Application of ionic liquids in ion-selective electrodes and reference electrodes: A review.

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.

Effect of Modification of a Laccase-Based Electrochemical Biosensor with Carbon Nanotubes on Signal Separation of Dihydroxybenzene Isomers.

This work describes a new electrochemical biosensor for the simultaneous determination of catechol and hydroquinone. A laccase biorecognition layer was deposited using an innovative soft plasma polymerization technique onto a multiwalled carbon nanotube (MWCNT)-modified glassy carbon electrode (GCE) to sufficiently separate catechol (CT) and hydroquinone (HQ) oxidation peaks. The electrochemical analysis carried out for MWCNTs with various morphologies was supported by density functional theory (DFT) calculations showing differences in the electronic structures of both dihydroxybenzene isomers and the MWCNTs forming the biosensor interlayer. The best biosensor peak separation and biosensor analytical parameters were observed for the device containing 75 µg of MWCNTs with a higher internal diameter. For this laccase-based biosensor, a linearity range from 0.1 to 57 µM for catechol and 0.5 to 57 µM for hydroquinone as well as a sensitivity of 0.56 and 0.54 µA/µM for catechol and hydroquinone was observed, respectively. The limit of detection (LOD) values were 0.028 and 0.15 µM for CT and HQ, respectively. This biosensor was also characterized by good selectivity, stability, and reproducibility. It was successfully applied for the quantification of contaminants in the analysis of natural water samples.

Ion-Selective Electrodes with Solid Contact Based on Composite Materials: A Review.

Potentiometric sensors are the largest and most commonly used group of electrochemical sensors. Among them, ion-selective electrodes hold a prominent place. Since the end of the last century, their re-development has been observed, which is a consequence of the introduction of solid contact constructions, i.e., electrodes without an internal electrolyte solution. Research carried out in the field of potentiometric sensors primarily focuses on developing new variants of solid contact in order to obtain devices with better analytical parameters, and at the same time cheaper and easier to use, which has been made possible thanks to the achievements of material engineering. This paper presents an overview of new materials used as a solid contact in ion-selective electrodes over the past several years. These are primarily composite and hybrid materials that are a combination of carbon nanomaterials and polymers, as well as those obtained from carbon and polymer nanomaterials in combination with others, such as metal nanoparticles, metal oxides, ionic liquids and many others. Composite materials often have better mechanical, thermal, electrical, optical and chemical properties than the original components. With regard to their use in the construction of ion-selective electrodes, it is particularly important to increase the capacitance and surface area of the material, which makes them more effective in the process of charge transfer between the polymer membrane and the substrate material. This allows to obtain sensors with better analytical and operational parameters. Brief characteristics of electrodes with solid contact, their advantages and disadvantages, as well as research methods used to assess their parameters and analytical usefulness were presented. The work was divided into chapters according to the type of composite material, while the data in the table were arranged according to the type of ion. Selected basic analytical parameters of the obtained electrodes have been collected and summarized in order to better illustrate and compare the achievements that have been described till now in this field of analytical chemistry, which is potentiometry. This comprehensive review is a compendium of knowledge in the research area of functional composite materials and state-of-the-art SC-ISE construction technologies.

Cold Plasma as an Innovative Construction Method of Voltammetric Biosensor Based on Laccase.

Development of new, faster methods of biosensor construction is a huge challenge for current science and industry. In this work, biosensor construction was carried out using a new soft plasma polymerization (SPP) method in which a bio-recognition layer of laccase enzyme was polymerized and bonded to a glassy carbon electrode (GCE) substrate under atmospheric pressure with a corona discharge jet. Laccase belongs to the oxidoreductase enzyme group with four copper atoms in its active center. Application of the corona SPP plasma method allows reduction of the time needed for biosensor construction from several hours to minutes. The presented work includes optimization of the laccase bio-recognition layer deposition time, structural studies of the deposited laccase layer, as well as study of the fabricated biosensor applicability for the determination of Rutin in real pharmaceutical samples. This method produces a biosensor with two linear ranges from 0.3 µmol/dm³ to 0.5 µmol/dm³ and from 0.8 µmol/dm³ to 16 µmol/dm³ of Rutin concentration. Results shown in this work indicate that application of the one-step, corona SPP method enables biosensor construction with comparable analytical parameters to biosensors fabricated by conventional, multi-step, wet methods.

