Solid-contact Ion-selective Electrodes Research Articles

Gold-modified paper as microfluidic substrates with reduced biofouling in potentiometric ion sensing

Microfluidic sampling media based on paper and its modifications with either gold nanoparticles or sputtered gold were evaluated for potentiometric determination of Na+, K+, and Cl– ions in clinically relevant samples. The measurements were conducted in comparison to other commonly considered microfluidic substrates, i.e. sponge, polyester textile, and polyamide textile. Ion determination was done by using solid-contact ion-selective electrodes based on plasticized PVC membranes for Na+, K+, and Cl– ions and utilizing PEDOT(PSS) or PEDOT(Cl) as the ion-to-electron transducer. The solid-contact ion-selective electrodes and a solid-state reference electrode were placed directly on the substrate into which the sample solution was wicked. Transport of bovine serum albumin (BSA) through the paper substrate was studied by ellipsometry. Modification of the paper substrates by gold nanoparticles (AuNPs) was found to slow down the transport of BSA through the paper, when compared with unmodified paper substrates and when compared with all the other alternative sampling matrices studied. The retention of BSA obtained with AuNP-modified paper substrates significantly improved the accuracy of the potentiometric ion determinations in sweat, saliva, artificial tears, and artificial serum. The potentiometric results were validated by inductively coupled plasma optical emission spectrometry (ICP-OES) and ion chromatography (IC). The study indicates that modification of paper by AuNPs is a feasible approach to reduce biofouling of sensors that are used in the paper-based analysis of clinically relevant samples.

Determination of Tedizolid Phosphate Using Graphene Nanocomposite Based Solid Contact Ion Selective Electrode; Green Profile Assessment by Eco‐scale and GAPI Approach

AbstractAntibiotics determination plays a major role in minimizing antimicrobial resistance starting from quality control of pharmaceutical formulations to therapeutic drug monitoring. Green modified glassy carbon electrode has been developed for determination of tedizolid phosphate; new antibiotic prodrug; in presence of its active metabolite. The graphene transducer interlayer, dispersed with PVC, improved the electrode stability and standard potential reproducibility. Graphene hydrophobicity prevented the water layer formation between the sensing layers that decreased the potential drift down to 267 μV h−1. Electrochemical impedance showed a low resistance value for graphene containing sensor due to its high electron transfer ability.

Solid-Contact Ion Sensing Without Using an Ion-Selective Membrane through Classic Li-Ion Battery Materials.

The solid-contact ion-selective electrodes (SC-ISEs) are a type of potentiometric analytical device with features of rapid response, online analysis, and miniaturization. The state-of-the-art SC-ISEs are composed of a solid-contact (SC) layer and an ion-selective membrane (ISM) layer with respective functions of ion-to-electron transduction and ion recognition. Two challenges for the SC-ISEs are the water-layer formation at the SC/ISM phase boundary and the leaking of ISM components, which are both originated from the ISM. Herein, we report a type of SC-ISE based on classic Li-ion battery materials as the SC layer without using the ISM for potentiometric lithium-ion sensing. Both LiFePO4- and LiMn2O4-based SC-ISEs display good Li+ sensing properties (sensitivity, selectivity, and stability). The proposed LiFePO4 electrode exhibits comparable sensitivity and a linear range to conventional SC-ISEs with ISM. Owing to the nonexistence of ISM, the LiFePO4 electrode displays high potential stability. Besides, the LiMn2O4 electrode shows a Nernstian response toward Li+ sensing in a human blood serum solution. This work emphasizes the concept of non-ISM-based SC-ISEs for potentiometric ion sensing.

3D-printed manifold integrating solid contact ion-selective electrodes for multiplexed ion concentration measurements in urine

Urinalysis is a simple and non-invasive approach for the diagnosis and monitoring of various health disorders. While urinalysis is predominantly confined to clinical laboratories the non-invasive sample collection makes it applicable in wide range of settings outside of central laboratory confinements. In this respect, 3D printed devices integrating sensors for measuring multiple parameters may be one of the most viable approaches to ensure cost-effectiveness for widespread use. Here we evaluated such a system for the multiplexed determination of sodium, potassium and calcium ions in urine samples with ion-selective electrodes based on state of the art octadecylamine-functionalized multi-walled carbon nanotube (OD-MWCNT) solid contacts. The electrodes were tested in the clinically relevant concentration range, i.e. ca. 10−4 - 10−1 mol L−1 and were proven to have Nernstian responses under flow injection conditions. The applicability of the 3D printed flow manifold was investigated through the analysis of synthetic samples and two certified reference materials. The obtained results confirm the suitability of the proposed system for multiplexed ion analysis in urine.

