The Use of an Acylhydrazone-Based Metal-Organic Framework in Solid-Contact Potassium-Selective Electrode for Water Analysis

A solid-contact ion-selective electrode was developed for detecting potassium in environmental water. Two versions of a stable cadmium acylhydrazone-based metal organic framework, i.e., JUK-13 and JUK-13_H2O, were used for the construction of the mediation layer. The potentiometric and electrochemical characterizations of the proposed electrodes were carried out. The implementation of the JUK-13_H2O interlayer is shown to improve the potentiometric response and stability of measured potential. The electrode exhibits a good Nernstian slope (56.30 mV/decade) in the concentration range from 10−5 to 10−1 mol L−1 with a detection limit of 2.1 µmol L−1. The long-term potential stability shows a small drift of 0.32 mV h−1 over 67 h. The electrode displays a good selectivity comparable to ion-selective electrodes with the same membrane. The K-JUK-13_H2O-ISE was successfully applied for the determination of potassium in three certified reference materials of environmental water with great precision (RSD < 3.00%) and accuracy (RE < 3.00%).

Fabrication of an All-Solid-State Ammonium Paper Electrode Using a Graphite-Polyvinyl Butyral Transducer Layer

A planar solid-state ammonium-selective electrode, employing a composite mediator layer of graphite particles embedded in a polyvinyl butyral matrix on top of an inkjet-printed silver electrode, is presented in this paper. The effect of graphite powder mass fraction on the magnitude of the potentiometric response of the sensor was systematically verified using a batch-mode and a flow injection measurement setup. Under steady-state conditions, the paper electrode provided a Nernstian response of 57.30 mV/pNH4 over the concentration range of 10−5 M to 10−1 M with a detection limit of 4.8 × 10−6 M, while the analytical performance of the array in flow mode showed a narrower linear range (10−4 M to 10−1 M; 60.91 mV/pNH4 slope) with a LOD value of 5.6 × 10−5 M. The experimental results indicate that the prepared electrode exhibited high stability and fast response to different molar concentrations of ammonium chloride solutions. The pH-response of the paper NH4-ISE was also investigated, and the sensor remained stable in the pH range of 2.5–8.5. The potentiometric sensor presented here is simple, lightweight and inexpensive, with a potential application for in-situ analysis of environmental water samples.

Parallel Potentiometric and Capacitive Response in a Water-Gate Thin Film Transistor Biosensor at High Ionic Strength

We show that an SnO2-based water-gate thin film transistor (WGTFT) biosensor responds to a waterborne analyte, the spike protein of the SARS-CoV-2 virus, by a parallel potentiometric and capacitive mechanism. We draw our conclusion from an analysis of transistor output characteristics, which avoids the known ambiguities of the common analysis based on transfer characteristics. Our findings contrast with reports on organic WGTFT biosensors claiming a purely capacitive response due to screening effects in high ionic strength electrolytes, but are consistent with prior work that clearly shows a potentiometric response even in strong electrolytes. We provide a detailed critique of prior WGTFT analysis and screening reasoning. Empirically, both potentiometric and capacitive responses can be modelled quantitatively by a Langmuir‒Freundlich (LF) law, which is mathematically equivalent to the Hill equation that is frequently used for biosensor response characteristics. However, potentiometric and capacitive model parameters disagree. Instead, the potentiometric response follows the Nikolsky-Eisenman law, treating the analyte ‘RBD spike protein’ as an ion carrying two elementary charges. These insights are uniquely possible thanks to the parallel presence of two response mechanisms, as well as their reliable delineation, as presented here.

Potentiometric Surfactant Sensor Based on 1,3-Dihexadecyl-1H-benzo[d]imidazol-3-ium for Anionic Surfactants in Detergents and Household Care Products

A 1,3-dihexadecyl-1H-benzo[d]imidazol-3-ium-tetraphenylborate (DHBI-TPB) ion-pair implemented in DHBI-TPB surfactant sensor was used for the potentiometric quantification of anionic surfactants in detergents and commercial household care products. The DHBI-TPB ion-pair was characterized by FTIR spectroscopy and computational analysis which revealed a crucial contribution of the C–H∙∙∙π contacts for the optimal complex formation. The DHBI-TPB sensor potentiometric response showed excellent analytical properties and Nernstian slope for SDS (60.1 mV/decade) with LOD 3.2 × 10−7 M; and DBS (58.4 mV/decade) with LOD 6.1 × 10−7 M was obtained. The sensor possesses exceptional resistance to different organic and inorganic interferences in broad pH (2–10) range. DMIC used as a titrant demonstrated superior analytical performances for potentiometric titrations of SDS, compared to other tested cationic surfactants (DMIC > CTAB > CPC > Hyamine 1622). The combination of DHBI-TPB sensor and DMIC was successfully employed to perform titrations of the highly soluble alkane sulfonate homologues. Nonionic surfactants (increased concentration and number of EO groups) had a negative impact on anionic surfactant titration curves and a signal change. The DHBI-TPB sensor was effectively employed for the determination of technical grade anionic surfactants presenting the recoveries from 99.5 to 101.3%. The sensor was applied on twelve powered samples as well as liquid-gel and handwashing home care detergents containing anionic surfactants. The obtained results showed good agreement compared to the outcomes measured by ISE surfactant sensor and a two-phase titration method. The developed DHBI-TPB surfactant sensor could be used for quality control in industry and has great potential in environmental monitoring.

