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Nowadays, using a potentiometric ion sensor to achieve detection of biological analytes is still a big challenge, since these analytes usually do not yield a measurable ion signal. To address this challenge, a simple and robust potentiometric sensing protocol based on a delayed Nernstian response is proposed for the label-free detection of biological analytes. The proposed sensor platform is composed of two layers: the surface recognition layer and the indicator-ion-selective electrode (ISE) membrane layer. It is based on a surface blocking mechanism in which the surface recognition interactions between the surface recognition element and the target can impede the diffusion of the indicator ion from the aqueous phase to the sensing membrane phase to reach the final Nernstian-response equilibrium, thus resulting in a delayed potential change. Such a potential change could be used to measure the concentration of a biological target in the sample. Thus, a sensing system was designed by using phage MS2, its host bacterium Escherichia coli ATCC 15597(abbreviated as E. coli H), and a solid-contact butyrylcholine ISE as a surface recognition element, a target, and an indicator electrode, respectively. This new concept offers a simple, sensitive, and extremely selective potentiometric method for detection of E. coli H with a detection limit of 100 CFU mL -1 . It can be expected that the present approach may pave the way to using ISEs to detect various important nonionic biological targets in clinical and environmental applications.

The aim of this paper is to investigate the influence of the molecules of conducting polymers on the properties of potentiometric sensors. Two conducting polymers, poly(3-octylthiophene-2,5-diyl) and poly(3,4-ethylene-1,4-dioxythiophene), were compared in the context of the design of ion-selective electrodes. This study offers a comparison of the most popular conducting polymers in the context of the design of potentiometric sensors. Firstly, the properties of both materials, such as their microstructure, electrical performance, wettability, and thermic properties, were examined. Subsequently, conducting polymers were applied as transducer layers in potassium-selective sensors. The properties of both groups of sensors were evaluated using the potentiometry method. Research has shown that the presence of poly(3-octylthiophene-2,5-diyl) (POT) in the transducer layer makes it superhydrophobic, leading to a long lifetime of sensors. On the other hand, the addition of poly(3,4-ethylene-1,4-dioxythiophene) polystyrene sulfonate (PEDOT:PSS) allows for the enhancement of electrical capacitance parameter values, which beneficially influence the stability of the potentiometric response of sensors. Both examined conducting polymers turned out to be perfect materials for transducer layers in potentiometric sensors, each being responsible for enhancing different properties of electrodes.

A novel miniaturized, solid-contact potentiometric screen-printed electrode was developed for highly sensitive and selective determination of lidocaine anesthetic. The electrode integrated single-walled carbon nanotubes as a solid-contact material and a molecularly imprinted polymer as a recognition sensory material. The performance characteristics of the electrode were evaluated and optimized to display a Nernstian slope of 58.92 ± 0.98 mV/decade over a linear concentration range of 4.53 × 10 -7 to 6.18 × 10 -3  mol/l within < 6 s. The detection limit was 7.75 × 10 -8  mol/l (18.16 ng/ml) of lidocaine. The use of the molecularly imprinted polymer significantly enhanced the selectivity of the electrode, and carbon nanotubes increased the sensitivity, accuracy, and potential stability. The electrode was successfully used for determining lidocaine in pharmaceutical preparations and human urine. The results favorably compared with data obtained by liquid chromatography-tandem mass spectrometry., Competing Interests: Declarations Ethics approval All the experiments adhered to the guidelines set forth in the Declaration of Helsinki (1964) and the Clinical Medical Research Regulation Act of 2020. Approval was granted by the Ethical Committee (EC) of the Faculty of Science, Ain Shams University, Cairo, Egypt. Competing interests The authors declare no competing interests., (© 2024. The Author(s).)

Potassium and sodium ions (K + and Na + ) play crucial roles in influencing plant growth and health status. Unfortunately, current strategies to determine the concentrations of such ions are destructive for the plants because it is necessary to collect/extract the sap for further analysis and produce either scattered or delayed results. Here, we introduce a new potentiometric dual microneedle sensor for nondestructive, real-time, and continuous monitoring of K + and Na + concentrations in living plants. The developed sensors show a response time <5 s, close-to-Nernstian slope (∼55 mV dec -1 ), resiliency to five insertions on the stem, good repeatability (max. %RSD = 0.3%) and reversibility (max. %RSD = 3%), appropriate continuous operation for 24 h, and linear range of responses that cover expected plant physiological levels (5-50 mM for Na + and 50-120 mM for K + ). Moreover, the accuracy was successfully investigated by comparing the results provided by the microneedle sensors to those obtained by a standard reference method (e.g., ion chromatography). Finally, we demonstrate that the developed analytical device is capable of tracking K + and Na + transportation from the hydroponic solution to the stem within 5-10 min. This research will contribute to establishing a new generation of analytical platforms for smart agriculture offering real-time information.

Disruption and dysregulation of cellular calcium channel function can lead to diseases such as ischemic stroke, heart failure, and arrhythmias. Corresponding calcium channel drugs typically require preliminary efficacy evaluations using in vitro models such as cells and simulated tissues before clinical testing. However, traditional detection and evaluation methods often encounter challenges in long-term continuous monitoring and lack calcium specificity. In this study, a dynamic monitoring system based on ion-sensitive membranes for light-addressable potentiometric sensor (LAPS) was developed to meet the demand for monitoring changes in extracellular calcium ion (Ca 2+ ) concentration in live cells. The effects of Ca 2+ channel agonists and blockers on 2D and 3D HL-1 cells were investigated, with changes in extracellular Ca 2+ concentration reflecting cellular calcium metabolism, facilitating drug evaluation. Additionally, calcium imaging technology with optical addressing capability complemented the LAPS system's ability to perceive 3D cell morphology, enhancing its drug evaluation capabilities. This work provides a novel, label-free, specific, and stable technique for monitoring cellular calcium metabolism. It achieves both continuous monitoring at single points and custom sensing area calcium imaging, holding significant implications for drug screening and disease treatment related to human calcium homeostasis., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Selective and nondisruptive in vivo neurochemical monitoring within the central nervous system has long been a challenging endeavor. We introduce a new sensing approach that integrates neurocompatible galvanic redox potentiometry (GRP) with customizable phosphorothioate aptamers to specifically probe dopamine (DA) dynamics in live rat brains. The aptamer-functionalized GRP (aptGRP) sensor demonstrates nanomolar sensitivity and over a 10-fold selectivity for DA, even amidst physiological levels of major interfering species. Notably, conventional sensors without the aptamer modification exhibit negligible reactivity to DA concentrations exceeding 20 μM. Critically, the aptGRP sensor operates without altering neuronal activity, thereby permitting real-time, concurrent recordings of both DA flux and electrical signaling in vivo. This breakthrough establishes aptGRP as a viable and promising framework for the development of high-fidelity sensors, offering novel insights into neurotransmission dynamics in a live setting.

