A mechanistic evaluation of the amperometric response of reduced thiols in quinone mediated systems

The specificity of the reaction of benzoquinone with reduced thiol species has been investigated and the nature of the amperometric electrode response elucidated. The analytical applicability of the methodology has been assessed and it has been shown that through appropriate selection of the redox properties of the indicating quinone, interference from other electroactive species can be minimised. A discrepancy in the reaction stoichiometry has however been found between the glutathione and cysteine quinone adducts and the implications in interpreting the resulting sensor response are rationalised. The adaptation of the approach to disposable, screen printed electrode assemblies has been investigated.     

Fabrication of Potentiometric Sensors for the Selective Determination of Ketoconazole

Abstract

The fabrication and analytical applications of two types of potentiometric sensors for the determination of ketoconazole (KET) are described. The sensors are based on the use of KET-molybdophosphoric acid (MPA) ion pair as electroactive material. The fabricated sensors include both polymer membrane and carbon paste electrodes. Both sensors showed a linear, stable and near Nernstian slope of 57.8 mV/decade and 55.2 mV/decade for PVC membrane and carbon paste sensors respectively over a relatively wide range of KET concentration (1 × 10^?2 ? 5 × 10^?5and 1 × 10^?2 ? 1 × 10^?6). The sensors showed a fast response time of < 30 sec and < 45 sec. A useful pH range of 3–6 was obtained for both types of sensors. A detection limit of 2.96 × 10^?5M was obtained for PVC membrane sensor and 6.91 × 10^?6 M was obtained for carbon paste sensor. The proposed sensors proved to have a good selectivity for KET with respect to a large number of ions. The proposed sensors were successfully applied for the determination of KET in pharmaceutical formulations. The results obtained are in good agreement with the values obtained by the standard method.     

Antioxidant Activity Evaluation Assay Based on Peroxide Radicals Generation and Potentiometric Measurement

A new version of potentiometric evaluation of antioxidant activity in biological liquids, food, drinks, and so forth, based on the mediator system combined with the free radicals generation has been proposed. A radical initiator, 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH), and K₃[Fe(CN)₆]/K₄[Fe(CN)₆] as a mediator system were used. Interactions of the mediator system with radicals, radicals with antioxidants, and erythrocytes have been investigated. The correlation coefficient between the data obtained in the presence and the absence of AAPH equals 0.98. In addition, the possibility to determine a free radical generation rate by using the mediator system has been demonstrated.     

离子选择性电极电位法测定钼矿石和钨矿石中氟

采用过氧化钠熔融钼矿石、钨矿石样品,乙二胺四乙酸钠和5-磺基水杨酸混合溶液浸取盐分,将样品溶液静置12h,吸取上层清液,以乙二胺四乙酸钠-硝酸钾组成的混合溶液作为总离子强度缓冲剂,控制溶液pH值为5.1,使用pF-1型氟离子选择电极,以饱和甘汞电极作参比电极测定溶液的平衡电位值。采用标准曲线法测定钼矿石和钨矿石中氟。钼矿石标准物质测定值的相对标准偏差(n=11)为3.36%,经4种国家一级钼矿石、钨矿石标准物质的分析验证,测定结果与标准值吻合。     

Potentiometric Study of the Growth of a Single Au Nanoparticle

A single nanoparticle (NP) attached to a nanoelectrode is a very useful system in understanding the relationship between the size of nanoparticles and their electrochemical properties. In this study, a single Au NP was spontaneously formed on a Pt nanoelectrode. The potential measured on such a system can be employed to study the effect of size of an Au nanoparticle on the Nernst potential of the reaction, AuCl₄⁻ +3e → Au(s) +4Cl⁻. Moreover, the nucleation period and the growth period can be distinguished from the potential graph, and the nucleation rate of the spontaneously formed Au NP can be evaluated.     

Construction and Performance Characterization of Ion‐Selective Electrodes for Potentiometric Determination of Paroxetine Hydrochloride in Pharmaceutical Preparations and Biological Fluids

Three types of ion‐selective electrodes: PVC membrane, modified carbon paste (CPE), and coated graphite electrodes (CGE) have been constructed for determining paroxetine hydrochloride (Prx). The electrodes are based on the ion pair of paroxetine with sodium tetraphenylborate (NaTPB) using dibutyl phthalate as plasticizing solvent. Fast, stable and potentiometric response was obtained over the concentration range of 1.1×10^?5–1×10^?2 mol L^?1 with low detection limit of 6.9×10^?6 mol L^?1 and slope of a 56.7±0.3mV decade^?1 for PVC membrane electrode, the concentration range of 2×10^?5–1×10^?2 mol L^?1 with low detection limit of 1.2×10^?5 mol L^?1 and slope of a 57.7±0.6 mV decade^?1 for CPE, and the concentration range of 2×10^?5–1×10^?2 mol L^?1 with low detection limit of 8.9×10^?6 mol L^?1 and slope of a 56.1±0.1 mV decade^?1 for CGE. The proposed electrodes display good selectivity for paroxetine with respect to a number of common inorganic and organic species. The electrodes were successfully applied to the potentiometric determination of paroxetine hydrochloride in its pure state, its pharmaceutical preparation, human urine and plasma.     

