Search Results (768)

Solid-contact ion-selective electrodes (SC-ISEs) are typically constructed using ion-selective membrane (ISM)-based configurations. However, such structures often suffer from water-layer formation and the weak mechanical stability of the ISM. Herein, we report an ISM-free K⁺-SC-ISE based on a Prussian blue analogue transducer, KMnFe(CN)₆, eliminating the need for a conventional ionophore-based ISM layer. KMnFe(CN)₆ was synthesized via a one-step citrate-assisted co-precipitation method. The material functions as a bifunctional transducer, in which the open framework structure with ion-transport channels enables selective K⁺ recognition, while the redox-active Mn centers facilitate ion-to-electron transduction. The fabricated KMnFe(CN)₆-based K⁺ sensor exhibits a near-Nernstian response with a sensitivity of 52.3 ± 1.0 mV dec⁻¹ and a rapid response time of 25 s. The linear range and limit of detection were determined to 10⁻⁴ to 10⁻¹ M and 5.8 × 10⁻⁵ M, respectively. The sensor also demonstrates selectivity to representative interfering ions, with log K_ij of −2.39 ± 0.12 (Na⁺), −2.86 ± 0.09 (Li⁺), −3.06 ± 0.09 (Ca²⁺), −2.74 ± 0.12 (Mg²⁺) and −0.95 ± 0.08 (NH₄⁺). By eliminating the ISM layer, the water-layer effect is effectively avoided, resulting in excellent long-term stability with a potential drift of 57.2 ± 6.1 μV h⁻¹ over 7 days. The sensor was further applied to the analysis of K⁺ in real lake water samples, where the measured concentration showed good agreement with ion chromatography results. This work provides an ISM-free SC-ISE strategy for ion analysis in water environments. Full article

Objectives: This study characterised the bioactive properties (i.e., ion release, pH rise, and apatite formation) of a newly developed Voco Profluorid + BioMin F varnish. Three additional varnishes were investigated for comparison: Clinpro™ White Varnish (3M™, St. Paul, MN, USA), MI Varnish (GC, Tokyo, Japan), and Profluorid varnish (VOCO GmbH, Cuxhaven, Germany). The Clinpro™ White and MI varnishes were chosen for comparison due to their similar composition of active ingredients. Profluorid served as a standard fluoride-only varnish reference. Methods: Dental varnish ingredients were characterised using ATR-FTIR, XRD, and ¹⁹F and ³¹P MAS-NMR. Coated coverslips were immersed in Tris buffer and artificial saliva (pH 4.0 and 7.0) for 2–24 h. Ion release was analysed using ICP-OES and a fluoride ion-selective electrode whilst monitoring pH changes. Post-immersion, coverslips were analysed by XRD and MAS-NMR to assess possible apatite formation. Results: XRD and ¹⁹F MAS-NMR detected NaF in all four varnishes. BioMin F varnish showed a ³¹P peak matching BioMin F glass, with an additional brushite peak, indicating partial reaction of the bioactive glass (BAG) with rosin resin water. All varnishes released fluoride and calcium, but only BioMin F and MI varnishes released phosphate, which is essential for the formation of calcium fluorapatite. Post-immersion analysis confirmed fluorapatite formation in BioMin F and, to a lesser extent, the Profluorid varnish. No apatite formation was observed in the other two varnishes. MI varnish exhibited calcium fluoride formation before and after immersion, as evidenced by XRD and ¹⁹F MAS-NMR analysis. Conclusions: The novel BioMin F varnish potentially promotes remineralisation by providing a sustained and slow release of therapeutic ions that are essential for the formation of fluorapatite. Full article

This review examines the reported research on the potential responses of ion-selective electrodes over time when exposed to sudden changes in the concentration of the primary ion (ion initially present in the ion-selective electrode membrane) and/or foreign interfering ions. Particular attention is given to the responses of liquid- and plasticized polymeric membrane-based ion-selective electrodes to foreign ions. The review provides an in-depth discussion of the theoretical models proposed to describe transient potential signals obtained experimentally with these ion-selective electrodes. In chronological order, the different contributions are presented and commented on in terms of their assumptions and mathematical treatments. The final equations obtained in each case, as well as some stages of their derivations, are presented. Additionally, the various models are classified and critically commented upon. Lastly, the review discusses the analytical applications reported for identifying and quantifying ions using the transient potential signals. Full article