Currently, Nernstian-response-based polymeric membrane potentiometric sensors using molecularly imprinted polymers (MIPs) as receptors have been successfully developed for determination of organic ionic species. However, the preparation of these MIP receptors usually involves tedious and time-consuming template-removal procedures. Herein, a template-removal-free MIP is proposed and used as a receptor for fabrication of a potentiometric sensor. The proposed methodology not only significantly shortens the preparation time of MIP-based potentiometric sensors but also improves the batch-to-batch reproducibility of these sensors. By using antibiotic vancomycin as a model, the new concept offers a linear concentration range of 1.0 × 10 -7 to 1.0 × 10 -4 mol L -1 with a detection limit of 2.51 × 10 -8 mol L -1 . It can be expected that the template-removal-free MIP-based sensing strategy could lay the foundation for simple fabrication of electrochemical sensors without the need for template removal such as potentiometric and capacitive sensors and ion-sensitive field-effect transistors.

This paper reports on the development of a flexible-wearable potentiometric sensor for real-time monitoring of sodium ion (Na + ), potassium ion (K + ), and pH in human sweat. Na 0.44 MnO 2 , polyaniline, and K 2 Co[Fe(CN) 6 ] were used as sensing materials for Na + , H + and K + monitoring, respectively. The simultaneous potentiometric Na + , K + , and pH sensing were carried out by the developed sensor, which enables signal collection and transmission in real-time to the smartphone via a Wi-Fi access point. Then, the potentiometric responses were evaluated by a designed android application. Na + , K + , and pH sensors illustrated high sensitivity (59.7 ± 0.8 mV/decade for Na + , 57.8 ± 0.9 mV/decade for K + , and 54.7 ± 0.6 mV/pH for pH), excellent stability, and good batch-to-batch reproducibility. The results of on-body experiments demonstrated that the proposed platform is capable of real-time monitoring of the investigated ions., (© 2024. The Author(s).)

Copper levels in biological fluids are associated with Wilson's, Alzheimer's, Menke's, and Parkinson's diseases, making them good biochemical markers for these diseases. This study introduces a miniaturized screen-printed electrode (SPE) for the potentiometric determination of copper(II) in some biological fluids. Manganese(III) oxide nanoparticles (Mn 2 O 3 -NPs), dispersed in Nafion, are drop-casted onto a graphite/PET substrate, serving as the ion-to-electron transducer material. The solid-contact material is then covered by a selective polyvinyl chloride (PVC) membrane incorporated with 18-crown-6 as a neutral ion carrier for the selective determination of copper(II) ions. The proposed electrode exhibits a Nernstian response with a slope of 30.2 ± 0.3 mV/decade (R 2  = 0.999) over the linear concentration range 5.2 × 10 -9 - 6.2 × 10 -3  mol/l and a detection limit of 1.1 × 10 -9  mol/l (69.9 ng/l). Short-term potential stability is evaluated using constant current chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS). A significant improvement in the electrode capacitance (91.5 μF) is displayed due to the use of Mn 2 O 3 -NPs as a solid contact. The presence of Nafion, with its high hydrophobicity properties, eliminates the formation of the thin water layer, facilitating the ion-to-electron transduction between the sensing membrane and the conducting substrate. Additionally, it enhances the adhesion of the polymeric sensing membrane to the solid-contact material, preventing membrane delamination and increasing the electrode's lifespan. The high selectivity, sensitivity, and potential stability of the proposed miniaturized electrode suggests its use for the determination of copper(II) ions in human blood serum and milk samples. The results obtained agree fairly well with data obtained by flameless atomic absorption spectrometry., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Austria, part of Springer Nature.)

Increasing acidity of seawater caused by increasing anthropogenic carbon dioxide absorbed into the seawater attracted the interest of researchers due to increased concern on the deterioration of marine systems and food supply to humans. Total alkalinity (TA) is one of the important parameters in determining carbonate chemistry and is described as the capacity of the sample to neutralize acids. Over the last two decades, many analytical techniques have been developed to determine TA. This article presents a review of different analytical techniques including titration, colorimetric, spectrophotometric, and potentiometric analyses in measuring TA. Among these analytical techniques, potentiometry analysis, which utilizes electrode systems such as glass electrode and ion-selective electrode used as indicator electrodes, is the most used technique. Important features such as principle, limitations, and challenges of the involved technique are discussed in detail.

Glypican-3 (GPC3) is exclusively overexpressed in most Hepatocellular carcinoma (HCC) tissue but not in normal liver tissue, making it a promising biomarker for the precise detection of HCC. In this paper, a label-free light-addressable potentiometric sensor (LAPS) decorated by platinumpalladium-hemin-reduced graphene oxide nanocomposites (PtPd@H-rGO NCs) was constructed for determination of GPC3. The GPC3 aptamer (GPC3 Apt ) and PtPd@H-rGO NCs were modified on the surface of silicon-based LAPS chip to build sensitive unit of LAPS system. A readout photocurrent elicited from a modulated light source, registers the localized surface potential change. When a bias voltage is provided to the LAPS system, the GPC3-GPC3 Apt complexes formed by the specific reaction between GPC3 and GPC3 Apt at the sensing interface can cause the sensitive membrane surface potential to change, resulting in the photocurrent-voltage (I-V) curves generate a corresponding offset response. Therefore GPC3 concentration can be determined by monitoring the potential shifts (△V). Under optimal conditions, the potential shift is linearly related to the concentration of GPC3 in the range of 0.001-3.00 μg/mL with the limit of detection (LOD) of 0.0001 μg/mL. The LAPS has a good analytical performance with good specificity, reproducibility and stability, and can be used for the detection of GPC3 in actual serum samples, which provides a broad application prospect for the combined application of LAPS and aptamers in biooassay., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Biotin is widely used in infant formula to prevent biotin deficiency of newborn babies and in beauty products as nutritional supplements for coenzymatic functions and having strong nails, shiny hair, and skin over the last few years. There is a need for the development of a fast, simple and reusable assay method to perform biotin determination at very low concentrations. Biotin determination has achieved with a prepared potentiometric biotin sensor that has a very wide concentration range (10 -15 M-10 -7 M) and a lower detection limit (0.3 10 -15 M) with a very good regression coefficient (0.9925). A quick response (7 min), good accuracy (recovery 100.4-103.7%), reproducible, reusable (10 times), and long-term stability (3 months) have been obtained using the prepared potentiometric sensor. The obtained results have proved that the prepared potentiometric sensor can be used for biotin determination in real samples., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Despite technological advances in biomolecule detections, evaluation of molecular interactions via potentiometric devices under ion-enriched solutions has remained a long-standing problem. To avoid severe performance degradation of bioelectronics by ionic screening effects, we cover probe surfaces of field effect transistors with a single film of the supported lipid bilayer, and realize respectable potentiometric signals from receptor-ligand bindings irrespective of ionic strength of bulky solutions by placing an ion-free water layer underneath the supported lipid bilayer. High-energy X-ray reflectometry together with the circuit analysis and molecular dynamics simulation discovered biochemical findings that effective electrical signals dominantly originated from the sub-nanoscale conformational change of lipids in the course of receptor-ligand bindings. Beyond thorough analysis on the underlying mechanism at the molecular level, the proposed supported lipid bilayer-field effect transistor platform ensures the world-record level of sensitivity in molecular detection with excellent reproducibility regardless of molecular charges and environmental ionic conditions.