Analytical application of solid contact ion-selective electrodes for determination of copper and nitrate in various food products and drinking water.

A simple, fast and cheap method for monitoring copper and nitrate in drinking water and food products using newly developed solid contact ion-selective electrodes is proposed. Determination of copper and nitrate was performed by application of multiple standard additions technique. The reliability of the obtained results was assessed by comparing them using the anodic stripping voltammetry or spectrophotometry for the same samples. In each case, satisfactory agreement of the results was obtained, which confirms the analytical usefulness of the constructed electrodes.

A new voltammetric strategy for sensitive and selective determination of gallium using cupferron as a complexing agent.

This article describes a differential pulse adsorptive stripping voltammetric method for the trace determination of gallium in environmental water samples. It is based on the adsorptive deposition of the complex Ga(III)-cupferron at the hanging mercury drop electrode (HMDE) at -0.4 V (versus Ag/AgCl) and its cathodic stripping during the potential scan. The method was optimized as concerns the main electrochemical parameters that affect the voltammetric determination (supporting electrolyte, pH, cupferron concentration, deposition potential and time). The calibration graph is linear from 5 × 10(-10) to 5 × 10(-7) mol L(-1) with a detection limit calculated as 1.3 × 10(-10) mol L(-1) for deposition time of 30 s. The influence of interfering substances such as surfactants and humic substances present in the matrices of natural water samples on the Ga(III) signal was examined and a satisfying minimization of these interferences was proposed. The procedure was applied to direct determination of gallium in environmental water samples.

Effect of Temperature on the Removal of Interferences in the Voltammetric Procedure for the Determination of Cr(VI).

The aim of this paper was to investigate the effect of temperature on the removal efficiency of surfactant-induced interferences. Surfactants were removed as a result of mixing with XAD-7 resin. The study was carried out using the example of Cr(VI) determination by adsorption stripping voltammetry (AdSV). Measurements were carried out using a solution containing Cr(VI), acetate buffer (pH = 6.2), DTPA, KNO3, and different surfactants. Ten mL of the solution was mixed with 0.5 g of XAD-7 resin at different temperatures for 5 min prior to voltammetric measurement. The effect of the mixing temperature of the sample with the resin on the voltammetric Cr(VI) signal in the presence of different surfactants was studied in the range from 20 to 60 °C. The proposed method of removing interference from surfactants by mixing the sample with the XAD-7 resin at 60 °C was used for the determination of trace amounts of Cr(VI) in river water containing non-ionic, anionic, cationic surfactants, and biosurfactants.

New Materials Used for the Development of Anion-Selective Electrodes-A Review.

Ion-selective electrodes are a popular analytical tool useful in the analysis of cations and anions in environmental, industrial and clinical samples. This paper presents an overview of new materials used for the preparation of anion-sensitive ion-selective electrodes during the last five years. Design variants of anion-sensitive electrodes, their advantages and disadvantages as well as research methods used to assess their parameters and analytical usefulness are presented. The work is divided into chapters according to the type of ion to which the electrode is selective. Characteristics of new ionophores used as the electroactive component of ion-sensitive membranes and other materials used to achieve improvement of sensor performance (e.g., nanomaterials, composite and hybrid materials) are presented. Analytical parameters of the electrodes presented in the paper are collected in tables, which allows for easy comparison of different variants of electrodes sensitive to the same ion.

Improved Lead Sensing Using a Solid-Contact Ion-Selective Electrode with Polymeric Membrane Modified with Carbon Nanofibers and Ionic Liquid Nanocomposite.

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 E0 or slope values. It was used to analyze a real sample and correct results of lead content determination were obtained.

An Electrochemical Sensor for the Determination of Trace Concentrations of Cadmium, Based on Spherical Glassy Carbon and Nanotubes.

The practical application of a novel, eco-friendly electrochemical sensor based on low-dimensional structures, spherical glassy carbon microparticles, and multiwall carbon nanotubes is described. This sensor, modified with a bismuth film, was used for the determination of Cd(II) by the anodic stripping voltammetric method. The instrumental and chemical factors influencing the sensitivity of the procedure were thoroughly investigated and their most favorable values were selected (acetate buffer solution pH = 3 ± 0.1; 0.15 mmol L-1 Bi(III); activation potential/time: -2 V/3 s; accumulation potential/time: -0.9 V/50 s). Under the selected conditions, the method exhibited linearity in the range of 2 × 10-9 to 2 × 10-7 mol L-1 Cd(II) with a detection limit of 6.2 × 10-10 mol L-1 Cd(II). The results obtained also showed that the application of the sensor for Cd(II) detection did not experience any significant interference in the presence of a number of foreign ions. The applicability of this procedure was evaluated using TM-25.5 Environmental Matrix Reference Material and SPS-WW1 Waste Water Certified Reference Material as well as river water samples through addition and recovery tests.

