Ion-selective Membrane Electrodes Research Articles

OFF–ON stirring potentiometry with solvent polymeric membrane ion-selective electrodes: A theory-guided approach to foreign ions

The response of ion-selective electrodes (ISEs) towards a foreign ion is comprehensively investigated as a function of the nature and concentration of the ion, and of the mass transport conditions in the outer solution. Notably, a striking transient potential drift is evidenced by sheer activation of stirring in an initially quiescent solution of the foreign ion, both in the absence and presence of the primary ion. This phenomenon is rationalized in terms of the ion exchange at the outer membrane side coupled to the mass transfer of ions. This has been modelled through a novel theoretical treatment of the corresponding time-dependent mass transport problem, leading to simple closed-form expressions for the membrane potential and for the interfacial ion concentrations in the unstirring and stirring periods. The theoretical predictions are corroborated experimentally by monitoring the potential of a nitrate ISE exposed to ions of very different affinity towards the membrane (tetraphenylborate, perchlorate and chloride) before and after switching on the agitation of the solution. Such OFF-ON stirring program enables the study of foreign ions, even simultaneously with the determination of the primary species by the joint analysis of the potentials before and after the activation of the stirring.

Ion-selective electrode based on polyurethane-immobilized di-(2-ethyl hexyl) phosphoric acid for low-concentration aqueous Pb2+ detection and quantification

This study used a polyurethane (PU)-based ion selective electrode (ISE) immobilized with di-(2-ethyl hexyl) phosphoric acid (D2EHPA) to detect and quantify Pb2+ ions at low concentrations (10−10 to 10−1 M) in aqueous solution. PU, synthesized from castor oil (Ricinus communis L.), was utilized as the ISE membrane matrix. The ISE demonstrated a sensitivity of 26.24 ± 0.12 mV/decade, a detection limit of 1.44 × 10−7 M, and a response time of 10 s. We maintained the measurement stability for up to six days of storage.The results of Pb2+ quantification produced by ISE were compared with the results using atomic absorption spectroscopy (AAS), indicating similar Pb2+ concentrations in both artificial and real wastewater samples (calculated t-value < theoretical t-value). Therefore, this ISE is suitable for detecting trace levels of Pb2+ and quantifying them with high accuracy.

Influences of marine biofouling on the potential responses of polymeric membrane ion-selective electrodes

Using polymeric membrane ion-selective electrodes (ISEs) for reliable long-term marine environmental observations is still a challenge due to the formation of biofilms on electrode surfaces. Unfortunately, the contributions of the specific biofilm components to sensor failure have not been studied. Herein, the influences of the specific biofilm components on the performance of the neutral carrier-based polymeric membrane ISEs are systematically investigated in terms of sensitivity, selectivity, and stability. More importantly, the spatial distributions of these foulants in the fouled sensing membrane phase are studied by confocal laser scanning microscopy for the first time to give insight into the fouling mechanisms. Three typical biochemicals (i.e., proteins, polysaccharides, microbial lipids) in biofilms are selected as the representative foulants. The poly (vinyl chloride)-based CO32--ISEs and K+-ISEs/Ca2+-ISEs have been selected as the model sensors for detection of anions and cations, respectively. Experiments show that depending on the type of the biofoulants, the adsorption of the foulants on the polymeric membrane surface and/or their extraction into the organic membrane phase could occur and induce a change in the potential responses. This study provides a deep insight into the influences of the specific biofilm components on the polymeric membrane ISEs, which is of importance for development of the polymeric membrane marine sensors with high antifouling capabilities for long-term marine monitoring.

A cathodically polarized PANI-based lead ion-selective electrode: achieving high stability with antibiofouling capabilities.

Solid-state contact ion-selective electrodes (SC-ISEs) are an efficacious means of monitoring heavy metal contamination. Instability of the electrode potential is a key factor limiting their development, with biofouling in real water samples posing a significant challenge to maintaining stability. Therefore, addressing biofouling is crucial for optimizing solid-state ion-selective electrodes. In this work, high stability and antibiofouling capability in a solid-state contact lead ion-selective electrode (SC-Pb2+-ISE) based on polyaniline (PANI) was achieved through cathodic polarization. Specifically, PANI played a dual role in the ion-selective membrane (ISM) as an ion-to-electron transducer and antifouling agent. Given the excellent electrochemical performance of PANI, the prepared electrode (GC/PANI-Pb2+-ISM) demonstrated a remarkable antibiofouling efficiency of 98.2% under a cathodic polarization of -0.2V. Furthermore, a standard deviation of standard potential (Eθ) as low as ± 0.5mV was realized successfully. The excellent chrono-potentiometric stability of 17.0 ± 2.9μV/s was also demonstrated. The electrode maintained a Nernstian response slope of 30.7 ± 0.2 (R2 = 0.998) after applying a cathode potential (-0.2V) for 30min. The developed GC/PANI-Pb2+-ISM electrode is suitable for practical applications in real environmental water sample monitoring.

