O presente trabalho visou a construção e avaliação de eletrodos de membrana sólida cristalina seletivos a cobre e prata. Obteve-se o sulfeto de prata, material eletroativo usado na preparação de membranas seletivas a íons Ag+, por precipitação com gás sulfídrico em meio ácido. Eletrodos com membranas de 1,0 e 0,50 mm de espessura apresentaram respectivamente limites nernstianos de 10-4 e 10-5 Mol.L-1 e precisão de ± 0,1 e 1 mV nas leituras de potencial. Os sulfetos de cobre e prata, usados na preparação de membranas seletivas para determinação de cobre, foram obtidos por precipitação simultânea com gás sulfídrico, tioacetamida em meio ácido e tiouréia em meio amoniacal. Difratogramas de Raios X revelaram que o material obtido com tiouréia corresponde ao sulfeto ternário, Cu2S.3Ag2S ou Ag1,55Cu0,45S, responsável pela resposta seletiva do sensor em soluções de Cu2+. O eletrodo construído a partir deste sulfeto, onde o cobre aparece no estado monovalente, apresentou limite nernstiano da ordem de10-7Mol.L-1, fornecendo resultados satisfatórios na determinação deste metal em amostras de aguardente e álcool. Cálculos termodinâmicos mostraram que quando membrana é constituída de CuS, um contacto elétrico efetuado através de cobre ou prata é instável...
Atualmente, a preocupação com a redução da poluição industrial tem motivado os pesquisadores na busca de novas tecnologias para o tratamento de resíduos industriais. Tecnologias limpas, como a eletrodiálise, são capazes de tratar alguns destes resíduos, como por exemplo o efluente da indústria de galvanoplastia, minimizando os impactos que ocorreriam caso eles fossem descartados diretamente no meio ambiente. O componente principal desta técnica é a membrana na qual ocorre a etapa de retirada dos íons da solução. Atualmente estas membranas são importadas e caras, o que justifica o desenvolvimento de membranas eficientes e acessíveis. Neste sentido, no presente trabalho membranas de poliestireno sulfonado/ poliestireno de alto impacto (SPS/HIPS), polianilina dopada com ácido canforsulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniCSA/SPS/HIPS), polianilina sulfonada/ poliestireno sulfonado/ poliestireno de alto impacto (SPAN/SPS/HIPS), e polianilina dopada com ácido p-tolueno sulfônico/ poliestireno sulfonado/ poliestireno de alto impacto (PAniTSA/SPS/HIPS) foram desenvolvidas usando o método de mistura química. As membranas foram caracterizadas utilizando as técnicas Análise termogravimétrica (TGA)...
This paper describes the recent progress in the development of polymeric membranes for ion-selective electrodes. The importance of knowing the mechanism of potential development in membranes for ion-selective electrodes to reach lower detection limits and improve selectivity are discussed. Recent advances and future trends of research on ion-selective electrodes are also reported.
This paper gives an overview of the newest developments of polymeric membrane ion-selective electrodes. A short essence of the underlying theory is given, emphasizing how the electromotive force may be used to assess binding constants of the ionophore, and how the selectivity and detection limit are related to the basic membrane processes. The recent developments in lowering the detection limits of ISEs are described, including recent approaches of developing all solid state ISEs, and breakthroughs in detecting ultra-small quantities of ions at low concentrations. These developments have paved the way to use potentiometric sensors as in ultra-sensitive affinity bioanalysis in conjunction with nanoparticle labels. Recent results establish that potentiometry compares favorably to electrochemical stripping analysis. Other new developments with ion-selective electrodes are also described, including the concept of backside calibration potentiometry, controlled current coulometry, pulsed chronopotentiometry, and localized flash titration with ion-selective membranes to design sensors for the direct detection of total acidity without net sample perturbation. These developments have further opened the field for exciting new possibilities and applications.
We report here on an experimental system that utilizes ion-selective microelectrodes to measure the electrochemical potential gradients for H+ and K+ ions within the unstirred layer near the root surface of both intact 4-day-old corn seedlings and corn root segments. Analysis of the steady state H+ and K+ electrochemical potential gradients provided a simultaneous measure of the fluxes crossing a localized region of the root surface. Net K+ influx values obtained by this method were compared with unidirectional K+ (86Rb+) influx kinetic data; at any particular K+ concentration, similar values were obtained by either technique. The ionspecific microelectrode system was then used to investigate the association between net H+ efflux and net K+ influx. Although the computed H+:K+ stoichiometry is dependent upon the choice of diffusion coefficients, the values obtained were extremely variable, and net K+ influx rarely appeared to be charge-balanced by H+ efflux. In contrast to earlier studies, we found the cortical membrane potential to be highly K+ sensitive within the micromolar K+ concentration range. Simultaneous measurements of membrane potential and K+ influx, as a function of K+ concentration, revealed similar Km values for the depolarization of the potential (Km 6-9 micromolar K+) and net K+ influx (Km 4-7 micromolar K+). These data suggest that K+ may enter corn roots via a K+-H+ cotransport system rather than a K+/H+ antiporter.
