Ca2+-ISEs are comparable to the best ones obtained earlier with optimized inner solutions. Additionally, a monolithic Na+-selective ISE has been obtained exhibiting a lower detection limit of 3 x 10(-8) M Na+. With monolithic capillaries of higher porosity and fused-silica GC capillaries, the transmembrane flux effects are noticeable but still significantly smaller than with conventional PVC membranes.     

Fiber-optic microsensor array based on fluorescent bulk optode microspheres for the trace analysis of silver ions

An optical microsensor array is described for the rapid analysis of silver ions at low parts per trillion levels. Because the ionophore o-xylylenebis(N,N-diisobutyldithiocarbamate) (Cu-I) was reevaluated and shown to exhibit excellent selectivity for silver ions, ion-selective electrode (ISE) membranes were optimized and found to exhibit the lowest reported detection limit so far (3 x 10(-10) M). A corresponding Ag+-selective fluorescent optical microsensor array for the rapid sensing of trace level Ag+ was then developed. It was fabricated using plasticized PVC-based micrometer-scale fluorescent microspheres that were produced via a sonic particle casting device. They contained 156 mmol/kg Cu-I, 10 mmol/kg 9-(diethylamino)-5-[4-(15-butyl-1,13-dioxo-2,14-dioxanodecyl) phenylimino]benzo[a]phenoxazine (chromoionophore VII, ETH 5418), 2.3 mmol/kg 1,1' '-dioctadecyl-3,3,3',3'-tetramethylindocarbocyanine perchlorate (internal reference dye), and 14 mmol/kg sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate and were deposited onto the etched distal end of a 3200-microm-diameter optical fiber bundle. The microarray was characterized by fluorescence spectroscopy in samples containing 10(-12)-10(-8) M AgNO3 at pH 7.4, with selectivity characteristics comparable to the corresponding ISEs. The response time of the microsensor array was found to be less than 15 min for 10(-9) M AgNO3, which is drastically shorter than earlier data on optode films (8 h) and corresponding ISEs (30 min). A detection limit of 4 x 10(-11) M for Ag+ was observed, lower than any previously reported optode or silver-selective ISE. The microsensor array was applied for measurement of free silver levels in buffered pond water samples.     

Polymeric membrane electrodes for monohydrogen phosphate and sulfate

A zwitterionic bis(guanidinium) ionophore bearing an anionic closo-borane cluster (1) and a dihydrochloride analogue (2) are investigated in polymeric membrane ion-selective electrodes (ISEs). Both compounds have been previously shown to complex and selectively extract oxoanions. By systematic variation of the kind and concentration of the ion-exchanger sites in the membrane, the optimal performance with the so far best sulfate selectivity is found for ISE membranes based on the dihydrochloride, whereas those with the zwitterion analogue are shown to possess a reasonably good selectivity for monohydrogen phosphate.     

How to assess the limits of ion-selective electrodes: method for the determination of the ultimate span, response range, and selectivity coefficients of neutral carrier-based cation selective electrodes

The span and range of an ion-selective electrode (ISE) has been identified by IUPAC as a potential or activity difference between the upper and lower detection limits of the electrode. Once the span is known, the ultimately attainable detection limit of the ISE can be calculated using its theoretical response slope. In this paper, we propose an original method for the determination of the ultimate span and response range of ISEs. The simple measurement of span is recommended to aid the fast screening of novel ionophores and help to focus optimization processes to the most promising candidates. The measurement of span is combined with a generally applicable procedure for the determination of the three seminal parameters of ISEs: the response slope, the ultimate selectivity coefficients, and detection limit. In the proposed procedure, following the span measurement, two subsequent exponential dilution experiments are completed in which the responses of the electrode for the primary and the interfering ions are tested using a solution of a discriminated ion and deionized water as diluting electrolytes in consecution. The advantages and the practical usefulness of the proposed methods and procedures are demonstrated through the evaluation of the performance characteristics of novel and well-characterized ionophore-based potassium and calcium sensors.     