The development of high-performance and sustainable carbon electrodes is increasingly important for next-generation supercapacitors, yet controlling heteroatom doping and hierarchical pore evolution in biomass-derived carbons remains a key challenge. Lignin, as an abundant aromatic biopolymer, offers a structurally rich platform for designing functional carbons, but its rigid cross-linked architecture limits precise pore regulation and efficient nitrogen incorporation. In this work, nitrogen-doped hierarchical porous carbons were engineered from enzymatically treated lignin through a synergistic urea-assisted nitrogen doping and KOH activation strategy. The urea–KOH co-activation drives the coordinated evolution of micropores and mesopores. This approach yields an optimized carbon material possessing a high BET surface area of 2569 m² g⁻¹, an interconnected micro–mesoporous architecture, and a favorable distribution of pyridinic, pyrrolic, and graphitic nitrogen species. The engineered pore hierarchy is correlated with enhanced ion transport kinetics, as evidenced by a high b value of 0.99 and a capacitive contribution of 98.5% at 100 mV s⁻¹; nitrogen functionalities introduce redox-active sites and improve interfacial wettability. As a result, the selected material delivers a high specific capacitance of 221 F g⁻¹ at 0.5 A g⁻¹, strong rate capability with 84.4% retention at 20 A g⁻¹, and excellent cycling durability with 90.7% capacitance retention after 50,000 cycles. This study demonstrates a potentially mechanistically informed, scalable pathway for coupling enzymatic structural regulation with chemical activation, offering a sustainable route for transforming lignin into high-value carbon electrodes suitable for advanced supercapacitor applications. Full article

The rapid detection of organophosphorus (OP) compounds is crucial for safeguarding human health and ensuring food safety. This study presents a novel wearable electrochemical biosensor that integrates miniaturized screen-printed electrodes with wearable devices to achieve real-time, on-site OP detection. The biosensor was fabricated by constructing a screen-printed carbon electrode (SPCE) on a thermoplastic polyurethane (TPU) substrate, sequentially modified with graphene (GR), gold nanoparticles (AuNPs), and organophosphorus hydrolase (OPH), and finally encapsulated with Nafion. This SPCE/GR/AuNPs/OPH/Nafion configuration yields a highly flexible and portable device. The detection principle relies on the enzymatic hydrolysis of methyl paraoxon (MPOX) by OPH, generating p-nitrophenol (PNP), which is quantitatively measured via square wave voltammetry (SWV). The sensor exhibits a broad linear detection range (30–400 μM) with a strong linear correlation (R² = 0.995) and a low detection limit (0.321 μM). It demonstrates excellent selectivity against common interfering substances, including urea, sucrose, and various metal ions. Application to real-world samples such as cabbage and tap water yielded high recoveries (107.2% for cabbage and 101.2% for tap water), with relative standard deviations (RSDs) below 8%. Furthermore, the biosensor maintains robust flexibility and mechanical resilience, with less than 5% signal loss after 100 bending cycles, confirming its suitability for wearable applications and reliable operation under mechanical stress. This innovative, flexible electrochemical biosensor provides a powerful and reliable platform for rapid OP detection, particularly in complex testing environments. Full article

An important challenge for materials researchers in the modern era is the fabrication of high-performance electrodes with novel designs and structures to enhance electrochemical sensing and energy storage performance. Recently, perovskite-structured bimetallic hydroxide materials, owing to their high conductivity, decent surface area, abundant redox activity, and good stability, have emerged as promising candidates for bifunctional electrochemical applications. In this study, we designed perovskite-type CuSn(OH)₆ microspheres via a facile coprecipitation method for nifedipine (NFD) sensing and supercapacitors (SCs). Various characterization techniques were employed to confirm the successful synthesis of CuSn(OH)₆. The uniform formation and distribution of CuSn(OH)₆ within the sphere structure provide rich reactive sites and enhance structural stability, thereby improving electrochemical activity. This architecture also induces a synergistic effect between Cu and Sn, which increases conductivity and accelerates redox kinetics. Consequently, the electrode modified with CuSn(OH)₆/GCE exhibited a wide linear concentration range of 0.4–303.3 µM and a low detection limit of 0.44 µM for NFD detection. This sensor further demonstrated superior analytical reliability, with selectivity of <5%, cycling stability of 84.79%, reproducibility of 3.3%, and recovery rates of 99.2–99.8% in the serum sample. Concurrently, the CuSn(OH)₆/NF showcased a high specific capacitance of 514 F g⁻¹ at 1 A g⁻¹, good longevity of 83.05% retention after 5000 cycles, and low charge transfer resistance of 6.56 Ω and solution resistance of 1.04 Ω, validating fast ion–electron transport. These results underscore that perovskite-based CuSn(OH)₆ is an efficient dual-functional electrocatalyst for sensitive electrochemical detection and high-performance SCs. Full article