Triple-function carbon-based Ca2+ ion-selective pH ring microelectrode to study real-time bacteria-mediated hydroxyapatite corrosion

BackgroundThe local pH change mediated by the pathogenic bacterial species Streptococcus mutans plays a significant role in the corrosion of hydroxyapatite (HA) present in the tooth in the dynamic oral cavity. The acid produced by the bacteria decreases the local pH and releases Ca2+ ions from the HA. We studied the bacteria-mediated demineralization of HA by scanning electrochemical microscopy (SECM) after growing S. mutans biofilm on HA for 7 days. ResultsWe notably developed a triple-function SECM-compatible tip that could be positioned above the biofilm. It can also measure the pH and [Ca2+] change simultaneously above the biofilm-HA substrate. The triple-function SECM tip is a combination of a potentiometric pH sensor deposited with iridium oxide and a dual-function carbon-based Ca2+ ion-selective membrane electrode with a slope of 67 mV/pH and 34.3 mV/log [Ca2+], respectively. The distance-controlled triple-function SECM tip monitored real-time pH and [Ca2+] changes 30 μm above the S. mutans biofilm. The high temporal resolution pH data demonstrated that after approximately 20 min of sucrose addition, S. mutans started to produce acid to titrate the solution buffer, causing a pH change from 7.2 to 6.5 for HA and from 7.2 to 5 for the glass substrate. We observed that, after 30 min of acid production, ∼300 μM of Ca2+ ions were increased at pH 6.5 above the biofilm surface as a result of the pH change in the local microenvironment. After the release of Ca2+ from HA, the pH environment again shifted toward the neutral side, from 6.5 to 7.2. Therefore, precipitation of Ca2+ happens at the top of the biofilm, thus corroding the HA from underneath. For a glass substrate, in contrast, no Ca2+ ions were released, and the pH did not change back to 7.2. We were able to observe the dynamics of the HA demineralization–remineralization process simultaneously with our newly developed triple-function SECM tip or microprobe. SignificanceThis technique could notably advance the study of similar complex processes, such as bacteria-mediated corrosion in biomedical and environmental contexts.

Potentiometric/time resolved chronopotentiometric sensing for an all-solid-state ion-selective electrode based on MXene/MWCNTs as solid contact

Solid-contact polymeric membrane ion-selective electrodes (ISEs) have been an attractive tool for potentiometric sensors. Sufficient transducing performance evaluation and multiple potentiometric analysis are critical to evaluate whether the solid contact transducer material used in ISE is promising. Herein, we describe sandwich-like MXene/MWCNTs-based polymeric membrane ISEs with three-readout strategies of potential response, chronopotentiometric response, and transition time response. The MXene/MWCNTs can be readily prepared by the electrostatic self-assembly strategy, which not only prevented the aggregation of MXene nanosheets and facilitated charge-transfer, but also significantly contributed to the large double-layer capacitance and water-layer free from interference. With Ca2+ as a model, two kinds of Ca2+-ISEs based on thermodynamic response and dynamic response by modulating the polymeric membrane components with three readouts were explored. Moreover, the proposed Ca2+-ISEs under different background electrolytes exhibit the similar Nernstian responses in potentiometry, variable super-Nernstian ranges in chronopotentiometry, and the consistent transition time readout. This study offers a facile MXene/MWCNTs transducer to develop a highly reliable polymeric membrane ISE.

Maintenance-free antifouling polymeric membrane potentiometric sensors based on self-polishing coatings.

