Miniature Ion‐selective Electrodes with Mesoporous Carbon Black as Solid Contact

Improving the stability of Pb2+ ion-selective electrodes by using 3D polyaniline nanowire arrays as the inner solid-contact transducer

Rectifying effect for ion-selective electrodes with conducting polymer solid contact

A simple and powerful method based on UV-visible spectroscopy is presented for studying the stability of the inner electrically conducting polyaniline (PANI) solid contact (SC) layer in all-solid-state ion-selective electrodes (ISE). The influence of the plasticized poly(vinyl chloride) (PVC) membrane (ISM) composition and the pH of the sample solution on the stability of the solid contact is reported. PANI is used as a model compound in this study, but the method presented is universal and can be applied to different types and combinations of SCs and ISMs. It provides a tool for finding the best combination of conducting polymer and ISM for solid contact ISEs. PANI is deposited electrochemically either on glassy carbon or quartz glass covered with a thin layer of tin oxide, and a K+-selective ISM is deposited on top of the PANI layer. The short-term stability of the inner PANI layer is good for all membrane types in buffer solutions with pH 2, 6, and 9, indicating that the outer plasticized PVC membrane hinders the emeraldine salt-emeraldine base transition of the highly pH sensitive PANI layer. The solid contact K+-selective electrodes studied showed a Nernstian response of 58.2 +/- 0.1 mV/log aK. Significant differences are observed in the long-term stability of the inner PANI layer between the different membrane types. This indicates that water uptake of the PVC membrane and its permeability to OH- ions are critical parameters affecting the stability of the PANI layer. The solid contact electrodes based on PANI may require a composition of the PVC membrane different from those typically used in conventional ISEs with an inner solution.

The high-temperature potentiometry operated by nonisothermal heating is a promising way to break through the traditional potentiometric responses of ion-selective electrodes (ISEs) at room temperature. Herein, a locally heated strategy through near-infrared region (NIR) laser irradiation upon the photothermal mesoporous carbon material placed between the ion-selective membrane and the glassy carbon substrate is introduced to obtain the high-temperature potentiometric performance of a solid-contact Ca2+-ISE for detection of Ca2+ in seawater. Based on the light-to-heat conversion of the mesoporous carbon-based solid contact, the temperature of the solid-contact Ca2+-ISE upon continuous NIR laser irradiation can be increased from room temperature to 60-70 °C, and the slope of the electrode is promoted up to about 30% according to the thermodynamic steady-state potentiometric response. The pulsed potentiometric response of the solid-contact Ca2+-ISE upon a pulsed NIR laser irradiation of 5 s also shows a linear change as a function of Ca2+ activities, and the improved slope from 27.1 ± 0.6 to 38.1 ± 0.9 mV/dec can be obtained under dual control of the temperature of the electrode and the transient current induced by the pulsed NIR laser irradiation. As compared to the traditional potentiometric measurement under zero-current conditions at room temperature, the NIR laser-modulated high-temperature potentiometric response provides an alternative way for measurement of the solid-contact ISEs.

This study aimed to develop a novel approach for the production of analytically robust and miniaturized polymeric ion sensors that are vitally important in modern analytical chemistry (e.g., clinical chemistry using single blood droplets, modern biosensors measuring clouds of ions released from nanoparticle-tagged biomolecules, laboratory-on-a-chip applications, etc.). This research has shown that the use of a water-repellent poly(methyl methacrylate)/poly(decyl methacrylate) (PMMA/PDMA) copolymer as the ion-sensing membrane, along with a hydrophobic poly(3-octylthiophene 2,5-diyl) (POT) solid contact as the ion-to-electron transducer, is an excellent strategy for avoiding the detrimental water layer formed at the buried interface of solid-contact ion-selective electrodes (ISEs). Accordingly, it has been necessary to implement a rigorous surface analysis scheme employing electrochemical impedance spectroscopy (EIS), in situ neutron reflectometry/EIS (NR/EIS), secondary ion mass spectrometry (SIMS), and small-angle neutron scattering (SANS) to probe structurally the solid-contact/membrane interface, so as to identify the conditions that eliminate the undesirable water layer in all solid-state polymeric ion sensors. In this work, we provide the first experimental evidence that the PMMA/PDMA copolymer system is susceptible to water "pooling" at the interface in areas surrounding physical imperfections in the solid contact, with the exposure time for such an event in a PMMA/PDMA copolymer ISE taking nearly 20 times longer than that for a plasticized poly(vinyl chloride) (PVC) ISE, and the simultaneous use of a hydrophobic POT solid contact with a PMMA/PDMA membrane can eliminate totally this water layer problem.