Neutral carrier-based liquid membrane ion-selective microelectrodes for NH4+ and NO3− were developed and used to investigate inorganic nitrogen acquisition in two varieties of barley, Hordeum vulgare L. cv Olli and H. vulgare L. cv Prato, originating in cold and warm climates, respectively. In the present paper, the methods used in the fabrication of ammonium- and nitrate-selective microelectrodes are described, and their application in the study of inorganic nitrogen uptake is demonstrated. Net ionic fluxes of NH4+ and NO3− were measured in the unstirred layer of solution immediately external to the root surface. The preference for the uptake of a particular ionic form was examined by measuring the net flux of the predominant form of inorganic nitrogen, with and without the alternative ion in solution. Net flux of NH4+ into the cold-adapted variety remained unchanged when equimolar concentrations (200 micromolar) of NH4+ and NO3− were present. Similarly, net flux of NO3− into the warm-adapted variety was not affected when NH4+ was also present in solution. The high temporal and spatial resolution afforded by ammonium- and nitrate-selective microelectrodes permits a detailed examination of inorganic nitrogen acquisition and its component ionic interactions.
Net fluxes of NH4+ and NO3− into roots of 7-day-old barley (Hordeum vulgare L. cv Prato) seedlings varied both with position along the root axis and with time. These variations were not consistent between replicate plants; different roots showed unique temporal and spatial patterns of uptake. Axial scans of NH4+ and NO3− net fluxes were conducted along the apical 7 centimeters of seminal roots of intact barley seedlings in solution culture using ion-selective microelectrodes in the unstirred layer immediately external to the root surface. Theoretically derived relationships between uptake and concentration gradients, combined with experimental observations of the conditions existing in our experimental system, permitted evaluation of the contribution of bulk water flow to ion movement in the unstirred layer, as well as a measure of the spatial resolution of the microelectrode flux estimation technique. Finally, a method was adopted to assess the accuracy of this technique.
The linear phenomenological equations giving particle and practical fluxes of a single electrolyte across an ion-selective membrane are stated and interrelated. It is shown that the experimental measurements commonly made in biological and synthetic membrane studies may be used, with minor modification, to obtain the phenomenological transport coefficients and their concentration dependences. It is demonstrated that the electrical properties of a homogeneous membrane may be obtained as functions of the bathing solution concentration by combining fluxes measured under open and short circuit. Attention is paid to the use of radiotracers when measuring ionic fluxes. To obtain all the phenomenological coefficients at least one measurement must be made under a pressure gradient. The experimental difficulties in such measurements are discussed and the merits and demerits of various experiments considered. The problems of measuring potentials and concentrations at the low pressure face of a supported membrane make several mathematically simple approaches experimentally unattractive. The best methods appear to be either the measurement of a succession of “apparent osmotic pressures” under concentration differences sufficiently small that the membrane does not require support or the study of “reverse osmosis”. Sets of equations are given which enable the phenomenological coefficients to be evaluated from convenient experiments. With a stable homogeneous membrane nine coefficients may be obtained thus enabling either the applicability of the reciprocal relations or the applicability of linear theory under the conditions of the experiments to be tested. For a discontinuous system the six independent coefficients may be obtained from experiments in a single membrane cell.
For about one hundred 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 key requirements 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...
Lipophilic background electrolytes consisting of a lipophilic cation and a lipophilic anion, such as tetradodecylammonium tetrakis(4-chlorophenyl) borate (ETH 500), or bis(triphenylphosphoranylidene) ammonium tetrakis[3,5bis(trifluoromethyl) phenyl] borate (BTPPATFPB) are incorporated into the membranes of ion-selective electrodes (ISEs) to improve the detection limit and selectivity of the electrodes and decrease the resistance of the sensing membrane. In this work, spectroelectrochemical microscopy (SpECM) is used in conjunction with chronopotentiometry to quantify the effects of a lipophilic background electrolyte on the concentration profiles induced inside current-polarized membranes and on the measured voltage transients in chronopotentiometric experiments. In agreement with the theoretical model, the lipophilic background electrolyte incorporated into o-NPOE or DOS plasticized membranes decreases the membrane resistance and thus the contribution of migration in the overall transport across ion-selective membranes. Consequently, it has a significant influence on the changing concentration profiles of the ion-ionophore complex during chronopotentiometric experiments.