Innovation in products and processes, traceability, food security and quality control are inherent challenges in agri-food sector. Trends in wine production are focused on obtaining natural wines with less chemical intervention. Following this goal, a low cost miniaturized, easy-to-use and highly automated microanalyzer to monitor total potassium in winemaking processes is presented. The microsystem monolithically integrates microfluidics as well as a potentiometric detection system and does not require any sample pretreatment. The analytical features provided are a linear range from 250 to 4000 mg L -1 K + , covering all the concentrations expected in must and wine samples, a detection limit of 75 ± 12 mg L -1 K + , and an adequate reproducibility and repeatability. Sample throughput is calculated at 20 h -1 with a waste volume generation lower than 4 mL per analysis. The microsystem lifetime is at least 4 months. Different wine and grape juice samples have been analyzed reaching outstanding results., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

This is the first report demonstrating proof of concept for the passive, non-invasive extraction and in situ potentiometric detection of human sweat chloride ions (Cl - ions) using a stable printed planar liquid-junction reference electrode-integrated hydrogel-based touch-sensor pad without activities such as exercise to induce perspiration, environmental temperature control, or requiring cholinergic drug administration. The sensor pad was composed entirely of a screen-printed bare Ag/AgCl-based chloride ion-selective electrode and a planar liquid-junction Ag/AgCl reference electrode, which were fully covered by an agarose hydrogel in phosphate-buffered saline (PBS). When human skin contacted the hydrogel pad, sweat Cl - ions were continuously extracted into the gel, followed by in situ potentiometric detection. The planar liquid-junction Ag/AgCl reference electrode had a polymer-based KCl-saturated inner electrolyte layer to stabilize the potential of the Ag/AgCl electrode even with a substantial change in the chloride ion concentration in the hydrogel pad. We expect this fully screen-printed sensor to achieve the low-cost passive and non-invasive daily monitoring of human Cl - ions in sweat in the future.

Despite tremendous complexity in glycan structure, sialic acid (SA) provides an analytically accessible index for glycosylation, owing to its uniquely anionic nature and glycan-chain terminal occupation. Taking advantage of boronic acid (BA) based SA-recognition chemistry, we here demonstrate a label-free, no enzymatic, potentiometric determination of fetuin, a blood-circulating glycoprotein implicated in physiological and various pathological states. A phenylboronic acid (PBA) ω-end-functionalized poly(ethylene glycol) (PEG) with an α-tethering unit bearing pendent alkyne groups was "grafted-to" a gold electrode modified with 11-azide-undecathiol by a copper-catalyzed azide-alkyne cycloaddition reaction. Using the electrode, fetuin was potentiometrically detectable with a μM-order-sensitivity that is comparable to what is found in blood-collected specimen. Our finding may have implications for developing a remarkably economic hemodiagnostic technology with ease of downsizing and mass production.

Potentiometry is one of the most important electrochemical methods and potentiometric based sensors have been extensively studied by researchers for many years. The fact that potentiometric sensors have several advantages over other analytical devices is another reason for intensive research on the topic. In this area, hundreds of different sensors have been developed till today and introduced into the literature. The successful use of the developed sensors, particularly in real sample analysis, has made potentiometric sensors the center of attention. In this review, we highlight the studies which have been successfully applied to the developed drug samples and also to many real samples, with high recovery rates.

Anionic surfactants are important components of many products used in everyday life in all households. They are also applied in various industrial fields at a very large scale. Since they have a negative influence on the environment, it is an imperative to monitor their concentration in aquatic ecosystems. Therefore, it is of great importance to develop new methods for the determination of a wide spectra of anionic surfactants in complex environmental samples in a short time. A comprehensive review of potentiometric sensors for the determination of anionic surfactants in the last 50 years is given with special concern to papers published since 2000, but noting some earlier published important papers. The latest development in use of new ionophores, polymer formulations, and nanomaterials is presented. Additionally, the application of new potentiometric sensors in batch mode or in miniaturized microfluidic methods is discussed.

A molecularly imprinted polymer-modified potentiometric histamine (HIS) sensor was prepared and used for quantitative determination of HIS in bovine serum. The calibration curve using the potential responses measured in 1 × 10 -3 mol L -1 phosphate buffer (pH 7.4) showed good linearity in the HIS concentration range of 3 × 10 -4 to 1 × 10 -2 mol L -1 (r = 0.92), with a detection limit of 1.6 × 10 -4 mol L -1 . In bovine serum samples, the HIS sensor showed good recovery values of 91 - 104%. Therefore, this HIS sensor successfully determined the HIS concentration in bovine serum samples.

A handful of bis/tetra-phosphonate calix[4]pyrroles with recognition sites embedding in hydrophobic cavitands were evaluated for the first time as ionophores for polymeric membrane Ach + -selective electrodes. Highly selective potentiometric Ach + could be achieved over its analogues, especially for Ch + , which differs only by an acetate tail from Ach + . The superior performance of the proposed ISEs might be ascribed to a dual-site binding mode, in which the trimethylammonium head and acetate tail were accommodated by the phosphonate group-bridged aryl walls and the bowl-shaped aromatic cavity, through cation-π/charge-dipole interaction and the convergent four N-H···O hydrogen bonds, respectively. To gain more insight into the performance of the proposed ISEs, the cation-ionophore complex constants in the membrane phase were determined, and the binding affinity trend correlates well with the selectivity pattern. These results suggest that conformational preorganization of the ionophores and complementary weak interactions do change the selectivity of the ionophores. Studies on the influence of the sample solution pH demonstrated that the developed ISEs can be employed in a wide pH range of 4.0-9.6 with a fast response (<60 s), good reversibility, and long lifetime. Optimizing the membrane components, such as ionophores, lipophilic additives, and plasticizers, yielded ISEs, showing Nernstian responses to Ach + with improved linear ranges and detection limits (a slope of -59.5 mV/dec in the linear range of 1 × 10 -6 -1 × 10 -2 M with a detection limit of 3 × 10 -7 M), which led to the success of the determination of Ach + in spiked urine and milk samples.

In this letter, the innate ability of nitric oxide (NO) to inhibit platelet activation/adhesion/thrombus formation is employed to improve the hemocompatibility and in vivo accuracy of an intravascular (IV) potentiometric P CO 2 (partial pressure of carbon dioxide) sensor. The catheter-type sensor is fabricated by impregnating a segment of dual lumen silicone tubing with a proton ionophore, plasticizer, and lipophilic cation-exchanger. Subsequent filling of bicarbonate and strong buffer solutions and placement of Ag/AgCl reference electrode wires within each lumen, respectively, enables measurement of the membrane potential difference across the inner wall of the tube, with this potential changing as a function of the logarithm of sample P CO 2 . The dual lumen device is further encapsulated within a S -nitroso- N -acetyl-DL-penicillamine (SNAP)-doped silicone tube that releases physiological levels of NO. The NO releasing sensor exhibits near-Nernstian sensitivity toward P CO 2 (slope = 59.31 ± 0.78 mV/decade) and low drift rates (<2 mV/24 h after initial equilibration). In vivo evaluation of the NO releasing sensors, performed in the arteries and veins of anesthetized pigs for 20 h, shows enhanced accuracy (vs non-NO releasing sensors) when benchmarked to measurements of discrete blood samples made with a commercial blood gas analyzer. The accurate, continuous monitoring of blood P CO 2 levels achieved with this new IV NO releasing P CO 2 sensor configuration could help better manage hospitalized patients in critical care units.