Polymeric membrane ion-selective electrodes (ISEs) have been widely used in environmental monitoring. However, in complicated marine environments, marine biofouling usually becomes a sticky problem for these electrodes. Herein, for the first time, a novel maintenance-free antifouling potentiometric marine sensor based on a self-polishing coating (SPC) is proposed. The SPC is synthesized by using the seeded emulsion polymerization method based on the triisopropylsilyl methacrylate monomer as the regulator of the self-renewal rate. This coating can be simply modified onto the electrode surface by drop-casting. The silyl acrylate side groups of the obtained SPC on the sensor surface can be hydrolyzed in the marine alkaline medium. The shear movement of seawater driven by sea waves, wind, gravity, or vibration removes the leftover (fouled) brittle polymer backbone and thus the fouling marine microorganisms. As a proof-of-concept experiment, a polymeric membrane Ca2+-ISE is chosen as a model. Compared to the unmodified electrode, the SPC-coated Ca2+-ISE exhibits remarkable improved antifouling properties in terms of superior anti-adhesive abilities towards marine microorganisms, such as bacterial cells and algae and excellent long-term stability even in the presence of high levels of marine microorganisms. Since no additional manual maintenance is required for maintaining the antifouling abilities of the sensor, the proposed self-polishing sensor may lay an important foundation for construction of unattended long-term potentiometric monitoring systems in real marine environments.

Polymeric membrane ion-selective electrode based on potential-modulated ion transfer: ultrasensitive measurement of oceanic pH.

The application of a potentiometric pH electrode in ocean acidification observation is still a challenge due to its poor sensitivity to small pH changes. Herein, a simple approach to remarkably improve the detection precision of a polymeric membrane ion-selective electrode is proposed based on the potential-modulated ion transfer mechanism. The present sensing strategy displays highly sensitive responses to small pH changes for seawater analysis with a precision of 5 μpH, which is 2 orders of magnitude lower than that of the conventional pH electrode.

The Influence of the Nature of the Polymer Incorporating the Same A3B Multifunctional Porphyrin on the Optical or Electrical Capacity to Recognize Procaine.

The multifunctionality of an A3B mixed-substituted porphyrin, namely 5-(4-carboxyphenyl)-10,15,20-tris(4-methylphenyl)porphyrin (5-COOH-3MPP), was proven due to its capacity to detect procaine by different methods, depending on the polymer matrix in which it is incorporated. The hybrid nanomaterial containing k-carrageenan and AuNPs (5-COOH-3MPP-k-carrageenan-AuNPs) was able to optically detect procaine in the concentration range from 5.76 × 10-6 M to 2.75 × 10-7 M, with a limit of detection (LOD) of 1.33 × 10-7 M. This method for the detection of procaine gave complementary results to the potentiometric one, which uses 5-COOH-3MPP as an electroactive material incorporated in a polyvinylchloride (PVC) membrane plasticized with o-NPOE. The detected concentration range by this ion-selective membrane electrode is wider (enlarged in the field of higher concentrations from 10-2 to 10-6 M), linearly dependent with a 53.88 mV/decade slope, possesses a detection limit of 7 × 10-7 M, a response time of 60 s, and has a certified stability for a working period of six weeks.

Modern Potentiometric Biosensing Based on Non-Equilibrium Measurement Techniques.

Modern potentiometric sensors based on polymeric membrane ion-selective electrodes (ISEs) have achieved new breakthroughs in sensitivity, selectivity, and stability and have extended applications in environmental surveillance, medical diagnostics, and industrial analysis. Moreover, nonclassical potentiometry shows promise for many applications and opens up new opportunities for potentiometric biosensing. Here, we aim to provide a concept to summarize advances over the past decade in the development of potentiometric biosensors with polymeric membrane ISEs. This Concept article articulates sensing mechanisms based on non-equilibrium measurement techniques. In particular, we emphasize new trends in potentiometric biosensing based on attractive dynamic approaches. Representative examples are selected to illustrate key applications under zero-current conditions and stimulus-controlled modes. More importantly, fruitful information obtained from non-equilibrium measurements with dynamic responses can be useful for artificial intelligence (AI). The combination of ISEs with advanced AI techniques for effective data processing is also discussed. We hope that this Concept will illustrate the great possibilities offered by non-equilibrium measurement techniques and AI in potentiometric biosensing and encourage further innovations in this exciting field.

Determination of forced convection effects on the response of membrane-based ion-selective electrodes via numerical solution to the Navier-Stokes-Nernst-Plank-Poisson equations

Ion selective electrodes (ISEs) enable measurements via the build-up of a phase boundary potential at the surface of a sensing membrane. While a framework exists to understand the performance of ISEs in stagnant samples, the influences of fluid flow on ISEs are less studied. We model the transport of ions in solution occurring near interfaces between ISE membranes and aqueous samples when subject to an external flow. We developed a numerical model extending the Pressure-Implicit with Splitting of Operators (PISO) algorithm to incorporate the Navier-Stokes-Nernst-Plank-Poisson system of equations. We find that external flow distorts the aqueous side of the formed double layer at the ISE membrane and aqueous sample interface, leading to an increase in the phase boundary potential. The change in potential is shown to be a function of a novel set of dimensionless numbers, most notably the Debye Length Reynolds number, i.e., the Reynolds number with the Debye Length as the system dimension.