The applications of ion-selective electrodes (ISEs) have been broadened through the introduction of galvanostatic current pulse methods in potentiometric analysis. An important requirement in these applications is the restoration of the uniform equilibrium concentration profiles in the ISE membrane between each measurement. The simplest restoration method is zero current relaxation, in which the membrane relaxes under open-circuit conditions in a diffusion-controlled process. This paper presents a novel restoration method using a reverse current pulse. An analytic model for this restoration method is derived to predict the concentration profiles inside ISE membranes following galvanostatic current pulses. This model allows the calculation of the voltage transients as the membrane voltage relaxes back towards its zero-current equilibrium value. The predicted concentration profiles and voltage transients are confirmed using spectroelectrochemical microscopy (SpECM).
Passing currents through ion-selective membranes has contributed to the development of a variety of novel methods. In this work, chronopotentiometric (CP) transients with two transition times (breakpoints) are presented for the first time, with the theoretical interpretation of such voltage transients. The validity of our theory has been confirmed in experiments utilizing ETH 5294 chromoionophore-based pH sensitive membranes with and without lipophilic background electrolyte and ETH 5234 ionophore-based calcium selective membranes in which the ionophore forms 3:1 complexes with Ca2+ ions. The conditions under which two breakpoints can be identified in the chronopotentiometric voltage transients are discussed.
A simple but powerful numerical simulation for analyzing the electrochemical behavior of ion-selective membranes and liquid junctions is presented. The computer modeling makes use of a finite-element procedure in the space and time domains, which can be easily processed (e. g., with MS Excel software) without the need for complex mathematical evaluations. It leads to convincing results on the dynamic evolution of concentration profiles, potentials, and fluxes in the studied systems. The treatment accounts for influences of convection, flow, or stirring in the sample solution that act on the boundary diffusion layer and it is even capable of including the effects of an electrolyte flow through the whole system. To minimize the number of arbitrary parameters, interfacial reactions are assumed to be near local equilibrium, and space-charge influences are considered via phase-boundary potential differences. The applicability of the computer simulation is demonstrated for different ion-selective membranes as well as for liquid junctions. The numerical results are in excellent agreement with experimental data.
A generalized description of the response behavior of potentiometric polymer membrane ion-selective electrodes is presented on the basis of ion-exchange equilibrium considerations at the sample—membrane interface. This paper includes and extends on previously reported theoretical advances in a more compact yet more comprehensive form. Specifically, the phase boundary potential model is used to derive the origin of the Nernstian response behavior in a single expression, which is valid for a membrane containing any charge type and complex stoichiometry of ionophore and ion-exchanger. This forms the basis for a generalized expression of the selectivity coefficient, which may be used for the selectivity optimization of ion-selective membranes containing electrically charged and neutral ionophores of any desired stoichiometry. It is shown to reduce to expressions published previously for specialized cases, and may be effectively applied to problems relevant in modern potentiometry. The treatment is extended to mixed ion solutions, offering a comprehensive yet formally compact derivation of the response behavior of ion-selective electrodes to a mixture of ions of any desired charge. It is compared to predictions by the less accurate Nicolsky-Eisenman equation. The influence of ion fluxes or any form of electrochemical excitation is not considered here...
In this paper, we report a novel method for fabricating ion-selective membranes in poly(dimethylsiloxane) (PDMS)/glass-based microfluidic preconcentrators. Based on the concept of capillary valves, this fabrication method involves filling a lithographically patterned junction between two microchannels with an ion-selective material such as Nafion resin; subsequent curing results in a high aspect-ratio membrane for use in electrokinetic sample preconcentration. To demonstrate the concentration performance of this high-aspect-ratio, ion-selective membrane, we integrated the preconcentrator with a surface-based immunoassay for R-Phycoerythrin (RPE). Using a 1×PBS buffer system, the preconcentrator-enhanced immunoassay showed an approximately 100× improvement in sensitivity within 30 minutes. This is the first time that an electrokinetic microfluidic preconcentrator based on ion concentration polarization (ICP) has been used in high ionic strength buffer solutions to enhance the sensitivity of surface-based immunoassay.