Application of Metal Oxide Nanoparticles in the Field of Potentiometric Sensors: A Review.

Recently, there has been rapid development of electrochemical sensors, and there have been numerous reports in the literature that describe new constructions with improved performance parameters. Undoubtedly, this is due to the fact that those sensors are characterized by very good analytical parameters, and at the same time, they are cheap and easy to use, which distinguishes them from other analytical tools. One of the trends observed in their development is the search for new functional materials. This review focuses on potentiometric sensors designed with the use of various metal oxides. Metal oxides, because of their remarkable properties including high electrical capacity and mixed ion-electron conductivity, have found applications as both sensing layers (e.g., of screen-printing pH sensors) or solid-contact layers and paste components in solid-contact and paste-ion-selective electrodes. All the mentioned applications of metal oxides are described in the scope of the paper. This paper presents a survey on the use of metal oxides in the field of the potentiometry method as both single-component layers and as a component of hybrid materials. Metal oxides are allowed to obtain potentiometric sensors of all-solid-state construction characterized by remarkable analytical parameters. These new types of sensors exhibit properties that are competitive with those of the commonly used conventional electrodes. Different construction solutions and various metal oxides were compared in the scope of this review based on their analytical parameters.

Chloride Ion-Selective Electrode with Solid-Contact Based on Polyaniline Nanofibers and Multiwalled Carbon Nanotubes Nanocomposite.

Use of the nanocomposite of chloride-doped polyaniline nanofibers and multiwalled carbon nanotubes (PANINFs-Cl:MWCNTs) for construction of ion-selective electrodes with solid-contact sensitive to chloride ions has been described. Many types of electrodes were tested, differing in the quantitative and qualitative composition of the layer placed between the electrode material and the ion-selective membrane. Initial tests were carried out, including tests of electrical properties of intermediate solid-contact layers. The obtained ion-selective electrodes had a theoretical slope of the electrode characteristic curve (-61.3 mV dec-1), a wide range of linearity (5 × 10-6-1 × 10-1 mol L-1) and good potential stability resistant to changing measurement conditions (redox potential, light, oxygen). The chloride contents in the tap, mineral and river water samples were successfully determined using the electrodes.

Hierarchical Nanocomposites Electrospun Carbon NanoFibers/Carbon Nanotubes as a Structural Element of Potentiometric Sensors.

This work proposes new carbon materials for intermediate layers in solid-contact electrodes sensitive for potassium ions. The group of tested materials includes electrospun carbon nanofibers, electrospun carbon nanofibers with incorporated cobalt nanoparticles and hierarchical nanocomposites composed of carbon nanotubes deposited on nanofibers with different metal nanoparticles (cobalt or nickel) and nanotube density (high or low). Materials were characterized using scanning electron microscopy and contact angle microscopy. Electrical parameters of ready-to-use electrodes were characterized using chronopotentiometry and electrochemical impedance spectroscopy. The best results were obtained for potassium electrodes with carbon nanofibers with nickel-cobalt nanoparticles and high density of nanotubes layer: the highest capacity value (330 µF), the lowest detection limit (10-6.3 M), the widest linear range (10-6-10-1) and the best reproducibility of normal potential (0.9 mV). On the other hand the best potential reversibility, the lowest potential drift (20 µV·h-1) in the long-term test and the best hydrophobicity (contact angle 168°) were obtained for electrode with carbon nanofibers with cobalt nanoparticles and high density of carbon nanotubes. The proposed electrodes can be used successfully in potassium analysis of real samples as shown in the example of tomato juices.

Metal oxide nanoparticles as solid contact in ion-selective electrodes sensitive to potassium ions.