Electrochemical Visualization of an Ion-Selective Membrane Using a Carbon Nanoelectrode.

Molecular and physical probes have been widely employed to investigate physicochemical properties and mechanisms of interfaces due to their ability to provide accurate measurements with temporal and spatial resolution. However, the direct measurement of electroactive species diffusion in ion-selective electrode (ISE) membranes and quantification of the water layer have been challenging due to the high impedance and optical opacity of polymer membranes. In the present work, carbon nanoelectrodes with ultrathin insulating encapsulation and good geometrical structure are reported as physical probes for direct electrochemical measurement of the water layer. The scanning electrochemical microscopy experiment exhibits positive feedback at the interface of the fresh ISE, and negative feedback after conditioning for 3 h. The thickness of the water layer was estimated to be ca. 13 nm. For the first time, we provide direct evidence that, during conditioning, the water molecules diffuse through the chloride ion selective membrane (Cl-ISM) until a water layer establishes at almost 3 h. Furthermore, the diffusion coefficient and concentration of oxygen molecules in the Cl-ISM are also directly electrochemical measured by introducing ferrocene (Fc) as a redox molecule probe. The oxygen concentration in the Cl-ISM decreases during conditioning, suggesting the diffusion of oxygen from ISM to the water layer. The proposed method can be used for the electrochemical measurement of solid contact, providing theoretical guidance and advice for the performance optimization of ISEs.

Solid-contact polymeric membrane ion-selective electrodes using a covalent organic framework@reduced graphene oxide composite as ion-to-electron transducer.

A solid-contact ion-selective electrode (SC-ISE) based on a covalent organic framework@reduced graphene oxide (rGO) composite is proposed. The composite can be synthesized through the polycondensation of 1,3,5-triformylphloroglucinol (TFP) and 2,6-diaminoanthraquinone (DAAQ) on the rGO nanosheets, which shows high capacitance and good redox-active properties. By applying Cd2+-ISE as a model, the electrode exhibits a Nernstian slope of 29.7±0.4 mV/decade in the activity range of 1.0×10-7 - 7.9×10-4M and the limit of detection is 6.8×10-8M. Particularly, the electrode based on DAAQ-TFP@rGO exhibits a low potential drift of 1.2±0.2μV/h over 70h due to the large capacitance of 2.0mF. Moreover, the DAAQ-TFP@rGO-based Cd2+-ISE shows good reproducibility and the standard deviations of the standard potentials for single batch and batch-to-batch are 0.28 (n=4) and 0.30mV (n=4), respectively. The developed SC-Cd2+-ISE is not disturbed by light or gas and no aqueous layer occurs between the sensing membrane and DAAQ-TFP@rGO layer. The DAAQ-TFP@rGO composite is highly promising for construction of calibration-free SC-ISEs.

Anti-fouling TiO2-Coated Polymeric Membrane Ion-Selective Electrodes with Photocatalytic Self-Cleaning Properties

Nowadays, using a polymeric membrane ion-selective electrode (ISE) to achieve reliable ion sensing in complex samples remains challenging because of electrode fouling. To address this challenge, we describe a polymeric membrane ISE with excellent anti-fouling and self-cleaning properties based on surface covalent modification of an anatase TiO2 coating. Under ultraviolet illumination, the reactive oxygen species produced by photocatalytic TiO2 can not only kill microorganisms but also degrade organic foulants into carbon dioxide and water, and a formed superhydrophilic film can effectively prevent the adsorption of foulants, thus inhibiting the occurrence of biofouling and organic fouling of the sensors. More importantly, residual foulants could be fully self-cleaned through the flow of water droplets. By using Ca2+-ISE as a model, an anti-fouling polymeric membrane potentiometric sensor has been developed. Compared to the unmodified electrode, the TiO2-coated Ca2+-ISE exhibits remarkably improved anti-biofouling properties with a low bacterial adhesion rate of 4.74% and a high inhibition rate of 96.62%. In addition, the proposed electrode displays unique properties of anti-organic dye fouling and a superior self-cleaning ability even after soaking in a concentrated bacterial suspension of 109 CFU mL-1 for 60 days. The present approach can be extended to improve the fouling resistance of other electrochemical or optical membrane sensors and is promising for the construction of contamination-free sensors.