Improved detection limits and sensitivities of potentiometric titrations

Zero-current ion fluxes through polymer membranes of ion-selective electrodes (ISEs) may lead to biased endpoints of potentiometric titrations. The bias is eliminated, and the sensitivity of the end-point detection is improved through reducing transmembrane ion fluxes by an appropriate choice of the inner solution. Surprisingly, ISE membranes that have a significant primary ion flux toward the inner solution show much larger sensitivities than expected by titration theory; however, depending on the experimental conditions, their application may bias the endpoint. With the optimal systems, endpoint detection is now possible with total sample concentrations below 10(-6) M, as demonstrated by the titration of EDTA with a Pb2+ solution.     

Rational design of potentiometric trace level ion sensors. A Ag+-selective electrode with a 100 ppt detection limit

Submicromolar to picomolar lower detection limits have recently been obtained with various polymer membrane ion-selective electrodes by minimizing biases due to ion fluxes through the membrane. For the best performance, the compositions of the membrane and inner solution should be optimized for each application. Given the number of parameters to be adjusted, it has been difficult to find the best parameters for a target sample. In this paper, a much simplified and more practical steady-state model of zero-current ion fluxes is derived, which is based on measurable parameters. The model allows one to predict achievable lower detection limits for a membrane with given selectivities. It can also be used to predict the optimal composition of the inner filling solution for the measurement of samples with a known, typical ionic background. Selectivity coefficients of monovalent and divalent analyte ions required for desired detection limits in drinking water are calculated. As an application of the proposed general recipe, a silver-selective electrode is developed on the basis of the ionophore O,O'-bis[2-(methylthio)ethyl]-tert-butylcalix[4]arene. With the predicted optimal composition of the inner electrolyte, its lower detection limit is found to be 10(-9) M or 100 ppt Ag+ with an ionic background of 10(-5) M LiNO3, which is very close to the expected value.     

A generalized model for apparently "non-Nernstian" equilibrium responses of ionophore-based ion-selective electrodes. 1. Independent complexation of the ionophore with primary and secondary ions

A generalized model that describes apparently "non-Nernstian" equilibrium responses of ionophore-based ion-selective electrodes (ISEs) is presented. It is formulated for primary and secondary ions of any charges that enter the membrane phase and independently form complexes with the ionophore, respectively. Equations for the phase boundary potential model were solved numerically to obtain whole response curves as a function of the sample activity of the primary ion, and analytical solutions could be obtained for apparently non-Nernstian response sections in these response curves. Ionophore-based ISEs can give three types of apparently non-Nernstian equilibrium responses, i.e., apparently "super-Nernstian", "inverted-Nernstian", and "sub-Nernstian" responses. The values of the response slopes depend on the charge numbers of the primary and secondary ions and on the stoichiometries of their complexes with the ionophore. The theoretical predictions for super-Nernstian responses agree well with the experimental results obtained with ISEs based on acidic ionophores or metalloporphyrin ionophores. Also, theoretical response curves with inverted-Nernstian slopes were found to be similar in character to the pH responses of Ca2+-selective electrodes based on organophosphate ionophores, which have been known to exhibit a so-called "potential dip". The quantitative understanding of apparently non-Nernstian response slopes presented here provides an insight into ionophore-analyte complexation processes in ISE membranes and should be helpful for the design of new ionophores.     

Selectivity of potentiometric ion sensors

Selectivities of solvent polymeric membrane ion-selective electrodes (ISEs) are quantitatively related to equilibria at the interface between the sample and the electrode membrane. However, only correctly determined selectivity coefficients allow accurate predictions of ISE responses to real-world samples. Moreover, they are also required for the optimization of ionophore structures and membrane compositions. Best suited for such purposes are potentiometric selectivity coefficients as defined already in the 1960s. This paper briefly reviews the basic relationships and focuses on possible biases in the determination of selectivity coefficients. The traditional methods to determine selectivity coefficients (separate solution method, fixed interference method) are still the same as those originally proposed by IUPAC in 1976. However, several precautions are needed to obtain meaningful data. For example, errors arise when the response to a weakly interfering ion is also influenced by the primary ion leaching from the membrane. Wrong selectivity coefficients may be also obtained when the interfering agent is highly preferred and the electrode shows counterion interference. Recent advances show how such pitfalls can be avoided. A detailed recipe to determine correct potentiometric selectivity coefficients unaffected by such biases is presented.     