In recent years, various types of nanomaterials and nanoparticles have been very popular, also in analytical chemistry for sensors preparation. Ion-selective electrodes with solid contact were constructed, in which a layer of nanoparticles of selected metal oxides (zinc, copper and iron oxides) obtained by pulsed laser liquid ablation (PLAL) was placed between the glassy carbon solid electrode material and the ion-selective membrane. The basic analytical parameters of the obtained sensors were determined using potentiometric methods. Additionally, the electrochemical impedance spectroscopy method (EIS) was also used to investigate the electrical properties of the sensors. The obtained results were compared for all types of electrodes, both modified and unmodified, in order to investigate the effect of the type of nanoparticles and the thickness of their layer used as solid contact. It was found that the addition of metal oxide nanoparticles improved the analytical parameters of the sensors, mainly the potential stability and electrical parameters. The best results were obtained for an electrode with an intermediate layer of zinc oxide nanoparticles. In this case, a slope of -56.07 mV/dec, a linearity range of 1 × 10-5 - 1 × 10-1 mol L-1 and a limit of detection of 3.66 × 10-6 mol L-1 were obtained. Particularly noteworthy is the significant improvement in the stability of the potential of this electrode and the long life of more than 5 months.

Application of cold plasma corona discharge in preparation of laccase-based biosensors for dopamine determination.

Laccase-based biosensors were successfully prepared using innovative, cheap, one-step Soft Plasma Polymerization technique by deposition of a bio-recognition layer on glassy carbon electrode and MWCNT (Multi-walled Carbon Nanotubes)-modified glassy carbon electrode. The Soft Plasma Polymerization technique is based on corona discharge of cold atmospheric plasma with close to room temperature. The presented work includes study of biosensor working conditions, optimization of the voltage value applied for corona discharge generation as well as applicability and interference studies for dopamine determination. The biosensor constructed under optimal conditions (corona discharge generated at a voltage of 3 kV and in 30 s time deposition, helium flow rate 10 L/min, laccase solution flow rate 200 µL/min) has two linear ranges from 0.1 µmol/dm3 to 10 µmol/dm3 and from 10 µmol/dm3 to 50 µmol/dm3 with dopamine detection sensitivities of 3.63 µA*dm3/µmol and 1.33 µA*dm3/µmol. Application of the MWCNT interlayer allows the dopamine detection sensitivity to be significantly increased to 22.35 µA* dm3/µmol for a linear range from 0.1 µmol/dm3 to 6 µmol/dm3. Additionally, the studied biosensors have stable and anti-interference ability. Both biosensors were successfully applied for dopamine determination in pharmaceutical preparation.

Ketoprofen ion-selective electrode and its application to pharmaceutical analysis.

The composition of a polymeric potential-determining phase for ketoprofen selective electrode has been determined and the following basic electrode parameters were examined: measurement range, slope characteristic, limit of detection, response time, lifetime and selectivity coefficients in relation to some organic and inorganic anions. The electrode have been used for ketoprofen determination in the range 25.43-25430 microg/mL.

Naproxen ion-selective electrode and its application to pharmaceutical analysis.

An ion-selective membrane electrode was prepared based on ion-pair complex of naproxen with methyltrioctylammonium. Its basic analytical parameters such as: slope characteristics, measuring range, detection limit, response time, life time were determined. The electrode showed Nernstian response from the 10(-1) to 10(-4) mol l(-1) concentration range and 5.5-8.5 pH range, low limit of detection 5 x 10(-5) mol l(-1) and short response time--20s. Selectivity was good over a number of organic and inorganic anions. The electrode was applied for the determination of naproxen tablets in aqueous solutions by the calibration curve method and standard addition method.

A highly selective lead-sensitive electrode with solid contact based on ionic liquid.

A new polyvinylchloride membrane sensor for Pb(2+) with solid contact based on ionic liquid has been prepared. The electrode shows a Nernstian response for lead ions over a wide concentration range (1×10(-8) to 1×10(-1) mol L(-1)) and the slope of 29.8 mV/decade. The limit of detection is 4.3×10(-9) mol L(-1). It has a fast response time of 5-7 s and can be used for 4 months without any divergence in potential. The proposed sensor is not pH sensitive in the range 3.5-7.3 and shows a very good discriminating ability towards Pb(2+) ion in comparison with some alkali, alkaline earth, transition and heavy metal ions. It was successfully applied as an indicator electrode in potentiometric titration of lead ions with K(2)CrO(4) and for direct determination of Pb(2+) ions in real sample solution.