Molecularly imprinted polymers (MIPs) have become a valuable material in the field of electrochemical sensors, due to their selective recognition capabilities towards target molecules. A low-cost potentiometric sensor based on molecular imprinting was developed for the measurement of gallic acid (GA) in edible plants. The imprinted polymer was synthesized by bulk polymerization in the presence of trimethylolpropane triacrylate as the cross-linker and 2,2'-azo-bisisobutyronitrile as the initiator. The sensing component of the sensor was fabricated by the incorporation of MIPs in a polyvinyl chloride matrix. The species and amount of MIPs were optimized, and the imprinted poly(methacrylic acid) sensor was examined and characterized by Fourier transform infrared spectroscopy, scanning electron microscopy and potential response. The proposed sensor exhibited a fast near-Nernst response to GA in the range of 1 × 10 -5 to 3.2 × 10 -4 mol/L. The potentiometric measurement of GA in edible plants was checked by high-performance liquid chromatography, and the two test results showed no significant difference (P > 0.05). The imprinted sensor is applicable to the electrochemical determination of GA in edible plants. PRACTICAL APPLICATION: The proposed MIP-based potentiometric sensor provided a low-cost, efficient, and green tool for the rapid determination of the bioactive ingredient GA in edible plants. The knowledge obtained will offer useful reference to the quality control and bioactive assessment of botanical food., (© 2020 Institute of Food Technologists®.)

Extracellular pH can indicate the variation in organelle function and cell state. It is important to measure extracellular pH (pHe) with a controllable distance. In this work, a potentiometric SECM dual-microelectrode was developed to monitor the pHe of MCF-7 cells under electrical stimulation. The distance between the dual-microelectrode and the cells was determined first with a gold microelectrode by recording the approaching curve, and the pH was determined using an open-circuit potential (OCP) technique with a polyaniline-modified Pt microelectrode. The pH microelectrode showed a response slope of 53.0 ± 0.4 mV/pH and good reversibility from pH 4 to pH 8, fast response within 10 s, and a potential drift of 1.13% for 3 h, and thus was employed to monitor the pHe of stimulated cells. The value of pHe decreased with the decrease in the distance to cells, likely due to the release of H + . With an increase in the stimulation potential or time, the pHe value decreased, as the cell membrane became more permeable, which was verified by fluorescence staining of calcein-AM/PI (propidium iodide). Based on these results, this method can be widely applied for determining the species released by biosystems at a controllable position.

Histamine intolerance results from a disequilibrium of accumulated histamine and the capacity for histamine degradation. An impaired histamine degradation based on reduced DAO activity and the resulting histamine excess may cause numerous symptoms mimicking an allergic reaction. For that, the determination of histamine in blood or in food products has great importance to identify risk factors. A new histamine-selective electrode is proposed using cucurbit[6]uril (CB[6]), as ionophore, in the analysis of biological samples. The selection of this smart supramolecular organic framework was based on its apparent stability constant of histamine-CB[6] (log β) of 4.33. The optimized electrode based on a polymeric membrane (PVC) combines the histamine-selective ionophore with 2-nitrophenyl octyl ether as solvent mediator and potassium tetrakis(4-chlorophenyl)borate as anionic additive. Furthermore, multi-walled carbon nanotubes particles were included in the membrane composition to partly lower the detection limit of the method, while improving stability and lowering the response drift (± 4 mV). The electrodes showed a rapid response (≃ 13 s) in the pH operational range of 2.7-5.4, with a Nernstian slope of 30.9 ± 1.2 mV/dec, a detection limit of (3.00 ± 0.61) × 10 -7  mol/L, and a lower limit of the linear range of (3.00 ± 0.00) × 10 -7  mol/L. After miniaturization, the electrode was used as a detector in a sequential-injection lab-on-valve flow setup. The optimized flow conditions were achieved for sample injection volumes of 197 μL propelled towards the cell under detection, at a flow rate of 30 μL/s during 100 s, making the analysis of 30 samples per hour possible. The developed system was used to analyze spiked blood serum samples previously cleaned by using solid-phase extraction. The sample pretreatment of the serum samples using Oasis MCX cartridges showed outstanding efficiency for histamine determination. The recovery values for three different levels of histamine concentration (1 × 10 -4  mol/L, 1 × 10 -5  mol/L, and 1 × 10 -6  mol/L) were (97 ± 6)%, (103 ± 1)%, and (118 ± 9)%, respectively, showing that this method was suitable for biological samples.

In this study, ultrathin and defect-free graphene (Gr) sheets were prepared through a fluid dynamics-induced shear exfoliation method using graphite. The high hydrophobicity and surface area of Gr make it attractive as a solid-contact ion-to-electron transducer for potentiometric K + sensors, in which the electrodes are fabricated through a screen-printing process. The electrochemical characterization demonstrates that Gr solid contact results in a high double-layer capacitance, potential stability, and strong resistance against water layer, gases, and light. The Gr-based K + sensors showed a Nernstian slope of 53.53 mV/log[K + ] within a linear concentration range of 10 -1 -10 -4 M, a low detection limit of 10 -4.28  M, a fast response time of ~8 s, good repeatability, and excellent long-term stability. Moreover, the Gr-based K + sensors provided accurate ion concentrations in actual samples of human sweat and sports drinks., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Potentiometric sensors have a great influence on the determination of most various compounds in their matrices. Therefore, efficient and new sensors were introduced to measure sodium Deoxycholate (NaDC) as a bile acid salt. These sensors are based on NaDC imprinted polymer (MIP) as sensory element. The MIP beads were synthesized using thermal polymerization pathway, in which acrylamide (AAm), ethylene glycol dimethacrylate (EGDMA), NaDC, and benzoyl peroxide (BPO) were used as the functional monomer, cross-linker, template, and initiator, respectively. The proposed sensors were fabricated using a coated screen-printed platform and the sensing membrane was modified by single-walled carbon nanotubes (SWCNTs) as an ion-to-electron transducer. The sensors exhibited high sensitivity that reached 4.7 × 10 -5 M of near-Nernestian slope (-60.1 ± 0.9 mV/decade, r 2 = 0.999 ( n = 5)). In addition, the sensors revealed high selectivity, long lifetime, high potential stability, and conductivity that ensure reproducible and accurate results over a long time. MIP characterization was performed using Fourier Transform-Infrared (FT-IR) and a scanning electron microscope (SEM). Regarding the interaction of NaDC with serum albumin (SA), albumin is determined in human serum samples as human serum albumin (HSA), which was collected from different volunteers of different ages and gender., Competing Interests: The authors declare no conflict of interest.