The self-directed channel (SDC) class of memristors employs a multilayer architecture that is designed to enable robust Ag ion conduction, long cycling lifetime, and thermal stability. While several layers contribute to mechanical and chemical reliability, two layers primarily govern the electrical behavior: the amorphous Ge–chalcogenide active layer that is adjacent to the bottom electrode and the overlying metal–chalcogenide source layer. In this work, we investigate how the variation in the chalcogen species in these two layers influences switching characteristics in the pre-write regime, both in the pristine state and after a write/erase cycle, as well as the conduction behavior at room temperature. The devices were fabricated using Ge-rich chalcogenides containing O, S, Se, or Te, combined with SnS, SnSe, or Ag₂Se metal–chalcogenide layers. The DC current-voltage measurements were analyzed using the standard linearization approaches to examine whether the transport behavior in the pre-write regime exhibits characteristics that are associated with Ohmic, Schottky, Poole–Frenkel, or space charge limited conduction. These measurements specifically probe the pre-write region of the I-V curve, where early ionic redistribution and structural rearrangement precede the abrupt formation of the conductive channels responsible for the resistive switching. The results show that the chalcogen composition strongly affects the threshold voltage, the resistance window, and the onset of field-enhanced transport, reflecting the differences in ionic distribution and channel formation dynamics. The results indicate that transport evolves with a bias and a compliance current, transitioning between regimes that are influenced by the interface injection and bulk-limited conduction, depending on the material stack. These findings clarify the role of chalcogen chemistry in governing the SDC switching behavior and provide guidance for the material selection in application-specific device design. Full article

Electrochemical sensors are user-friendly devices designed for the rapid and straightforward detection of target analytes. Serotonin (5-hydroxytryptamine, 5-HT) is a key neurotransmitter and neuromodulator that regulates diverse neuronal processes. Using a custom-designed screen-printed carbon electrode (SPCE) incorporating ordered mesoporous carbon–bimetal oxides of Cu and Ni (CuO–NiO–OMC), rapid and real-time detection of 5-HT was achieved. The CuO–NiO–OMC structure featured highly active CuO and NiO catalytic sites that effectively promoted the irreversible oxidation of 5-HT (vs. Ag/AgCl reference electrode). The CuO–NiO–OMC/SPCE sensor, connected to a portable potentiostat, exhibited exceptional electrocatalytic performance for the oxidation of 5-HT, with a detection limit of 42.5 nM. The sensitivity was 1.56 A M⁻¹ cm⁻², and the linear dynamic range was 0.0–80.0 µM. The CuO–NiO–OMC/SPCE sensor also demonstrated outstanding selectivity in the presence of competing neurochemicals, including norepinephrine, epinephrine, dopamine, and glutamate, as well as high concentrations of tested biomolecules and inorganic ions. Furthermore, the practicality of the sensor was demonstrated using human serum and urine samples, with recovery percentages ranging from 91.1% to 98.3%. Thus, the CuO–NiO–OMC/SPCE sensor offers an effective approach for 5-HT sensing, thereby permitting molecular-level understanding of brain function. Full article

In this work, a hybrid polymer electrolyte integrating single- and dual-ion conducting systems was developed for lithium-ion batteries using bio-based materials, namely oleic-acid derivatives and epoxidized soybean oil, through an in situ polymerization process. The fixed FSI anions in LiEFSOA enhance the selectivity of Li⁺ transport, while the cross-linked network formed by ESO provides mechanical stability, and the LiFSI incorporated into the polymer matrix helps maintain sufficient overall ionic conductivity. In addition, the long C18 oleic chains increase the internal free volume of the matrix, thereby improving segmental mobility within the amorphous phase. The in situ polymerization inside the cell causes intimate interfacial contact between the electrode and electrolyte, achieving an ionic conductivity of 1.05 × 10⁻⁴ S cm⁻¹ at 30 °C. Electrochemical evaluation using LiFePO₄/FSOA-2/Li cells shows an initial discharge capacity of 149.09 mAh g⁻¹ and a capacity retention of 81.09% after 100 cycles, and the average coulombic efficiency was 99.62%, demonstrating that the designed FSOA electrolyte exhibits stable cycling performance and competitive capacity. Overall, the combination of eco-friendly materials and a hybrid ion transport strategy provides a promising platform for developing sustainable and high-performance polymer electrolytes for lithium-ion batteries. Full article