The Influence of Plasticizers on the Response Characteristics of the Surfactant Sensor for Cationic Surfactant Determination in Disinfectants and Antiseptics

Surfactant liquid-membrane type sensors are usually made of a PVC, ionophore and a plasticizer. Plasticizers soften the PVC. Due to their lipophilicity, they influence the ion exchange across the membrane, ionophore solubility, membrane resistance and, consequently, the analytical signal. We used the DMI-TPB as an ionophore, six different plasticizers [2-nitrophenyl-octyl-ether (P1), bis(2-ethylhexyl) phthalate (P2), bis(2-ethylhexyl) sebacate (P3), 2-nitrophenyl phenyl ether (P4), dibutyl phthalate (P5) and dibutyl sebacate (P6)] and a PVC to produce ionic surfactant sensors. Sensor formulation with P1 showed the best potentiometric response to four usually used cationic surfactant, with the lowest LOD, 7 × 10−7 M; and potentiometric titration curves with well-defined and sharp inflexion points. The sensor with P6 showed the lowest analytical performances. Surfactant sensor with P1 was selected for quantification of cationic surfactant in model solutions and commercial samples of disinfectants and antiseptics. It showed high accuracy and precision in all determinations, with recovery from 98.2 to 99.6, and good agreement with the results obtained with surfactant sensor used as a referent one, and a standard two-phase titration method. RDS values were lower than 0.5% for all determinations.

Potentiometric Electronic Tongue for Pharmaceutical Analytics: Determination of Ascorbic Acid Based on Electropolymerized Films

This work deals with the design of an experimental potentiometric electronic tongue (ET) for the recognition of various samples of effervescent tablets with different ascorbic acid (vitamin C) contents. The ET consisted of twelve potentiometric sensors based on conductive polymers, which were derived from 4-amino-2,1,3-benzothiadiazole, 3,4-diaminobenzoic acid, and neutral red on the surface of the platinum electrode using cyclic voltammetry. The aim of the potentiometric study was to assess the influence of the vitamin C content and the composition of the matrix of commercial samples on the potentiometric response. The results obtained from the sensor array proved that the stability of the potentiometric signal and the accuracy of measurements are affected by individual sensors. The identification of the vitamin C content in the individual samples of effervescent tablets obtained by means of the potentiometric electronic tongue corresponded with the results of the coulometric titration.

The Origin of the Non-Constancy of the Bulk Resistance of Ion-Selective Electrode Membranes within the Nernstian Response Range

The dependence of the bulk resistance of membranes of ionophore-based ion-selective electrodes (ISEs) on the composition of mixed electrolyte solutions, within the range of the Nernstian potentiometric response, is studied by chronopotentiometric and impedance measurements. In parallel to the resistance, water uptake by the membranes is also studied gravimetrically. The similarity of the respective curves is registered and explained in terms of heterogeneity of the membranes due to the presence of dispersed aqueous phase (water droplets). It is concluded that the electrochemical equilibrium is established between aqueous solution and the continuous organic phase, while the resistance refers to the membrane as whole, and water droplets hamper the charge transfer across the membranes. In this way, it is explained why the membrane bulk resistance is not constant within the range of the Nernstian potentiometric response of ISEs.

Potassium-Selective Solid-Contact Electrode with High-Capacitance Hydrous Iridium Dioxide in the Transduction Layer

This work presents new material for solid-contact layers—hydrous iridium dioxide IrO2·2H2O, characterized by high electrical capacitance value, evaluated using chronopotentiometry (1.22 mF) and electrochemical impedance spectroscopy (1.57 mF). The remarkable electrical parameters of layers resulted in great analytical parameters of IrO2·2H2O-contacted potassium-selective electrodes. Various parameters of ion-selective electrodes were examined in the scope of this work using a potentiometry method including: linear range, repeatability, stability of potentiometric response and sensitivity to varying measurement conditions. The analytical parameters obtained for solid-contact electrodes were compared with the ones obtained for coated disc electrodes to evaluate the influence of the iridium dioxide layer. The linear range of the IrO2·2H2O-contacted K+-selective electrodes covered concentrations of K+ ions from 10−6 to 10−1 M and the potential stability was estimated at 0.097 mV/h. The IrO2·2H2O-contacted electrodes turned out to be insensitive to varying light exposure and changes in the pH values of measured solutions (in the pH range of 2 to 10.5). A water layer test proved that, contrary to the coated disc electrode, the substantial water film is not formed between the ion-selective membrane and iridium dioxide layer.

Potentiometric Response of Solid-State Sensors Based on Ferric Phosphate for Iron(III) Determination

A novel ion-selective electrode with membranes based on iron(III) phosphate and silver sulfide integrated into a completely new electrode body design has been developed for the determination of iron(III) cations. The best response characteristics with linear potential change were found in the iron(III) concentration range from 3.97× 10−5 to 10−2 mol L−1. The detection limit was found to be 2.41× 10−5 mol L−1 with a slope of –20.53 ± 0.63 and regression coefficient of 0.9925, while the quantification limit was 3.97× 10−5 M. The potential change per concentration decade ranged from –13.59 ± 0.54 to –20.53 ± 1.56 for Electrode Body 1 (EB1) and from –17.28 ± 1.04 to –24 ± 1.87 for Electrode Body 2 (EB2), which is presented for the first time in this work. The prepared electrode has a long lifetime and the ability to detect changes in the concentration of iron cations within 20 s. Membrane M1 showed high recoveries in the determination of iron cations in iron(III) standard solutions (98.2–101.2%) as well as in two different pharmaceuticals (98.6–106.5%). This proves that this type of sensor is applicable in the determination of ferric cations in unknown samples, and the fact that all sensor parts are completely manufactured in our laboratory proves the simplicity of the method.