The chloride gradient plays an important role in regulating cell volume, membrane potential, pH, secretion, and the reversal potential of inhibitory glycine and GABA A receptors. Measurement of intracellular chloride activity, [Formula: see text], using liquid membrane ion-selective microelectrodes (ISM), however, has been limited by the physiochemical properties of Cl - ionophores which have caused poor stability, drift, sluggish response times, and interference from other biologically relevant anions. Most importantly, intracellular [Formula: see text] may be up to 4 times more abundant than Cl - (e.g. skeletal muscle) which places severe constraints on the required selectivity of a Cl - - sensing ISM. Previously, a sensitive and highly-selective Cl - sensor was developed in a polymeric membrane electrode using a trinuclear Hg(II) complex containing carborane-based ligands, [9]-mercuracarborand-3, or MC3 for short. Here, we have adapted the use of the MC3 anion carrier in a liquid membrane ion-selective microelectrode and show the MC3-ISM has a linear Nernstian response over a wide range of a Cl (0.1 mM to 100 mM), is highly selective for Cl - over other biological anions or inhibitors of Cl - transport, and has a 10% to 90% settling  time of 3  sec. Importantly, over the physiological range of a Cl (1 mM to 100 mM) the potentiometric response of the MC3-ISM is insensitive to [Formula: see text] or changes in pH. Finally, we demonstrate the biological application of an MC3-ISM by measuring intracellular a Cl , and the response to an external Cl-free challenge, for an isolated skeletal muscle fiber.

Electronic tongue systems equipped with cross-sensitive potentiometric sensors have been applied to pharmaceutical analysis, due to the possibility of various applications and developing new formulations. Many studies already proved the complementarity between the electronic tongue and classical analysis such as dissolution tests indicated by Pharmacopeias. However, as a new approach to study pharmaceuticals, electronic tongues lack strict testing protocols and specification limits; therefore, their results can be improperly interpreted and inconsistent with the reference studies. Therefore, all aspects of the development, measurement conditions, data analysis, and interpretation of electronic tongue results were discussed in this overview. The critical evaluation of the effectiveness and reliability of constructed devices may be helpful for a better understanding of electronic tongue systems development and for providing strict testing protocols.

An electrochemical platform was proposed for highly sensitive and selective analysis of sialic acid based on molecularly imprinted polymers (MIPs), which were electropolymerized with the monomer molecules of 3-aminophenylboronic acid (ABA) on a carbon cloth (CC) electrode in the presence of template molecules. The fabricated sensor, named the PABA/CC-based MIP electrode, could be used for the detection of sialic acid because the reversible and covalent boronic acid-diol binding was sensitive to the electrochemical potential of the prepared sensor. The utilization of a CC film as the substrate could improve the sensitivity due to its good electrical conductivity and large surface area. Under the optimized conditions, a good relationship between the change in potential and the concentration of sialic acid was obtained in the range from 40 μM to 440 μM with a detection limit of 0.5 μM. The resulting MIP sensor also displayed good selectivity, reproducibility and stability. Moreover, this sensor was successfully applied for the evaluation of the sialic acid level in infant formulas.

Potentiometric glutathione (GSH) sensors were fabricated using a molecularly imprinted polymer prepared from GSH, methacrylic acid (MAA), and ethylene glycol dimethacrylate as the template molecule, functional monomer, and cross-linker, respectively. Five GSH sensors were prepared with different ratios of GSH to MAA. Their potential responses were measured in a GSH aqueous solution using Ag/AgCl as the reference electrode. A GSH sensor prepared with a GSH:MAA ratio of 2:32 had the best responsivity, while the sensor synthesized from a non-imprinted polymer prepared without GSH (NIP sensor) showed a potential response value of almost zero after the addition of GSH. The ratio of the potential responses of the GSH sensor to the NIP sensor was 8.21. Additionally, the GSH sensor had good linearity over a GSH concentration range of 1 × 10 -5 to 2 × 10 -4 mol L -1 . The GSH sensor provided good quantification and high specificity for GSH and is expected to be applicable for easy and direct determinations of GSH.

This work reports a new paper-based sensing platform and its application in a label-free potentiometric immunosensor for Salmonella typhimurium detection based on the blocking surface principle. A paper-based strip electrode was integrated with a filter paper pad which acted as a reservoir of the internal solution. The design offers a convenient platform for antibody immobilization and sampling, proving also that is a simple and affordable methodology to control an ionic flux through a polymer membrane. Two different immunosensing interfaces were assembled on the developed paper-strip electrode. The simplest interface relied on direct conjugation of the antibody to the polymer membrane and the second one resorted to an intermediate layer of a polyamidoamine dendrimer, with an ethylenediamine core from the fourth generation. Electrochemical impedance spectroscopy was used to assess the successive interface modification steps and the resulting analytical performance of both immunosensors was compared. For such, the potential shift derived from the blocking effect of the ionic flux caused by antigen-antibody conjugation was correlated with the logarithm of the Salmonella typhimurium concentration in the sample. In optimized conditions, a limit of detection of 5 cells mL -1 was achieved. As a proof-of-concept, the proposed method was applied to apple juice samples, demonstrating to be a suitable prototype to be used in real scenarios in useful time (<1 h assay)., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Herein, the reproducibility and a double validation of on-body measurements provided by new wearable potentiometric ion sensors (WPISs) is presented. Sweat collected during sport practice was first analyzed using the developed device, the pH-meter, and ion chromatography (IC) prior to on-body measurements (off-site validation). Subsequently, the accuracy of on-body measurements accomplished by the WPISs was evaluated by comparison with pH-meter readings and IC after collecting sweat (every 10-12.5 min) during sport practice. The developed device contains sensors for pH, Cl - , K + , and Na + that are embedded in a flexible sampling cell for sweat analysis. The electrode array was fabricated employing MWCNTs (as an ion-to-electron transducer) and stretchable materials that have been exhaustively characterized in terms of analytical performance, presenting Nernstian slopes within the expected physiological range of each ion analyte (Cl - , 10-100 mM; K + , 10-10 mM; and Na + , 10-100 mM and pH, 4.5-7.5), drift suitable for midterm exercise practice (0.3 ± 0.2 mV h -1 ), fast response time, adequate selectivity for sweat measurements, and excellent reversibility. Besides that, the designed sampling cell avoids any sweat contamination and evaporation issues while supplying a passive sweat flow encompassing specifically the individual's perspiration. The interpretation of ion concentration profiles may permit the identification of personal dynamic patterns in sweat composition while practicing sport.

The paper describes a wide-range practical application of the potentiometric multisensor system (MS) (1) for integral safety evaluation of a variety of natural waters at multiple locations, under various climatic conditions and anthropogenic stress and (2) for close to real consistency evaluation of waste water purification processes at urban water treatment plants. In total, 25 natural surface water samples were collected around St. Petersburg (Russia), analyzed as is, and after ultrasonic treatment. Toxicity of the samples was evaluated using bioassay and MS. Relative errors of toxicity assessment with MS in these samples were below 20%. The system was also applied for fast determination of integral water quality using chemical oxygen demand (COD) values in 20 samples of water from river and ponds in Kolkata (India) and performed with an acceptable precision of 20% to 22% in this task. Furthermore, the MS was applied for fast simultaneous evaluation of COD, biochemical oxygen demand, inorganic phosphorous, ammonia, and nitrate nitrogen at two waste water treatment plants (over 320 samples). Reasonable precision (within 25%) of such analysis is acceptable for rapid water safety evaluation and enables fast control of the purification process. MS proved to be a practicable analytical instrument for various real-world tasks related to water safety monitoring., Competing Interests: The authors declare no conflict of interest.