Solid-contact polymeric membrane electrodes with detection limits in the subnanomolar range

All-solid-state potassium ion-selective electrodes (K+ ISEs) using ordered mesoporous carbon (OMC) sphere as the solid contact (SC) are fabricated in this work, which exhibit excellent K+-sensing capability including the stable Nernstian response in a wide linear range of 10−4.19–10−0.21 M, a low detection limit of 5.4 μM, short response time, and good stability. The excellent performances of the K+ ISEs are attributable to the OMC spheres with interconnected mesopore structure, uniform spherical morphology, high surface area, high conductivity, and high capacitance, which provide the highly efficient ion-to-electron transduction between the ion-selective membrane and conductive component in the electrodes. More importantly, the OMC sphere-based SC layer can be deposited in the flexible ISEs by solution processing, which thus enables the construction of ion-sensitive field-effect transistor-based handheld K+-sensing system with high sensitivity and reproducibility, demonstrating the potentials of the OMC spheres in practical ion detection devices.

Printed potentiometric sensors require reliable solid contacts to provide stable and reproducible ion-selective electrodes. However, hampering fabrications and unfavorable maintenance often hinder their breakthrough on a commercial scale. Herein, we develop a solid-contact calcium-selective screen-printed electrode harnessing straightforward manufacturing based on the combination of carbon black (CB) and poly(3,4-ethylene dioxythiophene) doped with poly(sodium 4-styrenesulfonate) (PEDOT:PSS) as an ion-to-electron transducer. Drop-casting was used to simply deposit the CB layer, while PEDOT:PSS was rapidly electropolymerized (71 s) onto the working electrode to deliver affordable manufacturing of the printed electrode while ensuring valid potentiometric performance. Subsequently, the ion-selective membrane (ISM) and the polyvinyl butyral (PVB)-based reference membrane were, respectively, drop-cast onto the working electrode and reference electrode (RE). Upon the optimization of solid-contact layers, the solid-contact Ca2+-ISEs were investigated by evaluating their potentiometric performance versus a conventional RE. CB/PEDOT:PSS-modified screen-printed electrodes demonstrated a low-frequency capacitance of 55 μF, and an outstanding standard potential interelectrode reproducibility (±1 mV). The combination of both types of ion-to-electron transducers provided calcium detection in the linear range 10-1-10-7 M with a Nernstian sensitivity (28.3 ± 0.3 mV/decade), ensured over 28 days under dry storage. Furthermore, the absence of the water layer effect was also demonstrated. Lastly, the fully printed platform was assembled to achieve a miniaturized and easily field-deployable potentiometric device, consisting of CB/PEDOT:PSS/ISM configuration and PVB-based reference membrane on the working electrode and the RE, respectively. The resulted all-solid-state sensor revealed a Nernstian sensitivity with a 29.0 ± 0.5 mV/decade slope and a stable signal up to 72 h (drift = -0.2 mV/h). Analysis carried out using commercially available bottled water also demonstrated the sensor successful performance in the determination of calcium ion in real samples.

Conjugated redox polymer with poly(3,4-ethylenedioxythiophene) backbone and hydroquinone pendant groups as the solid contact in potassium-selective electrodes

The application of polyaniline nanofibers doped with chloride and nitrate ions (PANINFs-Cl and PANINFs-NO3) in potentiometry was described. Both kinds of nanofibers were used as an ion-to-electron transducer in ion-selective electrodes with solid contact (SCISEs). Extensive research on the properties of the nanofibers themselves (SEM, UV–Vis spectroscopy, FTIR) and the constructed electrodes (potentiometric methods, electrochemical impedance spectroscopy) has been carried out. Basic analytical parameters of electrodes containing various nanofibers contents in the ion-selective membrane and with nanofibers as an intermediate layer were determined. It was found that application of PANI nanofibers resulted in improvement of electrode performance (among others, better stability and reversibility of the electrode potential). The obtained sensors were characterized by a high slope of the calibration curve, a wide measuring range and a fast response time. Moreover, they were insensitive to change of redox potential, as well as light and the presence of oxygen in the solution, what is important from a practical point of view. They were also successfully used for nitrate determination in real environmental samples.