A new universal construction of intermediate-layer-free solid-contact ion-selective electrodes using a novel inner electrode, namely microelectrodes array composed of a large number of individual microelectrodes, was developed. This approach eliminates the need for a conventional solid-contact intermediate layer while maintaining excellent electrochemical performance. The studies were performed on two membrane model systems: potassium-ion-sensitive membranes based on valinomycin and nitrate-ion-sensitive membranes based on tridodecyldimethylammonium nitrate. In both cases, the membrane was applied directly onto the surface of the electrode substrate. The obtained results with such an ion-selective electrode based on a gold microelectrode array (GMA), a glassy carbon electrode (GCE), and a gold electrode (GE) were compared. It has been proven that, despite the lack of solid contact, whether in the form of an intermediate layer or as an addition directly to the membrane, ion-selective electrodes based on gold microelectrode arrays were characterized by very good analytical parameters. For those electrodes, a notable improvement in stability, reversibility, and repeatability of the electrode potential was observed and compared with electrodes using a glassy carbon disc electrode or a gold disc electrode as the electrode substrate. Thanks to the use of such an innovative electrode substrate, the final sensor preparation is shortened and simplified while maintaining good performance and stable readings. Full article

Ion-selective electrodes (ISEs) are widely used analytical tools for the determination of specific ions in a variety of analytical applications due to their simplicity, selectivity, and low cost. Recent developments in materials science and digital fabrication have opened new opportunities for redesigning ISEs using modern manufacturing techniques. Here, we present a new application of 3D printing for fabricating potassium-selective electrodes using a simplified membrane composition. The 3D printing cocktail was prepared by mixing potassium tetraphenylborate, silver sulfide or graphite, and industrial ABS (acrylonitrile Butadiene Styrene) polymer. Membranes were tested both without and with the addition of ZnO nanoparticles. Incorporation of ZnO NPs significantly enhanced the electrode slope, while graphite-based membranes exhibited faster response, with potential stabilizing within 3–7 s across a concentration range of 4.88 × 10⁻⁵ mol L⁻¹ to 1.00 × 10⁻² mol L⁻¹. The optimized 3D printed membrane containing 0.6% ZnO NPs showed near-Nernstian behaviour (slope: 59.178 mV per decade and R² = 0.9989), a limit of detection of 2.06 × 10⁻⁵ mol L⁻¹ and high selectivity against common interfering ions. These results demonstrate that 3D printing combined with a suitable membrane composition and nanoparticle incorporation provides a versatile platform for rapid, reproducible, and high-performance potassium ISEs. Full article

We report a versatile, CMOS-compatible fabrication module for sub-100 nm TiN and TaN pillar electrodes, a key building block for sandwich-type test structures. As a demonstration, the electrodes were integrated into carbon nanotube-based nonvolatile random-access memory (CRAM) test structures. High-resolution hydrogen silsesquioxane (HSQ) masks defined by electron beam lithography were transferred into TiN films using optimized Ar/Cl₂ inductively coupled plasma reactive ion etching. Optical emission spectroscopy was used for real-time endpoint detection, ensuring precise etch control. The process achieved a TiN-to-HSQ selectivity of ~1.6 and reproducible nanoscale features with smooth sidewalls and an average taper angle of ~77°. Buffered hydrogen fluoride treatment effectively removed residual HSQ, revealing sharp TiN features and preserving pillar geometry. Atomic force microscopy (AFM) confirmed pillar height and profile fidelity, while conductive AFM verified electrical conductivity after planarization. The module was further demonstrated through the fabrication of TiN pillar arrays, TaN pillars, and sub-100 nm TiN line arrays. A CRAM test structure incorporating TiN pillars exhibited preliminary switching, indicating that both the test structure and fabrication process are feasible. This fabrication module provides a reproducible platform for nanoscale TiN and TaN electrodes, supporting laboratory-scale research and providing a pathway toward future integration of emerging memory and nanoelectronic technologies. Full article