In this paper, we propose a novel concept of a biointerface, a polymeric nanofilter, for the potentiometric detection of small biomolecules using an extended-Au-gate field-effect transistor (EG-Au-FET). A Au electrode has the potential capability to detect various small biomolecules with ultrasensitivity at nM levels on the basis of a surface redox reaction, but it exhibits no selective response to such biomolecules. Therefore, a suitable polymeric nanofilter is designed and modified on the Au electrode, so that a small target biomolecule reaches the Au surface, resulting in an electrical signal, whereas low-molecular-weight interferences not approaching the Au surface are captured in the polymeric nanofilter. The polymeric nanofilter is composed of two layers. The first layer is electrografted as an anchor layer by a cyclic voltammetry method. Then, a filtering layer is precisely polymerized as the second layer by a photo-mediated surface-initiated atom transfer radical polymerization method. The thickness and density of the polymeric nanofilter are controlled to specifically detect a small target biomolecule with high sensitivity. As a model case, l-cysteine as the small target biomolecule at nM levels is specifically detected by filtering l-DOPA as a low-molecular-weight interference using the polymeric nanofilter-grafted EG-Au-FET on the basis of the following mechanism. The phenylboronic acid (PBA) that copolymerizes with the polymeric nanofilter captures l-DOPA through diol binding, whereas l-cysteine reaches the Au surface through the filter layer. The polymeric nanofilter can also effectively prevent the interaction between biomacromolecules such as albumin and the Au electrode. A platform based on a polymeric nanofilter-grafted EG-Au-FET biosensor is suitable for the ultrasensitive and specific detection of a small biomolecule in biological samples such as tears and sweat, which include small amounts of low-molecular-weight interferences, which generate nonspecific electrical signals.

Bilirubin is predominantly formed in the liver as a result of breakdown of hemoglobin. Knowing the concentration of bilirubin in serum is important in evaluating the health of the liver, and for the diagnosis of hyperbilirubinemia (a condition that afflicts approximately 60% of full-term and 80% of pre-term newborns). This paper describes the design and fabrication of a potentiometric sensor for the determination of free bilirubin in serum. The sensor has a polymeric ion-selective membrane, and selectively measures free ionic bilirubin ("unbound" bilirubin - i.e., bilirubin not complexed to albumin or other complexing agents), in the presence of other anions - chloride, phosphate, pyruvate, deoxycholate, and lactate - also present in serum. The linear response range of the sensor (1.0 mM to 0.10 μM bilirubin, measured in a sodium phosphate buffer with pH 8.6) covers the clinically-relevant concentration of bilirubin in serum (5-500 μM). Free bilirubin could be detected in human blood serum with this potentiometric sensor. The components of the potentiometric bilirubin sensor were embedded in a paper-based device to provide a sensor that is disposable and easy to use, and thus is suitable for applications at the point-of-care. The paper-based potentiometric bilirubin sensor exhibited a response range of 5.0-0.10 mM (sufficient to cover the clinically-relevant concentration of bilirubin in serum). Only 15 μL of sample is required for measurement of the concentration of free bilirubin, and the analysis can be performed in less than two minutes., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Wearable potentiometric sensors have received considerable attention owing to their great potential in a wide range of physiological and clinical applications, particularly involving ion detection in sweat. Despite the significant progress in the manner that potentiometric sensors are integrated in wearable devices, in terms of materials and fabrication approaches, there is yet plenty of room for improvement in the strategy adopted for the sample collection. Essentially, this involves a fluidic sampling cell for continuous sweat analysis during sport performance or sweat accumulation via iontophoresis induction for one-spot measurements in medical settings. Even though the majority of the reported papers from the last five years describe on-body tests of wearable potentiometric sensors while the individual is practicing a physical activity, the medical utilization of these devices has been demonstrated on very few occasions and only in the context of cystic fibrosis diagnosis. In this sense, it may be important to explore the implementation of wearable potentiometric sensors into the analysis of other biofluids, such as saliva, tears and urine, as herein discussed. While the fabrication and uses of wearable potentiometric sensors vary widely, there are many common issues related to the analytical characterization of such devices that must be consciously addressed, especially in terms of sensor calibration and the validation of on-body measurements. After the assessment of key wearable potentiometric sensors reported over the last five years, with particular attention paid to those for medical applications, the present review offers tentative guidance regarding the characterization of analytical performance as well as analytical and clinical validations, thereby aiming at generating debate in the scientific community to allow for the establishment of well-conceived protocols.

A new analytical all-solid-state platform for intradermal potentiometric detection of potassium in interstitial fluid is presented here. Solid microneedles are modified with different coatings and polymeric membranes to prepare both the potassium-selective electrode and reference electrode needed for the potentiometric readout. These microneedle-based electrodes are fixed in an epidermal patch suitable for insertion into the skin. The analytical performances observed for the potentiometric cell (Nernstian slope, limit of detection of 10 -4.9 potassium activity, linear range of 10 -4.2 to 10 -1.1 , drift of 0.35 ± 0.28 mV h -1 ), together with a fast response time, adequate selectivity, and excellent reproducibility and repeatability, are appropriate for potassium analysis in interstitial fluid within both clinical and harmful levels. The potentiometric response is maintained after several insertions into animal skin, confirming the resiliency of the microneedle-based sensor. Ex vivo tests based on the intradermal detection of potassium in chicken and porcine skin demonstrate that the microneedle patch is suitable for monitoring potassium changes inside the skin. In addition, the dimensions of the microneedles modified with the corresponding layers necessary to enhance robustness and provide sensing capabilities (1000 μm length, 45° tip angle, 15 μm thickness in the tip, and 435 μm in the base) agree with the required ranges for a painless insertion into the skin. In vitro cytotoxicity experiments showed that the patch can be used for at least 24 h without any side effect for the skin cells. Overall, the developed concept constitutes important progress in the intradermal analysis of ions related to an electrolyte imbalance in humans, which is relevant for the control of certain types of diseases.

The neurotransmitter acetylcholine (ACh) plays a key role in the pathophysiology of brain disorders such as Alzheimer's disease. Understanding the dynamics of ACh concentration changes and kinetics of ACh degradation in the living brain is crucial to unravel the pathophysiology of such diseases and the rational design of therapeutics. In this work, an electrochemical sensor capable of dynamic, label-free, selective, and in situ detection of ACh in a range of 1 nM to 1 mM (with temporal resolution of less than one second) was developed. The sensor was employed for the direct detection of ACh in artificial cerebrospinal fluid and rat brain homogenate, without any prior separation steps. A potentiometric receptor-doped ion-selective electrode (ISE) with selectivity for ACh was designed by taking advantage of the positive charge of ACh. The dynamic range, limit of detection (LOD), and the selectivity of the sensor were optimized stepwise by (i) screening of hydrophobic biomimetic calixarenes to identify receptors that strongly bind to ACh based on shape-selective multitopic recognition, (ii) doping of the ISE sensing membrane with an ACh-binding hydrophobic calixarene to enable selective detection of ACh in complex matrices, (iii) utilizing a hydrophilic calixarene in the inner filling solution of the ISE to buffer the concentration of ACh and, thereby, lower the LOD of the sensor, and (iv) introducing a surface treatment step prior to the measurement by placing the sensor for ∼1 min in a solution of a hydrophilic calixarene to lower the LOD of the sensor even further.