A Novel Glassy Carbon Electrode Modified with Multi-Walled Carbon Nanotubes for Potentiometric Xipamide Determination

Solid contact electrodes are widely used in analytical fields due to their outstanding performance over classical ones. However, they showed formation of a water layer affecting stability of those electrodes’ type. Herein, we develop a solid contact ion selective electrode to overcome this common drawback through application of multi-walled carbon nanotubes as a hydrophobic layer between the ion sensing membrane and a glassy carbon electrode. This fine modification improved stability of the electrode via preventing the formation of this water layer. The obtained potential was steady over 30 days with a drift of ∼0.8 mV h−1. The MWCNTs-modified electrode was used for determination of xipamide with a Nernstian slope of −56.01 over a linearity range of 1.0 × 10−5–1.0 × 10−2 mol l−1 and detection limit of 6.0 × 10−6 mol l−1. The proposed sensor was effectively applied for determination of the cited drug in its marketed pharmaceutical dosage form and spiked human plasma.

Ion-to-electron capacitance of single-walled carbon nanotube layers before and after ion-selective membrane deposition

The capacitance of the ion-to-electron transducer layer helps to maintain a high potential stability of solid-contact ion-selective electrodes (SC-ISEs), and its estimation is therefore an essential step of SC-ISE characterization. The established chronopotentiometric protocol used to evaluate the capacitance of the single-walled carbon nanotube transducer layer was revised in order to obtain more reliable and better reproducible values and also to allow capacitance to be measured before membrane deposition for electrode manufacturing quality control purposes. The capacitance values measured with the revised method increased linearly with the number of deposited carbon nanotube–based transducer layers and were also found to correlate linearly before and after ion-selective membrane deposition, with correlation slopes close to 1 for nitrate-selective electrodes, to 0.7 and to 0.5 for potassium- and calcium-selective electrodes.Graphical abstract

Low-cost flexible laminated graphene paper solid-contact ion-selective electrodes

We report here the fabrication of laminated graphene paper solid-contact ion-selective electrodes (SCISE) with performance characteristics equal to the state of the art SCISEs. Several identical and flexible graphene paper electrodes were first prepared from commercially available graphene paper with a standard pouch laminator in a single lamination step to a price of less than $1 per electrode. After that the solid contact consisting of polyaniline (PANI) doped with dinonylnaphthalene sulfonic acid and the K+-selective plasticized poly(vinyl chloride) membrane were deposited in two steps by drop casting on the surface of the graphene paper. The lamination of 10–15 identical graphene paper electrodes takes only one minute and we obtained fully functional graphene paper electrodes in ca. 40 min, including all manual pre-fabrication steps and 10 min of argon plasma cleaning to remove organic contaminants from the graphene surface. We found that plasma cleaning was necessary to improve the reversibility of the electron transfer of the Fe(CN)63−/4− redox couple. The laminated graphene paper K-SCISEs had a Nernstian slope of 56.9 ± 0.1 mV pK-1, a high E° reproducibility of ±4.4 mV (n = 6) still after more than 24 h, high selectivity against Na+, Li+, H+, Mg2+ and Ca2+, and they showed no water layer formation, light and oxygen gas sensitivity.· However, we observed a minor response to carbon dioxide (pH) because of the pH response of PANI. In this work, we show that laminated graphene paper electrodes are a cost-effective alternative for example to commercially available glassy carbon and platinum rod electrodes.

Flow injection amperometry as an alternative to potentiometry for solid contact ion-selective membrane-based electrodes.

In this work we propose a flow injection amperometry at constant potential as a perspective alternative to classical potentiometry for solid contact ion-selective electrodes (SC-ISEs). The amperometric readout mode eliminates the problem of background drift and potential instability – common limitations of potentiometry for SC-ISEs. The selectivity in flowinjection and constant flow amperometric modes is similar to the potentiometric one. Moreover, flow injection amperometry in comparison to potentiometry for ion-selective electrodes provides a shorter response time, within 15–30 s, by two orders of magnitude decreased detection limit and 5-6 fold increased signal-to-noise ratio. The proposed approach is an attractive readout mode that opens new horizons for the improvement of performance characteristics of solid contact ISEs.

An All-in-One Solid State Thin-Layer Potentiometric Sensor and Biosensor Based on Three-Dimensional Origami Paper Microfluidics.

