Potentiometric Measurements Research Articles

Sensitivity-enhanced potentiometric measurement by incorporating graphitic carbon nitride into the ion-to-electron transducer of potassium ion-selective electrodes.

In recent years, wearable sweat sensors have garnered significant attention for real-time monitoring of human physiological information because of their ability to continuously and non-invasively detect multiple sweat biomarkers. Among these, potentiometric sensors stand out for their low power consumption, low cost, compact design, and real-time monitoring capabilities, making them an ideal alternative for sweat analysis. However, enhancing the sensitivity of ion-selective electrodes (ISEs), a critical parameter of potentiometric sensors, remains a challenging research focus. In this work, the sensitivity of K+ ISEs was significantly enhanced by doping two-dimensional nanoparticles graphitic carbon nitride (g-C₃N₄) into the ion-to-electron transducer of the electrode via electrodeposition. The calibration curve slope of the K+ potentiometric sensors with doped g-C3N4 reached 59.6mV/dec, representing a 33% increase in sensitivity compared to the control sensor without g-C₃N₄. Furthermore, the developed sensors demonstrated excellent repeatability, and anti-interference capabilities. Finally, the feasibility of the prepared sensors was further validated in artificial sweat. The large specific surface area of g-C₃N₄ combined with the excellent conductivity of PEDOT: PSS, significantly improved the sensitivity of ISEs in this study. This innovative approach paves a new avenue for the application of two-dimensional materials in potentiometric sensors, potentially advancing the field of real-time sweat analysis.

Tailoring the surface of a polymeric membrane with a thin-layer Nafion membrane: Construction of an anti-surfactant solid-contact ion-selective electrode

Surfactants are a type of amphiphilic chemicals that comprise both hydrophilic and hydrophobic regions, and the presence of surfactants would bring a detrimental effect on the potential responses of the solid-contact ion-selective electrodes induced by their extraction from the aqueous solution into the polymeric membrane phase. Herein, an anti-surfactant solid-contact Ca2+-selective electrode is proposed based on tailoring the surface of the polymeric membrane with the thin-layer Nafion membrane. The extraction of surfactants into the polymeric membrane can be eliminated through using the hydrophobic group of Nafion acting as “a polymer brush”, while the Ca2+ diffusion from the aqueous solution to the membrane phase is promoted by the hydrophilic group of Nafion based on the electrostatic interaction. The Nafion-functionalized solid-contact Ca2+-ISE shows an improved potential stability and an excellent potentiometric performance for detection of Ca2+ in the presence of cationic and anionic surfactants as compared to the traditional solid-contact Ca2+-ISE. Moreover, the anti-surfactant solid-contact ion-selective electrode is feasible for in situ measurement of Ca2+ at the interface between the seawater and the sediment. This work provides a general and facile strategy to eliminate the interferences of surfactants during the potentiometric measurements, and is favorable for in situ, on-site measurement with high accuracy and precision in the aquatic environment.

LIG-Based High-Sensitivity Multiplexed Sensing System for Simultaneous Monitoring of Metabolites and Electrolytes.

With improvements in medical environments and the widespread use of smartphones, interest in wearable biosensors for continuous body monitoring is growing. We developed a wearable multiplexed bio-sensing system that non-invasively monitors body fluids and integrates with a smartphone application. The system includes sensors, readout circuits, and a microcontroller unit (MCU) for signal processing and wireless communication. Potentiometric and amperometric measurement methods were used, with calibration capabilities added to ensure accurate readings of analyte concentrations and temperature. Laser-induced graphene (LIG)-based sensors for glucose, lactate, Na+, K+, and temperature were developed for fast, cost-effective production. The LIG electrode's 3D porous structure provided an active surface area 16 times larger than its apparent area, resulting in enhanced sensor performance. The glucose and lactate sensors exhibited high sensitivity (168.15 and 872.08 μAmM-1cm-2, respectively) and low detection limits (0.191 and 0.167 μM, respectively). The Na+ and K+ sensors demonstrated sensitivities of 65.26 and 62.19 mVdec-1, respectively, in a concentration range of 0.01-100 mM. Temperature sensors showed an average rate of resistance change per °C of 0.25%/°C, within a temperature range of 20-40 °C, providing accurate body temperature monitoring.