Understanding the real-time correlation between chemical patterns and neural processes is critical for deciphering brain function. Voltammetry has enabled this task but with a number of challenges for current-based electrolysis in vivo. Herein, we report galvanic redox potentiometry (GRP) potentially as a universal strategy for in vivo monitoring of neurochemicals, with ascorbic acid (AA) as a typical example. The GRP sensor is constructed on a self-driven galvanic cell configuration, where AA is spontaneously oxidized at the indicating single-walled carbon nanotube-modified carbon fiber electrode (SWNT-CFE), while oxygen reduced at the laccase-modified reference CFE (Lac-CFE). At thermodynamic equilibrium, open-circuit potential (OCP) can be a linear indicator of the concentration of AA. The resulting sensor shows a high selectivity to AA dynamics in the presence of coexisting electroactive neurochemicals, which is mainly determined by the driving force for the cell reaction, as suggested by principal investigation. Sensing sensitivity of this OCP-based GRP method is not affected by nonspecific protein adsorption and electrode fouling. Moreover, a micropipette compartment of the reference electrode is designed to suppress mass crossover and prevent disturbance to oxygen reduction through confinement effect. The in vivo application of the GRP sensor is illustrated by measuring the basal level of cortical AA in live rat brain (230 ± 40 μM) and its dynamics during ischemia/reperfusion. The GRP concept is demonstrated as a prominent method for in vivo, real-time, quantitative analysis of brain neurochemistry.

Herein, an all-solid light addressable potentiometric sensor (LAPS) is presented for determination of cadmium (Cd) in rice. On the working surface of the LAPS, reduced graphene oxide (RGO) is introduced as a part of ion-to-electron transducer to improve ionophore behaviors. The composite modification of RGO and ionophore is validated with scanning electron microscopy. The as-fabricated sensor presents a rapid response in less than 10 s to target Cd. Meanwhile, it shows lower noise (0.23 mV) and better limit of detection (0.002 mg L -1 ) than LAPS (control) without RGO modification (0.37 mV; 0.008 mg L -1 ). With the proposed method, satisfactory precision, accuracy and selectivity are also established. This method is adopted in an extensive survey for 25 rice samples from 5 regions in China. The results are in very good agreement with those obtained using inductively-coupled plasma-mass spectrometry., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Small-holding farmers in the developing world suffer from sub-optimal crop yields because they lack a soil diagnostic system that is affordable, usable, and actionable. This paper details the fabrication and characterization of an integrated point-of-use soil-testing system, comprised of disposable ion-selective electrode strips and a handheld electrochemical reader. Together, the strips and reader transduce soil ion concentrations into to an alphanumeric output that can be communicated via text message to a central service provider offering immediate, customized fertilizer advisory. The solid-state ion-selective electrode (SS-ISE) strips employ a two-electrode design with screen-printable carbon nanotube ink serving as the electrical contacts for the working and reference electrodes. The working electrode comprises a plasticizer-free butyl acrylate ion-selective membrane (ISM), doped with an ion-selective ionophore and lipophilic salt. Meanwhile, the reference electrode includes a screen-printed silver-silver chloride ink and a polyvinyl-butyral membrane, which is doped with sodium chloride for stable reference potentials. As a proof of concept, potassium-selective electrodes are studied, given potassium's essential role in plant growth and reproduction. The ISE-based system is reproducibly manufactured to yield a Nernstian response with a sub-micromolar detection limit (pK+ of 5.18 ± 0.08) and near-Nernstian sensitivity (61 mV/decade) in the presence of a 0.02 M strontium chloride extraction solution. Analysis of soil samples using the printed electrodes and reader yielded a correlation coefficient of 𝑅2 = 0.89 with respect to values measured via inductively coupled plasma atomic emission spectroscopy (ICP-AES). The reliable performance of this system is encouraging toward its deployment for soil nutrient management in resource-limited environments., Competing Interests: The authors have declared that no competing interests exist.

Potentiometric and spectrophotometric pH-titrations of the lesinurad for three consecutive dissociation constants determination were compared. Lesinurad is a selective inhibitor of uric acid reabsorption as part of a combination of medicines to treat high levels of uric acid in blood, also called hyperuricemia. Nonlinear regression of the pH-spectra with REACTLAB and SQUAD84 and of the pH-titration curve with ESAB determined three multiple close dissociation constants. The protonation scheme of lesinurad was suggested. A sparingly soluble anion L - of lesinurad was protonated to the still soluble species LH, LH 2 + and LH 3 2+ in pure water. Three consecutive thermodynamic dissociation constants were estimated pK T a1  = 2.09, pK T a2  = 4.25, pK T a3  = 6.58 at 25 °C and pK T a1  = 1.96, pK T a2  = 4.16, pK T a3  = 6.32 at 37 °C by UV-metric spectra analysis. The graph of molar absorption coefficients shows that the spectrum of species LH 2 + and LH vary in colour, while protonation of chromophore LH 2 + to LH 3 2+ has less influence on chromophores in the lesinurad molecule. Three multiple thermodynamic dissociation constants of 1 × 10 -4  M lesinurad were determined by the pH-metric analysis pK T a1  = 2.39, pK T a2  = 3.47, pK T a3  = 6.17 at 25 °C and pK T a1  = 2.08, pK T a2  = 3.29, pK T a3  = 6.03 at 37 °C. The values of enthalpy ΔH 0 (pK a1 ) = 19.19 kJ mol -1 , ΔH 0 (pK a2 ) = 13.29 kJ mol -1 , ΔH 0 (pK a3 ) = 38.39 kJ mol -1 , show the dissociation process is endothermic. The positive values of ΔG 0 (pK a1 ) = 11.93 kJ mol -1 , ΔG 0 (pK a2 ) = 24.26 kJ mol -1 , ΔG 0 (pK a3 ) = 37.56 kJ mol -1 at 25 °C indicate that the dissociation process of pK a2 is not spontaneous, which was confirmed by its value of entropy ΔS 0 (pK a1 ) = 24.37 J mol -1 , ΔS 0 (pK a2 ) = -36.79 J mol -1 , ΔS 0 (pK a3 ) = 2.79 J mol -1 . Three macro-dissociation constants of lesinurad and protonation locations were predicted by MARVIN and ACD/Percepta., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This paper presents a dual functional extracellular recording biosensor based on a light-addressable potentiometric sensor (LAPS). The design and fabrication of this biosensor make it possible to record both extracellular membrane potential changes and ATP release from a single taste bud cell for the first time. For detecting ATP release, LAPS chip was functionalized with ATP-sensitive DNA aptamer by covalent immobilization. Taste bud cells isolated from rat were cultured on LAPS surface. When the desired single taste bud cell was illuminated by modulated light, ATP release from single taste bud cells can be measured by recording the shifts of bias voltage-photocurrent curves (I-V curves) when the LAPS chip is working in discrete mode. On the other hand, extracellular membrane potential changes can be monitored by recording the fluctuation of LAPS photocurrent when the LAPS chip is working in continuous mode. The results show this biosensor can effectively record the enhancive effect of the bitter substance and inhibitory effect of the carbenoxolone (CBX) on the extracellular membrane potential changes and ATP release of single taste bud cells. In addition, the inhibitory effect of CBX also confirms LAPS extracellular recordings are originated from bitter signal transduction. It is proved this biosensor is suitable for extracellular recording of ATP release and membrane potential changes of single taste bud cells. It is suggested this biosensor could be applied to investigating taste signal transduction at the single-cell level as well as applied to other types of cells which have similar functions to taste bud cells., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Light-addressable potentiometric sensors (LAPS) are of great interest in bioimaging applications such as the monitoring of concentrations in microfluidic channels or the investigation of metabolic and signaling events in living cells. By measuring the photocurrents at electrolyte-insulator-semiconductor (EIS) and electrolyte-semiconductor structures, LAPS can produce spatiotemporal images of chemical or biological analytes, electrical potentials and impedance. However, its commercial applications are often restricted by their limited AC photocurrents and resolution of LAPS images. Herein, for the first time, the use of 1D semiconducting oxides in the form of ZnO nanorods for LAPS imaging is explored to solve this issue. A significantly increased AC photocurrent with enhanced image resolution has been achieved based on ZnO nanorods, with a photocurrent of 45.7 ± 0.1 nA at a light intensity of 0.05 mW, a lateral resolution as low as 3.0 μm as demonstrated by images of a PMMA dot on ZnO nanorods and a pH sensitivity of 53 mV/pH. The suitability of the device for bioanalysis and bioimaging was demonstrated by monitoring the degradation of a thin poly(ester amide) film with the enzyme α-chymotrypsin using LAPS. This simple and robust route to fabricate LAPS substrates with excellent performance would provide tremendous opportunities for bioimaging.