Study on fabrication ion-selective membrane electrodes to improve electrochemical characteristics of electrodes for applied in water analysis

In this paper, we report the photolithography manufacturing of solid- ion selective membrane electrodes ammonium and nitrate in a cleanroom, using ammonium ionophore I (nonactin) and nitrate ionophore VI as starting materials. The developed probes are utilized with multipurpose electrochemical devices to potentiometrically monitor the concentration of ammonium and nitrate ions. &#x0D; The research results showed that, S-ISM ammonium and nitrate can be used to measure ammonium and nitrate ions with high selectivity; it is also stable under research circumstances, with hardly any change in the OCP signals over time and a low limit of detection (LOD) of 2.0 ppm for NH4+ and 2.5 ppm for NO3-.

Preparation of Nitrate Bilayer Membrane Ion-Selective Electrode Modified by Pericarpium Granati-Derived Biochar and Its Application in Practical Samples

Preparation of Nitrate Bilayer Membrane Ion-Selective Electrode Modified by Pericarpium Granati-Derived Biochar and Its Application in Practical Samples

Ion-Selective Membrane Electrode for Determination of the Octahydrotriborate Anion

Ion-Selective Membrane Electrode for Determination of the Octahydrotriborate Anion

Ion-Selective Membrane Electrode for Determination of the Octahydrotriborate Anion

An ion-selective electrode (ISE) based on a plasticized polyvinyl chloride membrane chemically doped with tetradecylammonium octahydrotriborate ([(С10H21)4N+]) has been developed. It is shown that the electrode has a reversible potentiometric response with respect to the octahydrotriborate anion in the presence of a number of other inorganic anions. The influence of the concentration of the electrode-active material and the nature of the plasticizer in the membrane phase on the electrochemical characteristics of the fabricated sensor have been studied. The optimal composition of the ion-sensitive membrane has been found. It has been found that the developed sensor provides a wide range of detectable concentrations of(1 × 10–7…1 × 10–2) and a low detection limit (10–7.3 M). The new ISE can be recommended for direct potentiometric detection of free octahydrotriborate anions in technological aqueous solutions.

Design and Synthesis of the Poly Vinyl Chloride (PVC) Membrane for Fe(III) Ion Selective Electrode (ISE) Based on Ester Modified Humic Acid (EHA) as an Ionophore

Design and synthesis of the poly vinyl chloride (PVC) membrane as Fe(III) ion selective electrode (ISE) sensor based on EHA ionophore as an excellent sensory molecule for monitoring Fe(III) in the sample solution had been done. Simple and efficient EHA was made by condensation of carboxylic acid HA with ethanol and sulfuric acid as catalist. PVC membrane was prepared by mixed all component such as PVC powder, EHA, plasticizer (o-NPOE and DOP) and anion lipophilic (Sodium-TPB and oleic acid) with a total weight of 100 mg and dissolved in 1 mL of dry THF. The electrode membrane responses showed that the electrodes were highly selective to ion Fe3+ at pH 3 with response time of ±50 seconds. The dynamic range of the membrane ISE sensor was 10-1–10-7 M with the value of Nernst factor was ±19 mV per decade. The membrane electrode can be used for at least 5 weeks. The analytical results of Fe(III) measurement showed good confirmity with reference method (AAS), suggesting that the developed analytical tool could be used to measure and monitor Fe(III) in the real water samples.

Potentiometric MIP-Modified Screen-Printed Cell for Phenoxy Herbicides Detection.

In this study, a molecularly imprinted polymer (MIP)-based screen-printed cell is developed for detecting phenoxy herbicides using 2-methyl-4-chlorophenoxyacetic acid (MCPA) as the template. MCPA is a phenoxy herbicide widely used since 1945 to control broadleaf weeds via growth regulation, primarily in pasture and cereal crops. The potentiometric cell consists of a silver/silver chloride pseudo-reference electrode and a graphite working electrode coated with a MIP film. The polymeric layer is thermally formed after drop-coating of a pre-polymeric mixture composed of the reagents at the following molar ratio: 1 MCPA: 15 MAA (methacrylic acid): 7 EGDMA (ethylene glycol dimethacrylate). After template removal, the recognition cavities function as the ionophore of a classical ion selective electrode (ISE) membrane. The detected ion is the deprotonated MCPA specie, negatively charged, so the measurements were performed in phosphate buffer at pH 5.5. A linear decrease of the potential with MCPA concentration, ranging from 4 × 10-8 to 1 × 10-6 mol L-1, was obtained. The detection limit and the limit of quantification were, respectively, 10 nmol L-1 and 40 nmol L-1. A Nernstian slope of about -59 mV/dec was achieved. The method has precision and LOD required for MCPA determination in contaminated environmental samples.