Designing new sulfate ionophores for potentiometric membrane sensors: Selectivity assessment and practical application

Developing potentiometric chemical sensors for sulfate determination is a rather challenging task due to a considerable hydrophilicity of this anion and its poor affinity to lipophilic plasticized polymeric membranes – one of the most popular sensor membrane materials nowadays. Not too many research works were devoted to this problem in the last years. Here we report on the successful development of several novel sulfate ionophores based on the synthetic modification of the commercially available sulfate ionophore I. The newly developed sensors outperform commercial analogue in terms of elelctrochemical sensitivity and selectivity. We have highlighted certain problems with numerical selectivity assessment in case when primary and interfering ions have different charges. The counterintuitive results yielded by conventional selectivity quantification methods implies the relevance of using alternative approach – visualizing sensor response curves towards primary ion in the presence of interfering ions. Novel sulfate sensors were applied for direct potentiometric measurements of sulfate content in river water samples demonstrating real applicability of the developed sensor membranes.

Stability constants of mixed-ligand cobalt(II) complexes with pyridinedicarboxylic acids and small bioligands studied by potentiometric measurements

In this work, we have studied the stability constants of ternary cobalt(II) complexes with the primary ligands: pyridine-2,3-dicarboxylic acid (H22,3-Dipic, H2L) and pyridine-3,4-dicarboxylic acid (H23,4-Dipic, H2L) and secondary ligands representing low molecular mass components of blood serum: lactic acid (HLac), oxalic acid (H2Ox), citric acid (H3Cit), and phosphoric acid (H3PO4). Potentiometric data were analyzed using the least squares computational program LETAGROP. Ionic strength and temperature were both kept constant using 1.0 mol dm−3 NaNO3 as ionic medium at 25 °C. Species distribution diagrams were generated to determine the speciation variations with respect to pH.

Efficient Taste Analysis via Single-Channel Hybrid Electronic Tongue

The prospective applications of electronic tongues (e-tongues) in the food, water, beverage, and pharmaceutical industries have long been hampered by the inconvenient nature of series measurements using expensive and specialised sensor arrays. A cost-efficeint and easier solution to this problem arises in the shape of a single-channel hybrid e-tongue, presenting a novel approach to overcoming restrictions. This progress uses data fusion from potentiometry and impedimetry to combine these measures into a single channel made up of unfunctionalized metal electrodes supported by a pH electrode.The hybrid e-tongue combines potentiometric response, which includes pH and open circuit potential, with impedimetric response, which takes into account comparable electric circuit parameters such as charge transfer resistance and double-layer capacitance. The taste discriminability of this low-cost single-channel hybrid e-tongue is validated using two metal electrodes, Pt and Ni, and two separate sample preparations of basic taste analytes, each at concentrations around the human tongue threshold.Principal component analysis (PCA) plots are used to test qualitative discrimination by reducing dimensionality and clustering analytes. Silhouette coefficients (SC) and hierarchical cluster analysis are used to assess clustering quality. Even without particular sample preparation, the Pt and Ni electrodes exhibit substantial clustering with SC values of 0.83 and 0.74, respectively. This significant outcome highlights the efficacy of the hybrid e-tongue in improving taste discriminability.Comparisons with potentiometric and impedimetric measurements performed independently show that the hybrid e-tongue, assisted by data fusion at a single channel, improves accuracy and clustering significantly. This finding not only speeds up the analysis process, but it also improves the overall effectiveness of taste discrimination.Correlations between taste analytes and physicochemical factors are formed using heatmap plots and PCA loading plots to provide a fuller knowledge of the hybrid e-tongue's mechanics. These visualisations provide vital insights into the complex interplay of several physicochemical processes, offering insight into the mechanism underlying the hybrid e-tongue's excellent performance.discrimination.Despite its remarkable capabilities, the study acknowledges that taste discriminability diminishes due to the buffer activity of the standard reference solution used for sample preparation. This recognition prompts further exploration and optimization of the solution to ensure the broad applicability of the hybrid e-tongue across various scenarios.In conclusion, the reported single-channel hybrid e-tongue represents a significant advancement in taste analysis technology. By addressing the challenges associated with series measurements on complex sensor arrays, this innovation opens new avenues for commercial e-tongues in diverse industries. The amalgamation of potentiometry and impedimetry in a single channel not only enhances accuracy and clustering but also provides valuable mechanistic insights. As the research community continues to refine and optimize this technology, the future holds great promise for the widespread adoption of single-channel hybrid e-tongues in analytical applications, advancing how we perceive and understand taste.