Cationic or anionic sites? Selectivity optimization of ion-selective electrodes based on charged ionophores

The influence of ionic sites on the selectivities of ionophore-based ion-selective electrodes (ISEs) is described on the basis of a phase boundary potential model. The discussion presented here is significantly more general than previous ones. It is formulated for primary and interfering ions of any charges and it is valid for ISEs based on electrically charged or neutral ionophores. Furthermore, it also applies to membranes that contain more than one type of complex of the primary or interfering ion. It has been believed thus far that only ionic sites of the same charge sign as the primary ion improve the selectivities of ISEs based on charged ionophores. However, it is shown here that the charge sign of the ionic sites that give the highest potentiometric selectivities depends on the charge number of the primary and interfering ions and on the stoichiometry of their complexes with the ionophore. The validity of our model was confirmed experimentally with three ISEs based on different charged ionophores. ISEs based on lasalocid or 1-(N,N-dicyclohexylcarbamoyl)-2- (N,N-dioctadecylcarbamoyl)ethylphosphonic acid monomethyl ester (ETH 5639) as the ionophore responded selectively to Sr2+ or Mg2+, respectively, and discriminated well against other alkaline earth cations when their membranes contained anionic sites. These two electrodes are the first examples of ISEs based on charged ionophores for which maximum selectivities are obtained with membranes containing ionic sites with a charge sign opposite to that of the primary ion. On the other hand, the experimental F- selectivities of membranes based on oxo(5,10,15,20-tetraphenylporphyrinato)molybdenum-(V) improved gradually when the concentration of anionic sites was increased from 0 to 75 mol%. The selectivity-modifying influence of ionic sites for these three types of ISEs can be explained by considering the different stabilities of the 1:2 ion-ionophore complexes of the primary and of the interfering ions.     

Lifetime of ion-selective electrodes based on charged ionophores

The lifetime of solvent polymeric ion-selective electrodes (ISEs) is limited by leaching of the membrane components into the sample solutions. In this article, leaching of charged ionophores is discussed. Because of the electroneutrality principle, the loss of the charged ionophore into the sample must be accompanied by parallel transport of an ion of the opposite charge sign into the sample or by ion exchange with a sample ion of the same charge sign. Because ionic sites of high lipophilicity are available, the loss of ionic sites is, in general, not a concern. Therefore, it is assumed here that the cotransported or ion-exchanging ions are primary or interfering ions forming complexes with the ionophore. A general theory that allows quantification of ionophore lipophilicities and a discussion of changes in the membrane composition and selectivity with time is presented. A high complex stability and high analyte concentrations diminish the rate of ionophore loss into the sample if a charged ionophore is coextracted from the membrane into the sample together with an analyte ion of opposite charge. On the other hand, if the charged ionophore has the same charge sign as the ion that it binds, a large binding constant and high analyte concentrations enhance ionophore leaching into the sample. The model is applied to interpret results for an electrically charged ionophore, for which selectivity changes as a function of the leaching time were observed and the lipophilicity was determined with potentiometric measurements. Using the lipophilicities of neutral ionophores, as described previously, and the lipophilicities of charged ionophores, as described here, a direct comparison of the expected leaching rates of charged and neutral ionophores has become possible.     