An origami three-dimensional design of a paper-based potentiometric sensor is described. In its simplest form, this electrochemical paper-based analytical device (ePAD) is made from three small parts of the paper. Paper layers are folded on each other for the integration of a solid contact ion selective electrode (here a carbon-paste composite electrode) and a solid-state pseudo-reference electrode (here writing pencil 6B on the paper), which are in contact with a hydrophilic channel fabricated on the middle part (third part) of the paper. In this case, the pseudo-reference and working electrodes are connected to the two sides of the hydrophilic channel and hence the distance between them is as low as the width of paper. The unmodified carbon paste electrode (UCPE) and modification with the crown ether benzo15-crown-5 (B15C5) represented a very high sensitivity to Cu (II) and Cd2+ ions, respectively. The sensor responded to H2O2 using MnO2-doped carbon paste electrode (CPE). Furthermore, a biosensor was achieved by the addition of glucose oxidase to the MnO2-doped CPE and hence made it selective to glucose with ultra-sensitivity. In addition to very high sensitivity, our device benefits from consuming a very low volume of sample (10.0 µL) and automatic sampling without need for sampling devices.

Solid-Contact Potentiometric Sensors Based on Main-Tailored Bio-Mimics for Trace Detection of Harmine Hallucinogen in Urine Specimens.

All-solid-state potentiometric sensors have attracted great attention over other types of potentiometric sensors due to their outstanding properties such as enhanced portability, simplicity of handling, affordability and flexibility. Herein, a novel solid-contact ion-selective electrode (SC-ISE) based on poly(3,4-ethylenedioxythiophene) (PEDOT) as the ion-to-electron transducer was designed and characterized for rapid detection of harmine. The harmine-sensing membrane was based on the use of synthesized imprinted bio-mimics as a selective material for this recognition. The imprinted receptors were synthesized using acrylamide (AA) and ethylene glycol dimethacrylate (EGDMA) as functional monomer and cross-linker, respectively. The polymerization process was carried out at 70 °C in the presence of dibenzoyl peroxide (DBO) as an initiator. The sensing membrane in addition to the solid-contact layer was applied to a glassy-carbon disc as an electronic conductor. All performance characteristics of the presented electrode in terms of linearity, detection limit, pH range, response time and selectivity were evaluated. The sensor revealed a wide linearity over the range 2.0 × 10−7–1.0 × 10−2 M, with a detection limit of 0.02 µg/mL and a sensitivity slope of 59.2 ± 0.8 mV/hamine concentration decade. A 40 mM Britton–Robinson (BR) buffer solution at pH of 6 was used for all harmine measurements. The electrode showed good selectivity towards harmine over other common interfering ions, and maintained a stable electrochemical response over two weeks. After applying the validation requirements, the proposed method revealed good performance characteristics. Method precision, accuracy, bias, trueness, repeatability, reproducibility, and uncertainty were also evaluated. These analytical capabilities support the fast and direct assessment of harmine in different urine specimens. The analytical results were compared with the standard liquid chromatographic method. The results obtained demonstrated that PEDOT/PSS was a promising solid-contact ion-to-electron transducer material in the development of harmine-ISE. The electrodes manifested enhanced stability and low cost, which provides a wide number of potential applications for pharmaceutical and forensic analysis.

Solid-contact ion-selective electrodes based on ferrocene-functionalized multi-walled carbon nanotubes

Solid contact materials based on hydrophobic conductors with a large surface area and high double-layer capacitance (e.g. nanostructured materials) have been reported to provide excellent potential stability to ionophore-based solid-contact ion-selective electrodes (SCISEs). In this respect various carbon materials have emerged as versatile and cost-effective solid contact materials. However, it is generally difficult to control and reproduce the standard potential of ISEs with such capacitive solid contacts. Here we introduce ferrocene-functionalized multi-walled carbon nanotubes to provide redox properties to purely capacitive solid contacts as a means of further controlling the standard potential of the corresponding SCISEs.