Study of Thermodynamic and Transport Properties of the Ternary System (1-Hexyl-3-Methylimidazolium Bromide + Ethanol + Water) Based on Potentiometric and Conductometric Measurements

Study of Thermodynamic and Transport Properties of the Ternary System (1-Hexyl-3-Methylimidazolium Bromide + Ethanol + Water) Based on Potentiometric and Conductometric Measurements

A multiplexed sensing system with multimodal readout electronics and thread-based electrochemical sensors for high throughput screening

High throughput screening (HTS) based on microwell (or bioreactor) arrays is a well-established approach for rapid screening and identification of lead molecules or target analytes for drug discovery and other applications in biotechnology. However, it has been challenging to scale up these platforms due to the lack of integrated sensors to monitor the microenvironment of each microwell in the array needed. In this work, we present a practical solution for a miniaturized multiplexed sensing system with integrated circuitry capable of performing continuous electrochemical potentiometric and amperometric measurements. The platform uses lightweight multiplexed electrochemical sensors implemented on thin textile threads, all of which share a single operational amplifier (op-amp) and a switch network for both voltage and current measurements. The resulting platform forgoes the need for large-area sensors or bulky multichannel potentiostat with a simple readout circuitry capable of multimodal measurements. The design and validation of the multiplexed sensing system have been reported in the context of measuring pH and oxygen (O2), which are crucial biomarkers for any HTS application. The thread-based pH and O2 sensors possess sensitivities of ∼65.87 mV/pH for the pH sensor (n = 3) and 0.6621 nA/mg L-1 for the O2 sensor (n = 3). This architecture is modular such that it can be easily extended to monitoring multiple biomarkers employing thread-based sensors and sharing the same readout circuitry, making it a practical and versatile tool for biotechnology research.

PdRuO2/PVP nanomaterial as a highly selective, stable, and applicable potentiometric sensor for the detection of Cr3+

PdRuO2/PVP nanomaterial was synthesized using a straightforward method and characterized using advanced analytical methods such as TEM, XRD, XPS, elemental mapping and SEM. The synthesized PdRuO2/PVP nanomaterial was used as an ionophore in potentiometric sensor electrodes and successfully adapted to Cr3+ ion detection in a large number of aqueous samples. Several experimental parameters of the PdRuO2/PVP sensor such as potentiometric behavior, selectivity, repeatability, response time, pH, titration, and recovery in real samples were investigated. Potentiometric behavioral characteristics were performed in the concentration range 1 × 10−6–1.0 × 10−1 M. The repeated experiments performed six times showed that there was no deviation in the measurements. The limit of detection of the PdRuO2/PVP potentiometric sensor was very low with a value of 8.6 × 10−8 M. The potentiometric measurements showed that the synthesized PdRuO2/PVP ionophore was highly effective in detecting Cr3+ in a wide pH range of 2.0–8.0 and was found to have a shelf life of over 1 year. As a result, the synthesized PdRuO2/PVP electrode material was found to be highly selective, stable, and applicable for Cr3+ detection.Graphical

Advancing Cholesterol Detection: A Simulation Study on SrTiO3-Based BioFET Biosensors

This study presents an analytical model of a strontium titanate (SrTiO3)-based biological field-effect transistor (BioFET) for cholesterol detection. Known for its high dielectric permittivity, surface charge regulation, and superior ionic and thermal conductivity, SrTiO3 enhances the functionality of biosensors. The BioFET employs a gate functionalized with a cholesterol-specific enzyme, which facilitates potentiometric measurements of cholesterol concentrations. The model establishes a quantitative relationship between cholesterol concentration and gate voltage in enzyme-immobilized SrTiO3, demonstrating the high selectivity of SrTiO3-based BioFETs for cholesterol detection. This indicates their potential in developing diagnostic tools for cholesterol-related conditions and monitoring food quality. Additionally, the analytical model effectively predicts the behavior of the detection mechanism in electrochemical BioFET biosensors, underscoring its innovative application in fields such as microelectronics, sensors, and catalysis.