We describe a method for the quantitative determination of cyanide and sulfide ions using specific ion electrodes in combination with Conway microdiffusion cells. The response of two types of electrodes to both ions in standard solutions is presented. The method is applicable to measurement of low to toxic concentrations of both ions in biologic specimens. Five autopsy cases with history of sudden death from noxious gases were studied using this technique, and high concentrations of sulfide ion (1.70 – 3.75 mg/L) were found in the blood samples.

This paper reports the implementation of a neural processing structure as a component of an intelligent measuring system that uses ion selective electrodes (ISEs) as sensing elements of heavy metal ions (Pb/sup +2/, Cd/sup +2/) concentration. The neural network (NN), designed and implemented to reduce errors due to ion interference and to pH and temperature variations, is of the multiple-input multiple-output Multilayer Perception (MLP-NN) type The NN is a component of a virtual instrument that includes a PC laptop, a PCMCI data acquisition board with associated conditioning circuits and the specific ISE sensors. A practical approach concerning the optimal neural processing solution (number of NN structures, number of neurons, neuron transfer functions) to increase the performance of low cost ISEs is presented. Results are presented to evaluate the performance of the NN intelligent ISE system and to discuss the possibility of transferring the acquisition and processing task to a low cost acquisition and control unit such as a microcontroller.

Ionic liquids (ILs) are organic chemical compounds that are composed only of ions, a large organic cation and a smaller inorganic or organic anion. These are salts whose melting point is lower than the boiling point of water. ILs have many interesting properties, thanks to which they find great practical applications in analytics, electrochemistry, separation techniques, catalysis and others. One of the many areas of application of ionic liquids is sensors especially electrochemical sensors including ion-selective electrodes. In this case, the properties of ILs that are particularly useful include very good electrical conductivity, high electrochemical stability, good extraction properties, hydrophobic character and compatibility with other materials, e. g. polyvinyl chloride plasticizers or carbon nanomaterials. ILs were used as components of ion-selective membranes, both polymeric ones based on PVC and membranes in carbon paste electrodes. ILs performed various functions in these membranes, including lipophilic ionic additive, ionophore/ion exchanger, plasticizer, transducer media and matrix. They were also used as a component of the intermediate layer in solid contact ISEs. The last chapter presents examples of the use of ILs in reference electrodes. This review discusses the use of ionic liquids in ion-selective electrodes (ISEs) and reference electrodes over the last ten years.

To improve the single-layer all-solid-state ion selective electrode’ defects including poor conductivity of PVC sensitive membrane and interference of water layer between substrate electrode and sensitive membrane, a double-layer all-solid-state ion selective electrode with nanomaterial as the solid contact layer and conductive polymer as the ion sensitive membrane was developed. A gold nanoparticles solid contact layer and a nitrate-doped polypyrrole molecularly imprinted polymer membrane were prepared by electrodeposition. The optimal parameters obtained by electrochemical performance test were 2.5 mmol/L HAuCl4 electrolyte for solid contact layer and 1800s electrodeposition time for sensitive membrane. The new electrode exhibited a Nernstian response of -50.4 mV/decade and a low detection limit of 5.25×10-5mol/L. Potentiometric water layer test showed no water film formed between the gold nanoparticles solid contact layer and nitrate-doped polypyrrole molecularly imprinted polymer membrane. The contact angle between droplet and the surface of solid contact layer was 112.35° and showed good hydrophobic property. Furthermore, the developed electrode exhibited fast response, excellent potential stability and long lifetime. This electrode is suitable for the detection of nitrate concentration in water and liquid fertilizer.

Small-volume radial flow cell for all-solid-state ion-selective electrodes