Enantioselective high performance new solid contact ion-selective electrode potentiometric sensor based on sulphated γ-cyclodextrin‑carbon nanofiber composite for determination of multichiral drug moxifloxacin

Multiple chiral centered drugs not only pose greater risk than single center in asymmetric medium of human bodies but also beneficial to them in many ways. Therefore, online monitoring and rapid chiral sensing method is always desirable for both isomers as well as their impurities. In the present paper, we have developed a new solid-contact ion-selective electrode (SC-ISE) for enantioselective recognition of RR and SS moxifloxacin (RR-MX/SS-MX) based on chiral nanocomposite of sulphated γ-cyclodextrin (Sγ-CD) and carbon nanofibers (CNF) incorporated into a plasticized poly vinyl chloride (PVC) employing potentiometry. CNF are used for the first time to fabricate SC-ISE as the intermediate layer between an ionophore-doped polymeric membrane and a glassy carbon electrode (GC) for MX enantiomers. The host-guest interaction takes place between γ-CD and RR/SS isomer in the polymeric membrane of the solid-contact electrode forming 1:1 chelate complex where enantioselectivity is achieved in the terms of stability constant (SS-MX = 1786 M−1 and RR-MX = 390 M−1 and Gibbs free energy employing square wave voltammetry (SWV). The new electrode displays a Nernstian slope (60.10 ± 0.25 mV/decade) with the linear range obtained was 1 × 10−2 to 6.5 × 10−7 M and the detection limit of 1.5 ± 0.16 × 10−7 M. The developed solid-contact electrode shows very small drift in potential (EΔ/tΔ = 154 μVh−1) and fast response time of less than 5 s throughout the linear range. The assay of SS-MX in the presence of its antimer RR-MX was carried out using different ratios of both enantiomers, recovery of SS-MX in the presence of RR clearly demonstrate the enantioselectivity and stereospecificity of the proposed SC-ISE. The practical analytical utility of developed chiral potentiometric sensor was demonstrated by measurement of SS-MX in pharmaceutical formulations, urine and blood serum samples. Surface characterization of solid-contact electrode was performed using Frequency Response Analyzer (FRA), Scanning electron microscopy (SEM) and the effect of the interfacial water film was evaluated using potentiometric water layer test.

Multi-Ion-Sensing Emulator and Multivariate Calibration Optimization by Machine Learning Models

One paramount challenge in multi-ion-sensing arises from ion interference that degrades the accuracy of sensor calibration. Machine learning models are here proposed to optimize such multivariate calibration. However, the acquisition of big experimental data is time and resource consuming in practice, necessitating new paradigms and efficient models for these data-limited frameworks. Therefore, a novel approach is presented in this work, where a multi-ion-sensing emulator is designed to explain the response of an ion-sensing array in a mixed-ion environment. A case study is performed emulating the concurrent monitoring of sodium, potassium, lithium, and lead ions, in a medium representative of sweat samples. These analytes are relevant examples of sweat ion-sensing applications for physiology, therapeutic drug monitoring, and heavy metal contamination. It is demonstrated that calibration datasets output by the emulator explain accurately the experimental response of polymeric solid-contact ion-selective electrodes, where root-mean-squared error of 1.37, 1.44, 1.78, 2 mV are obtained, respectively, for Na <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , K <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , Li <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , Pb <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2+</sup> sensor calibration in artificial sweat. Besides, synthetic datasets of custom size are generated to train, validate, and evaluate different types of multivariate regressors. A Multi-Output Support Vector Regressor (M-SVR) is proposed as a compact, accurate, robust, and efficient multivariate calibration model. It features 13.22% normalized root mean squares, and 20.29% mean root squares improvement compared to a simple linear regression model. It is an unbiased estimator for medium to large datasets, and its average generalization error is of 3.22%. Besides, M-SVR models have a lower computational complexity than single-output SVR or neural network models, making them a suitable solution for memory and energy-constrained edge devices used for continuous and real-time multi-ion monitoring.

Potentiometric Carboxylate Sensors Based on Carbazole-Derived Acyclic and Macrocyclic Ionophores

Solid-contact ion-selective electrodes with carbazole-derived ionophores were prepared. They were characterized as acetate sensors, but can be used to determine a number of carboxylates. The potentiometric response characteristics (slope, detection limit, selectivity, and pH sensitivity) of sensors prepared with different membrane compositions (ionophore, ionophore concentration, anion exchanger concentration, and plasticizer) were evaluated. The results show that for the macrocyclic ionophores, a larger cavity provided better selectivity. The sensors exhibited modest selectivity for acetate but good selectivity for benzoate. The carbazole-derived ionophores effectively decreased the interference from lipophilic anions, such as bromide, nitrate, iodide, and thiocyanate. The selectivity, detection limit, and linear range were improved by choosing a suitable plasticizer and by reducing the ionophore and anion exchanger concentrations. The influence of the electrode body’s material upon the composition of the plasticized poly(vinyl chloride) membrane, and thus also upon the sensor characteristics, was also studied. The choice of materials for the electrode body significantly affected the characteristics of the sensors.