Glass nanopore-based ion-selective electrodes

Glass nanopore-based all-solid-state ion-selective electrodes (ISEs) have been developed to probe the distribution of ionic species at micro- or submicrometer-length scales, e.g., mapping of ion flux through micrometer-sized pores. The all-solid-state ISE was fabricated by sealing a conically etched platinum wire (d = 25-microm; radius of etched tip <10 nm) into a soda lime glass capillary. A Pt disk was exposed by gentle polishing the glass and the disk etched to form a conical pore of submicrometer dimension (radius < approximately 500 nm; depth < approximately 30 microm). Ag was electroplated on the Pt electrode in the pore and gently chloridated to obtain a AgCl/Ag layer within the pore. The AgCl/Ag layer-coated ISE was used as a highly selective Cl- probe in scanning electrochemical microscope experiments to map the ion flux through a micropore. The same ISE was also used as the base transducer of the neutral carrier-doped solvent polymeric membrane. The optimized polymer membranes used for the glass nanopore-based all-solid-state ISE require a higher ratio of plasticizer/polymer (9/1) compared to those for conventional ISE (2/1). An ISE based on deposition of an IrO2 layer at the base of a glass nanopore electrode exhibited a highly sensitive response (79.7 +/- 2.3 mV/pH) to variations in pH and could be used for approximately 3 weeks.     

Pulsed galvanostatic control of ionophore-based polymeric ion sensors

This paper describes a pulsed galvanostatic technique to interrogate ion-selective electrodes (ISEs) with no intrinsic ion-exchange properties. Each applied current pulse is followed by a longer baseline potential pulse to regenerate the phase boundary region of the ion-selective membrane. The applied current fully controls the magnitude and sign of the ion flux into the membrane, thus offering instrumental control over an effect that has become very important in ion-selective electrode research in recent years. The resulting chronopotentiometric response curves essentially mimic traditional ISE behavior, with apparently Nernstian response slopes and selectivities that can be described with the Nicolsky equation. Additionally, the magnitude and sign of the current pulse may be used to tune sensor selectivity. Perhaps most important, however, appears to be the finding that the extent of concentration polarization near the membrane surface can be accurately controlled by this technique. A growing number of potentiometric techniques are starting to make use of nonequilibrium principles, and the method introduced here may prove to be very useful to advance these areas of research. The basic characteristics of this pulsed galvanostatic technique are here evaluated with plasticized poly(vinyl chloride) membranes containing the sodium-selective ionophore tert-butyl calix[4]arene tetramethyl ester and a lipophilic inert salt.     

Measurement of Calcium Activity in Oral Fluids by Ion Selective Electrode: Method Evaluation and Simplified Calculation of Ion Activity Products

The activity of calcium in plaque fluid is needed to calculate the saturation level of that fluid relative to the tooth mineral. One method to determine the calcium activity in very small plaque fluid samples is by micro ion-selective electrode (ISE). Two commercially available calcium ionophores, a neutral-carrier and a charged-carrier, were evaluated in micro ISEs and compared to a commercially available macro ISE using saliva as a model for plaque fluid. The neutral-carrier containing ISEs gave results consistent with those of the macro ISE. Calcium activity measurements made with micro ISEs that contained the neutral ion-carrier of whole plaque samples and plaque fluid samples obtained by centrifugation of whole plaque showed that the activities did not change due to centrifugation. Estimates of the saturation with respect to hydroxyapatite were made from these measurements. A simplified calculation method is presented to estimate the ion activity product (IAP) of the calcium-phosphate minerals. The method is based on the relative abundance of some of the possible calcium-binding species and a fixed ionic strength for plaque fluid. Calculations show that within a normal pH range for plaque fluid (5.0 to 7.5) the differences in the IAP calculations for hydroxyapatite using the simplified method are less than those estimated from propagation of uncertainty calculations.     

Solid state lithium metal batteries – Issues and challenges at the lithium-solid electrolyte interface

Solid-state Li-ion batteries employing a metallic lithium anode in conjunction with an inorganic solid electrolyte (ISE) are expected to offer superior energy density and cycle life. The realization of these metrics critically hinges on the simultaneous optimization of the ISE and the two electrode/electrolyte interfaces. In this Opinion article, we provide an overview of the materials and interfacial challenges that limit the performance of solid-state lithium metal batteries (SSLMBs). Owing to the importance of the Li/ISE interface, we dedicate a large section of this article to discuss the mechanistic aspects of lithium deposition at the Li/ISE interface. We further discuss a few recently proposed mechanisms that rationalize the growth of lithium through ISEs. We conclude our review with a brief discussion on the anode-free approach for fabricating SSLMBs where metallic lithium is generated in-situ from pre-lithiated cathodes.