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This study involved the preparation of an all-solid-state ion-selective electrode (ASS-ISE) with copper and a poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT/PSS) conversion layer through electrode deposition. The morphology of the PEDOT/PSS film was characterized, and the performance of the copper ion-selective film was optimized. Additionally, a microfluidic chip for the ASS-ISE with copper was designed and prepared. An integrated microfluidic chip test system with an ASS-ISE was developed using a self-constructed potential detection device. The accuracy of the system was validated through comparison testing with atomic absorption spectrophotometry (AAS). The experimental findings indicate that the relative standard deviation (RSD) of the integrated ASS-ISE with the copper microfluidic chip test system is 4.54%, as compared to the industry standard method. This value complies with the stipulated requirement of an RSD ≤ 5% in DL/T 955-2016.

A new solid-contact ion-selective electrode (ISE) sensitive to lead (II) ions, obtained by modifying a polymer membrane with a nanocomposite of carbon nanofibers and an ionic liquid 1-hexyl-3-methylimidazolium hexafluorophosphate, is presented. Electrodes with a different amount of nanocomposite in the membrane (0-9% w/w ), in which a platinum wire or a glassy carbon electrode was used as an internal electrode, were tested. Potentiometric and electrochemical impedance spectroscopy measurements were carried out to determine the effect of the ion-sensitive membrane modification on the analytical and electrical parameters of the ion-selective electrode. It was found that the addition of the nanocomposite causes beneficial changes in the properties of the membrane, i.e., a decrease in resistance and an increase in capacitance and hydrophobicity. As a result, the electrodes with the modified membrane were characterized by a lower limit of detection, a wider measuring range and better selectivity compared to the unmodified electrode. Moreover, a significant improvement in the stability and reversibility of the electrode potential was observed, and additionally, they were resistant to changes in the redox potential of the sample. The best parameters were shown by the electrode obtained with the use of a platinum wire as the inner electrode with a membrane containing 6% of the nanocomposite. The electrode exhibited a Nernstian response to lead ions over a wide concentration range, 1.0 × 10 -8 -1.0 × 10 -2 mol L -1 , with a slope of 31.5 mV/decade and detection limit of 6.0 × 10 -9 mol L -1 . In addition, the proposed sensor showed very good long term stability and worked properly 4 months after its preparation without essential changes in the E 0 or slope values. It was used to analyze a real sample and correct results of lead content determination were obtained.

This paper reviews the development of all-solid-state ion-selective electrodes (ASSISEs) for agricultural crop detection. Both nutrient ions and heavy metal ions inside and outside the plant have a significant influence on crop growth. This review begins with the detection principle of ASSISEs. The second section introduces the key characteristics of ASSISE and demonstrates its feasibility in crop detection based on previous research. The third section considers the development of ASSISEs in the detection of corps internally and externally (e.g., crop nutrition, heavy metal pollution, soil salinization, N enrichment, and sensor miniaturization, etc.) and discusses the interference of the test environment. The suggestions and conclusions discussed in this paper may provide the foundation for additional research into ion detection for crops.

A novel freestanding all-solid-state polymeric membrane Cu 2+ -selective electrode (Cu 2+ -ISE) is proposed based on three-dimensional graphene sponge (3D GS). The 3D GS electrode has been characterized by cyclic voltammetry, electrochemical impedance spectroscopy, and contact angle measurements. Experiments show that 3D GS possesses a large electrical double layer capacitance, good conductivity, and high hydrophobicity. Based on these superior properties, 3D GS has been applied as both electrode substrate and solid contact for construction of a freestanding all-solid-state polymeric membrane Cu 2+ -ISE. The 3D GS-based Cu 2+ -ISE shows a good Nernstian response ranging from 1.0 × 10 -8 to 7.9 × 10 -4  M with a low detection limit of 2.5 × 10 -9  M. Moreover, the proposed Cu 2+ -ISE exhibits a stable potential response with a reduced water layer at the sensing membrane/3D GS interface and is not affected by interferences from light, O 2 and CO 2 ., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Nanostructured materials have attracted considerable interest over the last few decades to enhance sensing capabilities thanks to their unique properties and large surface area. In particular, noble metal nanostructures offer several advantages including high stability, non-toxicity and excellent electrochemical behaviour. However, in recent years the great expansion of point-of-care (POC) and wearable systems and the attempt to perform measurements in tiny spaces have also risen the need of increasing sensors miniaturization. Fast constant potential electrodeposition techniques have been proven to be an efficient way to obtain conformal platinum and gold nanostructured layers on macro-electrodes. However, this technique is not effective on micro-electrodes. In this paper, we investigate an alternative one-step deposition technique of platinum nanoflowers on micro-electrodes by linear sweep voltammetry (LSV). The effective deposition of platinum nanoflowers with similar properties to the ones deposited on macro-electrodes is confirmed by morphological analysis and by the similar roughness factor (~200) and capacitance (~18 μ F/mm 2 ). The electrochemical behaviour of the nanostructured layer is then tested in an solid-contact (SC) L i + -selective micro-electrode and compared to the case of macro-electrodes. The sensor offers Nernstian calibration with same response time (~15 s) and a one-order of magnitude smaller limit of detection (LOD) ( 2.6 × 10 - 6 ) with respect to the macro-ion-selective sensors (ISE). Finally, sensor reversibility and stability in both wet and dry conditions is proven., Competing Interests: The authors declare no conflict of interest.