Solid-State Membrane Sensors Based on Man-Tailored Biomimetic Receptors for Selective Recognition of Isoproturon and Diuron Herbicides.

Solid-contact ion-selective electrodes (SC-ISEs) have shown great potential for routine and portable ion detection. The introduction of nanomaterials as ion-to-electron transducers and the adoption of different performance-enhancement strategies have significantly promoted the development of SC-ISEs. Herein, new solid-contact ion-selective electrodes, along with the implementation of multiwalled carbon nanotubes (MWCNTs) as ion-to-electron transducers and potassium tetrakis (p-chlorophenyl) borate (KTpClB) as lipophilic ionic additives, were presented for the detection of isoproturon (IPU) and diuron (DU) herbicides. Molecularly imprinted polymers (MIPs), with special molecule recognition properties for isoproturon (IPU) and diuron (DU), were prepared, characterized, and introduced as sensory recognition materials in the presented electrodes. Sensors revealed a near-Nernstian response for both isoproturon (IPU) and diuron (DU) with slopes of 53.1 ± 1.2 (r2 = 0.997) and 57.2 ± 0.3 (r2 = 0.998) over the linear ranges of 2.2 × 10−6–1.0 × 10−3 M and 3.2 × 10−6–1.0 × 10−3 M with detection limits of 8.3 × 10−7 and 1.4 × 10−6 M, respectively. The response time of the presented sensors was found to be <5 s and the lifetime was at least eight weeks. The sensors exhibited good selectivity towards isoproturon (IPU) and diuron (DU) in comparison with some other herbicides, alkali, alkaline earth, and heavy metal ions. The presented sensors were successfully applied for the direct determination of isoproturon (IPU) and diuron (DU) in real water samples.

Rapid Constant Potential Capacitive Measurements with Solid-Contact Ion-Selective Electrodes Coupled to Electronic Capacitor.

A constant potential capacitive readout of solid-contact ion-selective electrodes (SC-ISE) allows one to obtain easily identifiable current transients that can be integrated to obtain a charge vs logarithmic activity relationship. The resulting readout can therefore be much more sensitive than traditional open-circuit potentiometry. Unfortunately, however, comparatively long measurement times and significant baseline current drifts make it currently difficult to fully realize the promise of this technique. We show here that this challenge is overcome by placing the SC-ISE in series with an electronic capacitor, with pH probes as examples. Kirchhoff's law is shown to be useful to choose an adequate range of added capacitances so that it dominates the overall cell value. Two different ion-to-electron transducing materials, functionalized single-wall carbon nanotubes (f-SWCNTs) and poly(3-octylthiophene) (POT), were explored as solid-contact transducing layers. The established SC-ISE-based f-SWCNT transducer is found to be compatible with a wide range of external capacitances up to 100 μF, while POT layers require a narrower range of 1-4.7 μF. Importantly, the time for a charging transient to reach equilibrium was found to be less than 10 s, which is dramatically faster than without added electronic component. Owing to the ideal behavior of capacitor, the response current decays rapidly to zero, making the determination of the integrated charge practically applicable.

Design, synthesis and application of carbazole macrocycles in anion sensors.

Carboxylate sensing solid-contact ion-selective electrodes (ISEs) were created to provide a proof-of-concept ISE development process covering all aspects from in silico ionophore design to functional sensor characterization. The biscarbazolylurea moiety was used to synthesize methylene-bridged macrocycles of different ring size aiming to fine tune selectivity towards different carboxylates. Cyclization was achieved with two separate strategies, using either amide synthesis to access up to –[CH2]10– macrocycles or acyl halides to access up to –[CH2]14– macrocycles. Seventy-five receptor–anion complexes were modelled and studied with COSMO-RS, in addition to all free host molecules. In order to predict initial selectivity towards carboxylates, 1H NMR relative titrations were used to quantify binding in DMSO-d6/H2O solvent systems of two proportions – 99.5%:0.5% m/m and 90.0%:10.0% m/m, suggesting initial selectivity towards acetate. Three ionophores were selected for successful sensor prototype development and characterization. The constructed ion-selective electrodes showed higher selectivity towards benzoate than acetate, i.e., the selectivity patterns of the final sensors deviated from that predicted by the classic titration experiments. While the binding constants obtained by NMR titration in DMSO-d6/H2O solvent systems provided important guidance for sensor development, the results obtained in this work emphasize the importance of evaluating the binding behavior of receptors in real sensor membranes.