Physicochemical properties of pectin-Fe(III) gained by HG-type hawthorn with different esterification degree

In this study, the complexation ability of HG-type hawthorn pectin with trivalent iron ions after de-esterification was investigated. The moderate esterification reaction could significantly increase the iron content in HG-type hawthorn pectin. Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) experiments proved that -OH and -COOH in the pectin acted as a bridge connecting Fe3+ leading to the formation of β-FeOOH structure, and the trivalent iron ions were successfully complexed into the HG-type hawthorn pectin. In addition, infrared and ultraviolet spectroscopic scans, particle size, and potentiometric measurements were carried out to demonstrate the complexation coordination mechanism of hawthorn pectin with Fe3+, and there were differences in the complexation effect of HG-type hawthorn pectin with different degrees of esterification. The gelling properties of HG-type hawthorn pectin were subsequently verified by in vitro gastrointestinal tract simulation experiments to aid the smooth passage of ferric ions through the gastric juices and reduce irritation. The success of the experiments demonstrated that HG-type hawthorn pectin is an excellent raw material for metal complexation, and the degree of esterification is one of the important factors affecting its complexation effect, which proves its potential application value as an iron supplement.

Thermodynamic Investigation of Sodium Nitrate in N,N-dimethylformamide Aqueous Mixtures Based on Potentiometric Measurements at T = (298.2, 303.2, and 308.2) K

Thermodynamic Investigation of Sodium Nitrate in N,N-dimethylformamide Aqueous Mixtures Based on Potentiometric Measurements at T = (298.2, 303.2, and 308.2) K

A New Planar Potentiometric Sensor for In Situ Measurements.

A new construction of a potentiometric sensor was introduced for the first time. It relies on the use of two membranes instead of one, as in the well-known coated-disc electrode. For this purpose, a new electrode body was constructed, including not one, but two glassy carbon discs covered with an ion-selective membrane. This solution allows for the sensor properties to be enhanced without using additional materials (layers or additives) on the membrane. The new construction is particularly useful for in situ measurements in environmental samples. Two ion-selective polymeric membranes were used, namely H+ and K+-selective membranes, to confirm the universality of the idea. The tests conducted included chronopotentiometric tests, electrochemical impedance spectroscopy, and potentiometric measurements. The electrical and analytical parameters of the sensors were evaluated and compared for all tested electrodes to evaluate the properties of the planar electrode versus previously known constructions. Research has shown that the application of two membranes instead of one allows for the resistance of an electrode to be lowered and for the electrical capacitance to be elevated. Improving the electrical properties of an electrode resulted in the enhancement of its analytical properties. The pH measurement range of the planar electrode is 2-11, which is much wider in contrast to that of the single-membrane electrode. The linear range of the K+-selective planar electrode is wider than that of the coated-disc electrode and equals 10-6 to 10-1 M. The response time turned out to be a few seconds shorter, and the potential drift was smaller due to the application of an additional membrane in the electrode construction. This research creates a new opportunity to design robust potentiometric sensors, as the presented construction is universal and can be used to obtain electrodes selective to various ions.

BDNF- and VEGF-Responsive Stimulus to an NGF Mimic Cyclic Peptide with Copper Ionophore Capability and Ctr1/CCS-Driven Signaling.