Nowadays the development of stable and highly efficient Solid-Contact Ion-Selective Electrodes (SC-ISEs) attracts much attention in the research community because of the great expansion of portable analytical devices. In this work, we present highly stable Li + all-solid-state ISEs exploiting noble metals nanostructures as ion-to-electron transducers. The detection of lithium is essential for therapeutic drug monitoring of bipolar patients. In addition, greater environmental exposure to this ion is occurring due to the large diffusion of lithium-ion batteries. However, only a limited number of SC Li + ISEs already exists in literature based on Conductive Polymers (CPs) and carbon nanotubes. The use of noble metals for ion-to-electron transduction offers considerable advantages over CPs and carbon materials, including fast and conformal one-step deposition by electrochemical means, non-toxicity and high stability. We investigate for the first time the use of gold nanocorals obtained by means of a one-step electrodeposition process to improve sensor performance and we compare it to all-solid-state ISEs based on electrodeposited platinum nanoflowers. In addition, the effect of substrate electrode material, membrane thickness and conditioning concentration on the potentiometric response is carefully analysed. Scanning Electron Microscopy (SEM) and Current Reversal Chronopotentiometry (CRC) techniques are used to characterize the morphology and the electrochemical behaviour of the different ISEs. The use of nanostructured gold and platinum contacts allows the increase of the SC capacitance by one or two orders of magnitude, respectively, with respect to the flat metal, while the SC resistance is significantly reduced. We show that the microfabricated sensors offer Nernstian behaviour (58.7±0.8 mV/decade) in the activity range from 10 -5 to 0.1 M, with short response time (∼15 s) and small potential drift during CRC measurements (dEdt=3×10 -5 ±2×10 -5 V/s). The exceptional response stability is verified also when no potential is applied. The sensor shows high selectivity towards all clinically important ions, with values very similar to conventional ISEs. Furthermore, to our knowledge, the selectivity towards Ca +2 is the best ever reported for SC-ISEs. In conclusion, the present study opens up new interesting perspectives towards the development of simple and reproducible fabrication protocols to obtain high-quality and high-stability all-solid-state ISEs., (Copyright © 2018 The Author(s). Published by Elsevier B.V. All rights reserved.)

We report here the fabrication of solid-contact calcium-selective electrodes (Ca 2+ -SCISEs) made of a polyurethane acrylate ion-selective membrane (ISM) that was covalently attached to the underlying ion-to-electron transducer (solid-contact). Methacrylate-functionalized poly(3,4-ethylenedioxythiophene) (Meth-PEDOT) and Meth-PEDOT films containing either multiwalled carbon nanotubes (MWCNT) or carboxylated MWCNT (cMWCNT) were used as solid contacts. The solid contacts were deposited by drop-casting on screen-printed electrodes and characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and potentiometry. Covalent binding between the solid contact and the ISM was obtained via photopolymerization in order to increase the robustness of the Ca 2+ -SCISEs. The performance of the Ca 2+ -SCISEs was studied by measuring their potentiometric response and their sensitivity to light, oxygen and carbon dioxide. Meth-PEDOT was found to be a promising solid-contact material to develop low-cost and easy to prepare ISEs., (Copyright © 2018 Elsevier B.V. All rights reserved.)

A magnetic field-directed self-assembly solid contact has been proposed for developing an all-solid-state polymeric membrane Ca 2+ -selective electrode. The solid contact is prepared by physically adsorbing magnetic graphene powder on a magnetic gold electrode under the direction of the magnetic field. The proposed method for preparing solid contact avoids using the aqueous solutions and is simple, fast and general as compared to the multilayer drop-casting and electrodeposition methods. The all-solid-state Ca 2+ -selective electrode based on magnetic graphene as solid contact shows a stable potential response in the linear range of 1.0 × 10 -6 -1.0 × 10 -3  M with a slope of 28.2 mV/decade, and the detection limit is about 4.0 × 10 -7  M. Additionally, the magnetic graphene-based electrode shows a comparable potential stability performance to other graphene-based all-solid-state ion-selective electrodes, such as reduced undesirable water layer and insensitive to the interferences of O 2 , CO 2 and light. This work provides a favorable way to prepare solid contact for use in the field of all-solid-state ion-selective electrodes., (Copyright © 2017 Elsevier B.V. All rights reserved.)