Glassy carbon electrodes (GCEs) have gained increased attention for the sensitive electrochemical detection of heavy metals due to their excellent chemical stability, wide potential window, and good electrical conductivity. These characteristics make GCEs an effective platform for sensor development. In particular, nanomaterial-modified GCEs have emerged as a promising strategy, offering enhanced sensitivity, selectivity, and faster response compared to conventional analytical techniques. This review summarizes recent advances over the past five years in the use of GCEs modified with chemically synthesized nanoparticles for the simultaneous detection of multiple heavy metal ions, including cadmium, lead, mercury, and chromium. It also includes how quantum chemical methods have aided our understanding of these phenomena. Heavy metals pose significant environmental and public health risks, with well-documented neurological, cardiovascular, reproductive, and carcinogenic effects, highlighting the need for accurate and rapid monitoring methods. Regulatory limits established by organizations such as the World Health Organization and the Environmental Protection Agency further emphasize the demand for highly sensitive detection technologies. This review examines the fundamental properties of GCEs, common nanomaterial modification techniques, and their application in multi-ion detection systems. Key advantages such as cost-effectiveness, portability, and adaptability to diverse sample matrices are highlighted. Current challenges, including electrode fouling, selectivity, and matrix interference, are also addressed, along with future perspectives for improving GCE-based sensors for real-world environmental monitoring. Full article

High concentrations of ionized ammonia (${\mathrm{NH}}_4^{+}$) have been increasingly reported in municipal drinking water systems, posing a severe public health risk as excessive ingestion can lead to life-threatening conditions. Despite its importance, there is a significant lack of sensing technologies designed for continuous-flow monitoring outside laboratory settings, particularly those providing a robust, low-cost methodology suitable for resource-limited environments. To address these challenges, in this work, we report the development of an impedance sensor featuring a 3D-printed housing (3D-IS) for monitoring aqueous ionized ammonia (${\mathrm{NH}}_4^{+}$). The sensing electrodes, composed of zinc oxide and graphite, allow for the detection of concentrations 10 times lower and 60 times higher than current environmental limits. Its innovative, optimized design, analogous to that of industrial pressure gauges, highlights its potential for use in continuous water flow conditions outside the laboratory, such as water treatment plants. The level of ${\mathrm{NH}}_4^{+}$ in water is monitored by changes in impedance magnitude, with optimal performance observed at a frequency of 100 kHz. At this frequency, the impedance magnitude decreased by nearly two orders of magnitude as the ${\mathrm{NH}}_4^{+}$ concentration increased from 0 to 1 μM. Under these optimized conditions, the sensor exhibited a sensitivity of 2 kΩ/log(μM) and a linearity exceeding 90%. Furthermore, we propose an equivalent circuit model that accurately describes the experimental data, explaining the transduction process. We also describe, from an electrical perspective, the phenomenon of adsorption on the sensor’s transducer surface, thereby ensuring the device’s selectivity. The sensor was evaluated using dilutions of a standard ammonium solution for IC in distilled water, as well as with real groundwater samples, obtaining ∼99.7% of correlation with ion chromatography and a limit of detection of 2 μM. Finally, our device can provide information relatively quickly, with the added advantage of stable response under continuous-flow and real conditions, making it an attractive option for integration into a field sensor node. Full article

The rapid expansion of lithium-ion battery (LIB) applications and the imminent surge in end-of-life batteries have intensified the demand for efficient, scalable recycling technologies. Physical separation of cathode and anode materials is a crucial pretreatment step that enables high-value metal recovery and direct material regeneration. This review critically examines recent advances in three major physical separation technologies—magnetic separation, gravity separation, and flotation—for processing spent LIB electrodes. Rather than offering a descriptive summary, the review systematically analyzes separation mechanisms, key controlling parameters, and pretreatment strategies across representative cathode chemistries, including LiFePO₄ (LFP), LiCoO₂ (LCO), and Ni–Co–Mn (NCM) systems. Particular emphasis is placed on emerging flotation-enhancement strategies, such as nanobubble-assisted and ultrasonic-enhanced flotation, and their underlying mechanistic roles in improving selectivity and recovery. Comparative evaluation indicates that magnetic separation has reached industrial maturity for LFP–graphite systems but remains chemistry-specific. Gravity separation is effective for coarse particles and centrifugal-assisted graphite recovery yet shows limited selectivity for fine particles. Flotation has become the dominant research focus for complex, fine-particle separations due to its tunable surface chemistry. Despite significant laboratory progress, challenges remain, including incomplete binder removal, limited understanding of electrode surface reconstruction during pretreatment, fine-particle entrainment, and the gap between bench-scale research and industrial implementation. Future research priorities include green reagent development, intelligent separation control, and integration with direct regeneration routes to advance closed-loop LIB recycling towards sustainable development. Full article