Ionophore-doped sensing membranes exhibit greater selectivities and wider measuring ranges if their membrane matrixes are noncoordinating and solvate interfering ions poorly. This is particularly true for fluorous phases, which are the least polar and polarizable condensed phases known. In this work, fluorous membrane matrixes were used to prepare silver ion-selective electrodes (ISEs). Sensing membranes composed of perfluoroperhydrophenanthrene, sodium tetrakis[3,5-bis(perfluorohexyl)phenyl]borate, and one of four fluorophilic Ag+-selective ionophores with one or two thioether groups were investigated. All electrodes exhibited Nernstian responses to Ag+ in a wide range of concentrations. Their selectivities for Ag+ over interfering ions were found to depend on host preorganization and the length of the –(CH2)n– spacers separating the coordinating thioether group from the strongly electron withdrawing perfluoroalkyl groups. ISEs based on the most selective of the four ionophores, i.e., 1,3-bis(perfluorodecylethylthiomethyl)benzene, provided much higher selectivities for Ag+ over many alkaline and heavy metal ions than most Ag+ ISEs reported in the literature (e.g.,
logKAg,Jpot for K+, −11.6; Pb2+, −10.2; Cu2+, −13.0; Cd2+...
The applicability of extremely thin non-electroneutral membranes for ion-selective electrodes (ISEs) is investigated. A theoretical treatment of potential and concentration profiles in space-charge membranes of << 1 μm thickness is presented. The theory is based on the Nernst-Planck equation for ion fluxes, which reduces to Boltzmann’s formula at equilibrium, and on the Poisson relationship between space-charge density and electric field gradient. A general solution in integral form is obtained for the potential function and the corresponding ion profiles at equilibrium. A series of explicit sub-solutions is derived for particular cases. Membrane systems with up to three different ion species are discussed, including trapped ionic sites and co-extracted ions. Solid-contacted thin membranes (without formation of aqueous films at the inner interface) are shown to exhibit a sub-Nernstian response. The theoretical results are confirmed by numerical simulations using a simplified finite-difference procedure based on the Nernst-Planck-Poisson model, which are shown to be in excellent agreement.
Poly(vinylchloride) (PVC) is the most common polymer matrix used in the fabrication of ion-selective electrodes (ISEs). However, the surfaces of PVC-based sensors have been reported to show membrane instability. In an attempt to overcome this limitation, here we developed two alternative methods for the preparation of highly stable and robust ion-selective sensors. These platforms are based on the selective electropolymerization of poly(3,4-ethylenedioxythiophene) (PEDOT), where the sulfur atoms contained in the polymer covalently interact with the gold electrode, also permitting controlled selective attachment on a miniaturized electrode in an array format. This platform sensor was improved with the crosslinking of the membrane compounds with poly(ethyleneglycol) diglycidyl ether (PEG), thus also increasing the biocompatibility of the sensor. The resulting ISE membranes showed faster signal stabilization of the sensor response compared with that of the PVC matrix and also better reproducibility and stability, thus making these platforms highly suitable candidates for the manufacture of robust implantable sensors.
The effect of 1-decanol on the potentiometric response of three ion-selective electrodes to large cationic species is analyzed. The electrodes were constructed with plasticized PVC membranes. The results suggest that 1-decanol alters the ionic transport through the membrane/water interface to an extent that depends on the strength of the active ion pair. The water solubility of the cation, its molecular weight, and the size of the ion pair seem to be relevant factors in this type of behavior. The potentiometric selectivity coefficients are also dependent on the presence of 1-decanol in the membrane. These results are similar to those already described in ion-selective electrodes with membranes capable of sensing anionic benzene sulfonate-type systems. Thus, the effect of the alcohol appears to be general by affecting mainly the membrane surface polarity.
Lead(II) ion selective electrode, ISE, based on plasticized PVC membranes with 1-furoyl 3,3 diethyl thiourea as ionophore and tributylphosphate as plasticizer have been developed. The membrane was applied on a conducting epoxy resin support. Some parameters of evaluation of the electrode are presented in this work. The ISE have linear response in the concentration range of the 10(-6)-10(-3) mol/dm(3), with slope of 29.61 mV/decade. The static response time obtained was less than 20 seconds. The ISE is useful for more than one month. The selectivity coefficients (K-AB(Pot)) for Cu2+, Cd2+ and Ca2+ ions were calculated by employing the mixed solutions method and the pH dependence of the potential was analyzed. Scanning electron microscopy (SEM) of the membranes was registered at different time of the use of the ISE. The SEM images showed morphological changes of the membrane surface probably due to both the reaction between the Pb2+ and the ionophore and/or loss of the membrane components by exudation.