Solid reference electrode integrated with paper-based microfluidics for potentiometric ion sensing

A new concept of a solid reference electrode integrated with microfluidic paper-based sampling was introduced and applied in potentiometric ion sensing. The new reference electrode consisted of an Ag/AgCl reference element (reusable) that is in contact with a disposable paper substrate (DPS) containing solid KCl. Thus, no KCl reference solution was applied during the analysis step, but the applied sample solution dissolved the solid KCl in the paper providing the electrolyte for the Ag/AgCl reference element. Such reference electrode was found to give a relatively constant potential after less than ca 1 min of equilibration. Moreover, the response of the reference electrode was not affected by concentrations of background electrolytes in the sample. Thus the proposed reference electrode was integrated with a paper-based microfluidic device and solid-contact ion-selective electrodes (ISEs) sensitive to K+, Na+ and Cl−. The optimized systems were characterized with near-Nernstian sensitivities (59.1 ± 1.5, 57.5 ± 0.5 and –56.4 ± 0.6 mV dec−1) and detection limits (10−4.1 ± 0.1, 10−3.3 ± 0.1 and 10−4.1 ± 0.1 mol dm−3) for K+, Na+ and Cl− ions, respectively. The paper-based measurement setup was favourably used for potentiometric determination of ions in environmental (wastewater sludge) and clinically relevant (sweat) samples.

Alternative coulometric signal readout based on a solid-contact ion-selective electrode for detection of nitrate

Traditional potentiometric NO3−-selective electrodes suffer from a fundamental limitation of the Nernst slope (59.1 mV/dec at 25 °C) due to the relationship between the potential and the logarithmic of ionic activity. Herein, a coulometric signal readout is proposed instead of the potentiometric response for detection of NO3− based on an ordered mesoporous carbon (OMC)-based solid-contact ion-selective electrode (ISE). The mechanism for obtaining the coulometric signal is based on the electrical double layer capacitance of OMC compensating the potential change at the ion-selective membrane/solution interface during the measurements under the control of a constant applied potential. Under the optimized conditions, the coulometric signal for the OMC-based solid-contact NO3−-ISE shows two linear responses in the activity range of 1.0 × 10−6-8.0 × 10−6 M and 8.0 × 10−6-8.0 × 10−4 M, and the detection limit is 4.0 × 10−7 M (3σ/s). The proposed coulometric response also shows excellent reproducibility and stability in the presence of O2 and CO2 and light on/off. Additionally, the coulometric response shows acceptable and reliable results for detection of NO3− in mineral water as compared to the traditional potentiometric response and the ion chromatography. This work provides a promising alternative signal readout for detection of ions by using solid-contact ion-selective electrodes.

Characterization of nano-layered solid-contact ion selective electrodes by simultaneous potentiometry and quartz crystal microbalance with dissipation

Nano-layered solid-contact potassium-selective electrodes (K+-ISEs) were explored as model ion-selective electrodes for their practical use in clinical analysis. The ultra-thin ISEs ought to be manufactured in a highly reproducible manner, potentially making them suitable for mass production. Thus, their development is pivotal towards miniaturised sensors with simplified conditioning/calibration protocols for point-of-care diagnostics. To study nano-layered ISEs, the ultra-thin nature of ISEs for the first time enabled to combine potentiometry-quartz crystal microbalance with dissipation (QCM-D) to obtain value-added information on the ISE potentiometric response regarding their physical state such as mass/thickness/viscoelastic properties/structural homogeneity. Specifically, the studies were focused on real-time observations of the ISE potentiometric response in relation to changes of their physicochemical properties during the ISE preparation (conditioning) and operation (including biofouling conditions) to identify the occurring processes that may accordingly be critical for potential instability of the ISEs, impeding their practical application. The K+-ISEs were prepared on a QCM-D gold sensor by electrodepositing poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) layer serving as an ion-to-electron transducer subsequently covered by a spin-coated poly(vinyl chloride) based K+-ion selective membrane (K+-ISM). The studies demonstrated that the performance of the nano-layered design of K+-ISEs is detrimentally affected by such processes as water layer formation accordingly causing the instability of the electrode potential. The changes in the ISE physical state such mass/viscoelastic properties associated with water layer formation and origin of the potential instability was already observed at the ISE conditioning stage. The potential instability of nano-layered ISEs limits their practical applicability, indicating the need of new solutions in designing ISEs, for instance, exploiting new water-resistant materials and modifying preparation protocols.