Neurotrophins are a family of growth factors that play a key role in the development and regulation of the functioning of the central nervous system. Their use as drugs is made difficult by their poor stability, cellular permeability, and side effects. Continuing our effort to use peptides that mimic the neurotrophic growth factor (NGF), the family model protein, and specifically the N-terminus of the protein, here we report on the spectroscopic characterization and resistance to hydrolysis of the 14-membered cyclic peptide reproducing the N-terminus sequence (SSSHPIFHRGEFSV (c-NGF(1-14)). Far-UV CD spectra and a computational study show that this peptide has a rigid conformation and left-handed chirality typical of polyproline II that favors its interaction with the D5 domain of the NGF receptor TrkA. c-NGF(1-14) is able to bind Cu2+ with good affinity; the resulting complexes have been characterized by potentiometric and spectroscopic measurements. Experiments on PC12 cells show that c-NGF(1-14) acts as an ionophore, influencing the degree and the localization of both the membrane transporter (Ctr1) and the copper intracellular transporter (CCS). c-NGF(1-14) induces PC12 differentiation, mimics the protein in TrkA phosphorylation, and activates the kinase cascade, inducing Erk1/2 phosphorylation. c-NGF(1-14) biological activities are enhanced when the peptide interacts with Cu2+ even with the submicromolar quantities present in the culture media as demonstrated by ICP-OES measurements. Finally, c-NGF(1-14) and Cu2+ concur to activate the cAMP response element-binding protein CREB that, in turn, induces the brain-derived neurotrophic factor (BDNF) and the vascular endothelial growth factor (VEGF) release.

Light‐induced Delivery of Charged Species using Ion‐selective Core–Shell Nanoparticles

AbstractControlled release systems have gained considerable attention owing to their potential to deliver molecules, including ions and drugs, in a customized manner. We present a light‐induced ion‐transfer platform consisting of a dispersion of nanoparticles (NPs, ~300 nm) with the conductive polymer poly(3‐octylthiophene‐2,5‐diyl) (POT) in the core and a potassium (K+)‐selective membrane in the shell. Owing to the photoactive nature of POT, POT NPs can be used for a dual purpose: as a host for positively charged species and as an actuator to trigger the subsequent release. POT0 and doped POT+ coexist in the core, allowing K+ encapsulation in the shell. As POT0 is photo‐oxidized to POT+, K+ is released to the (aqueous) dispersion phase to preserve the neutrality of the NPs. This process is reversible and can be simultaneously assessed using the native fluorescence of POT0 and via potentiometric measurements. The NP structure and its mechanism of action were thoroughly studied with a series of control experiments and complementary techniques. Understanding the NP and its surrounding interactions will pave the way for other nanostructured systems, facilitating sophisticated applications. The delivery of ionic drugs and interference/pollutant catching for advanced sensing/restoration will be considered in future research.

Light-induced Delivery of Charged Species using Ion-selective Core-Shell Nanoparticles.

Controlled release systems have gained considerable attention owing to their potential to deliver molecules, including ions and drugs, in a customized manner. We present a light-induced ion-transfer platform consisting of a dispersion of nanoparticles (NPs, ~300 nm) with the conductive polymer poly(3-octylthiophene-2,5-diyl) (POT) in the core and a potassium (K+)-selective membrane in the shell. Owing to the photoactive nature of POT, POT NPs can be used for a dual purpose: as a host for positively charged species and as an actuator to trigger the subsequent release. POT0 and doped POT+ coexist in the core, allowing K+ encapsulation in the shell. As POT0 is photo-oxidized to POT+, K+ is released to the (aqueous) dispersion phase to preserve the neutrality of the NPs. This process is reversible and can be simultaneously assessed using the native fluorescence of POT0 and via potentiometric measurements. The NP structure and its mechanism of action were thoroughly studied with a series of control experiments and complementary techniques. Understanding the NP and its surrounding interactions will pave the way for other nanostructured systems, facilitating sophisticated applications. The delivery of ionic drugs and interference/pollutant catching for advanced sensing/restoration will be considered in future research.

Mesoporous Carbons and Highly Cross-Linking Polymers for Removal of Cationic Dyes from Aqueous Solutions-Studies on Adsorption Equilibrium and Kinetics.