A disposable potentiometric sensor was newly developed for the amplification-coupled detection of nucleic acids. The hydrogen-ion is generally released during isothermal amplification of nucleic acids. The surface potential on the oxide-functionalized electrode of the extended gate was directly measured using full electrical circuits with the commercial metal-oxide semiconductor field-effect transistors (MOSFETs) and ring oscillator components, which resulted in cost-effective, portable and scalable real-time nucleic acid analysis. The current-starved ring oscillator changes surface potential to its frequency depending on the square of the variation in pH with a high signal-to-noise ratio during isothermal amplification. The device achieves a conversion rate of 20.5 kHz/mV and a detection resolution of 200 µV for the surface potential. It is demonstrated that the sensor successfully monitors in real-time isothermal amplification of the extracted nucleic acids from Salmonella pathogenic bacteria. The in situ variations in the frequency of the pH-sensitive sensor were compared with the results of both a conventional optical device and pH-meter during isothermal amplification.

Innovative host-tailored polymers were prepared, characterized and used as recognition elements in potentiometric transducers for the selective quantification of 2,4-dichlorophenol (DCP).The polymer beads were synthesized using DCP as a template molecule, acrylamide (AM),methacrylic acid (MAA) and ethyl methacrylate (EMA) as functional monomers and divinylbenzene (DVB) and ethylene glycol dimethacrylate (EGDMA) as cross-linkers. The sensors were fabricated by the inclusion of MIPs in plasticized polyvinyl chloride (PVC) matrix. Response characteristics of the proposed sensors revealed anionic slopes of -59.2, -49.7 and -80.6 mV/decade with detection limits of 5.6 × 10 -5 ,5.9 × 10 -5 and 13.2 × 10 -5  mol/L for MIP/AM/DVB, MIP/MAA/DVB and MIP/EMA/EGDMA membrane based sensors, respectively. Good selectivity was observed over common inorganic/organic anions. Validation of the assay method according to IUPAC recommendations was justified ensuring the synthesis of good reliable novel sensors for DCP determination. The method was successfully applied for routine analysis of food taint in fish and fish farms water samples., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The application of traditional ion-selective electrodes for comparative enzymatic analysis was demonstrated for the first time in this study. A kinetic-potentiometric method based on the monitoring of the concentration of the ionic substrate involved in the enzymatic reaction catalyzed by different cholinesterases is used for this purpose. A comparative study was performed comprising both enzymatic assays using different ionic substrates and the corresponding inhibited reactions in presence of neostigmine (a synthetic anticholinesterase). The developed approach is used to obtain valuable comparative results through calculation of kinetic parameters, such as Michaelis and inhibition constants. Interesting results were obtained for acetylcholinesterase and butyrylcholinesterase enzymes, which were selected as proof-of-concept: (i) the binding affinity that these enzymes have for their natural substrates showed to be higher (acetylcholine and butyrylcholine respectively) than for their corresponding thiol derivatives (acetylthiocholine and butyrylthiocholine), which are traditionally used in spectrophotometric enzymatic assays; (ii) as expected, the maximum hydrolysis rate found in the assays of each enzyme was independent of the substrate used; (iii) acetylcholinesterase enzyme inhibition due to neostigmine was found to be higher (higher inhibition constant). Advantageously, the use of ion-selective electrodes permits to perform cholinesterases' enzymatic assays using their natural substrates and under physiological conditions, unlike the traditional spectrophotometric methods used in routine enzymatic assays. Importantly, while well-known enzymes are use throughout this work, this approach can be extended to other types of enzymatic assays as a tangible alternative to traditional spectrophotometric methods., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Foodborne bacteria, inducing outbreaks of infection or poisoning, have posed great threats to food safety. Potentiometric sensors can identify bacteria levels in food by measuring medium's pH changes. However, most of these sensors face the limitation of low sensitivity and high cost. In this paper, we developed a high-sensitivity ion-sensitive field-effect transistor sensor. It is small sized, cost-efficient, and can be massively fabricated in a standard 65-nm complementary metal-oxide-semiconductor process. A subthreshold pH-to-time-to-voltage conversion scheme was proposed to improve the sensitivity. Furthermore, design parameters, such as chemical sensing area, transistor size, and discharging time, were optimized to enhance the performance. The intrinsic sensitivity of passivation membrane was calculated as 33.2 mV/pH. It was amplified to 123.8 mV/pH with a 0.01-pH resolution, which greatly exceeded 6.3 mV/pH observed in a traditional source-follower based readout structure. The sensing system was applied to Escherichia coli (E. coli) detection with densities ranging from 14 to 140 cfu/mL. Compared to the conventional direct plate counting method (24 h), more efficient sixfold smaller screening time (4 h) was achieved to differentiate samples' E. coli levels. The demonstrated portable, time-saving, and low-cost prescreen system has great potential for food safety detection.

The compact potentiometer, based on an electronic circuit protected from electrostatic and electromagnetic interference, was developed for the measurement of low ion concentrations in liquids. The electronic circuit of the potentiometer, consisting of analogous and digital parts, enables the measurement of fA currents. This makes it possible to perform reliable measurements of ion concentrations in liquids that are as small as 10 -8 -10 -7 M. The instrument was tested using electrodes that were selective for tetraphenylphosphonium (TPP + ) ions. It was demonstrated that the characteristic response time of the potentiometer electronic circuit to changes in the concentration of these ions in a liquid was in the order of 10 s. An investigation of TPP + absorption by baker yeast has shown that this device can be successfully used for long term (several hours) measurements with zero signal drift, which was about 1 μV/s. Finally, due to the small dimensions of the electronic circuit (7.5 × 2 × 1.5 cm), this potentiometer can be easily installed at a large apparatus in the laboratory condition (≈25 °C), such as high pulsed electrical generators of magnetic fields that are used in electroporation studies of biological cells.