This study presents the results of applying the methods of synthesizing mesoporous carbon and mesoporous polymer materials with an extended porous mesostructure as adsorbents for cationic dye molecules. Both types of adsorbents are synthetic materials. The aim of the presented research was the preparation, characterisation, and utilisation of obtained mesoporous adsorbents. The physicochemical properties, morphology, and porous structure characteristics of the obtained materials were determined using low-temperature nitrogen sorption isotherms, X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and potentiometric titration measurements. The morphology and microstructure were imaged using scanning electron microscopy (SEM). The chemical characterisation of the surface chemistry of the adsorbents, which provides information about the surface-active groups, the elemental composition, and the electronic state of the elements, was carried out using X-ray photoelectron spectroscopy (XPS). The adsorption properties of the mesoporous materials were determined using equilibrium and kinetic adsorption experiments for three selected cationic dyes (derivatives of thiazine (methylene blue) and triarylmethane (malachite green and crystal violet)). The adsorption capacity was analysed to the nanostructural and surface properties of used materials. The Generalized Langmuir equation was applied for the analysis of adsorption isotherm data. The adsorption study showed that the carbon materials have a higher sorption capacity for both methylene blue and crystal violet, e.g., 0.88-1.01 mmol/g and 0.33-0.44 mmol/g, respectively, compared to the polymer materials (e.g., 0.038-0.044 mmol/g and 0.038-0.050 mmol/g, respectively). The kinetics of dyes adsorption was closely correlated with the structural properties of the adsorbents. The kinetic data were analysed using various equations: first-order (FOE), second-order (SOE), mixed 1,2-order (MOE), multi-exponential (m-exp), and fractal-like MOE (f-MOE).

PRESENT-DAY FLUORINE CONCENTRATION IN THE OB RIVER WATER

Based on the potentiometric measurements average fluorine concentrations for different phases of the hydrological regime were determined in water samples taken in 2018-2020 in the outlet of the Ob River: 0,103 mg/L in the winter low-water period, 0,079 mg/L in the spring - summer flood, and 0,095 mg/L in the summer - autumn low-water period. The present-day weighted average concentration of fluorine in the Ob River water (0,086 mg/L) closely corresponds to the values measured in 1954-1956 and 1976-1980 (0,090 and 0,084 mg/L, respectively), therefore the fluorine content of 0,08-0,09 mg/L could be taken as a natural background.

Taste sensor for detecting non-charged bitter substances: Xanthine derivatives of pharmaceutical applications

Novel taste sensors utilizing an allosteric mechanism for potentiometric measurement have demonstrated the ability to detect non-charged bitter substances, including caffeine. In this study, three xanthine derivatives commonly found in pharmaceuticals (i.e., etofylline, proxyphylline, and diprophylline) were detected by the sensor modified with 3-bromo-2,6-dihydroxybenzoic acid (3-Br-2,6-DHBA). The concentration-dependent experiments and selectivity tests revealed that the sensor exhibited remarkable sensitivity and selectivity for these materials. The sensory test results demonstrated a linear correlation with the measurements of the 3-Br-2,6-DHBA-modified taste sensor, particularly within the sample concentration range of 1 mM to 30 mM. Thus, this study provided an effective method to evaluate the bitterness of chemical substances with xanthine scaffold.

Room temperature nonlocal detection of charge-spin interconversion in a topological insulator

Topological insulators (TIs) are emerging materials for next-generation low-power nanoelectronic and spintronic device applications. TIs possess non-trivial spin-momentum locking features in the topological surface states in addition to the spin-Hall effect (SHE), and Rashba states due to high spin-orbit coupling (SOC) properties. These phenomena are vital for observing the charge-spin conversion (CSC) processes for spin-based memory, logic and quantum technologies. Although CSC has been observed in TIs by potentiometric measurements, reliable nonlocal detection has so far been limited to cryogenic temperatures up to T = 15 K. Here, we report nonlocal detection of CSC and its inverse effect in the TI compound Bi1.5Sb0.5Te1.7Se1.3 at room temperature using a van der Waals heterostructure with a graphene spin-valve device. The lateral nonlocal device design with graphene allows observation of both spin-switch and Hanle spin precession signals for generation, injection and detection of spin currents by the TI. Detailed bias- and gate-dependent measurements in different geometries prove the robustness of the CSC effects in the TI. These findings demonstrate the possibility of using topological materials to make all-electrical room-temperature spintronic devices.