Simultaneous Electroanalysis of Hypochlorite and H2O2: Use of I−/I2 as a Probing Potential Buffer

Sodium hypochlorite (NaClO) and hydrogen peroxide (H₂O₂) have been simultaneously analyzed, for the first time, using a simple and rapid potentiometric method. The present method shows a high sensitivity, selectivity and satisfactory reproducibility. Pt electrode was used as an indicator electrode and the I₂/I^? redox couple was used as a probing potential buffer. The large difference in the rates of the oxidation of I^? by the two oxidizing agents, that is, the oxidation of I^? by NaClO is by several orders of magnitude faster than that by H₂O₂, enabled the selective analysis of these two species. Based on such a large difference in the rates, a momentary potential response corresponding to the oxidation of I^? by NaClO and another quite slow one by H₂O₂ could be obtained. Factors affecting the selectivity as well as the sensitivity, such as the concentrations of molybdate (used as catalyst for the oxidation of I^? by H₂O₂), H⁺, I₂, and I^? in the potential buffer were examined. The expected Nernstian responses were obtained over a considerable range of the concentrations of the two oxidizing agents with slopes of 30.5 and 29.9 mV for NaClO and H₂O₂, respectively (in a close agreement with the theoretical value, that is, 29.6 mV) and with a detection limit in the submicromolar range (0.2 μM).     

Screening of Synthetic Cathinones by Potentiometric Sensor Array and Chemometrics

This work demonstrates the analytical applicability of single ion-selective membranes (ISMs) and potentiometric sensor array to distinguish and detect cathinone derivatives. Potentiometric data from ISMs based on cation exchanger and varying content of calix[4]arene derivative were processed by principal component analysis (PCA). Such a combination of methods allowed discriminating various individual synthetic cathinones and their recognition from the mixture comprising primary amines (substituted amphetamines+aminoindane). Analytical parameters of ISM containing 1wt % of calix[4]arene derivative were sufficient to detect 1.0×10⁻⁴ mol.l⁻¹ 1-(4-fluorophenyl)-2-(ethylamino)butan-1-one and 2-(methylamino)-1-phenylbutan-1-one (buphedrone) in both model and saliva samples.     

Potentiometric and spectrophotometric determination of the dissociation constants of cefetamet

Summary The dissociation constants of cefetamet-Na have been determined using potentiometric titrations and spectrophotometry. The investigations were carried on in water solutions at constant temperature and ionic strength, and at differentH ₀ andpH values. Potentiometric investigations were performed at three different temperatures and ionic strengths. The concentration dissociation constants and the corresponding thermodynamic dissociation constants were calculated by a computer program. The mixed dissociation constants (pK) of cefetamet-Na have been determined spectrophotometrically in theH ₀ range from -5.80 to 0.00 and atpH values from 0.00 to 12.70 and are in good agreement with values achieved by graphical methods as well as with those obtained by potentiometric methods. Based on the determined values, the thermodynamic parameters (G, H, S) were calculated atI=0.1M.

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Potentiometrische und spektrophotometrische Bestimmung der Dissoziationskonstanten von Cefetamet

Zusammenfassung Die Dissoziationskonstanten von Cefetamet-Na wurden mittels potentiometrischer Titrationen und auf spektrophotometrischem Weg bestimmt. Die Untersuchungen wurden in wäßriger Lösung bei konstanter Temperatur und Ionenstärke und verschiedenenH ₀- undpH-Werten durchgeführt. Potentiometrische Messungen wurden bei drei verschiedenen Temperaturen und Ionenstärken vorgenommen. Die stöchiometrische Dissozation und die entsprechenden thermodynamischen Dissoziationskonstanten wurden mit Hilfe eines Computerprogramms berechnet. Die gemischten Dissoziationskonstanten (pK) wurden spektrophotometrisch imH ₀-Bereich von -5.80 bis 0.00 und impH-Bereich von 0.00 bis 12.70 bestimmt und stimmen sowohl mit Werten, die mit Hilfe der graphischen Methode erhalten wurden, als auch mit potentiometrisch bestimmten gut überein. Aus den ermittelten Werten der Dissoziationskonstanten wurden die thermodynamischen Parameter (G, H, S) fürI=0.1M berechnet.

     

Determination of inorganic phosphate by electroanalytical methods: A review

Determination of inorganic phosphate is of very high importance in environmental and health care applications. Hence knowledge of suitable analytical techniques available for phosphate sensing for different applications becomes essential. Electrochemical methods for determining inorganic phosphate have several advantages over other common techniques, including detection selectivity, stability and relative environmental insensitivity of electroactive labels. The different electrochemical sensing strategies adopted for the determination of phosphate using selective ionophores are discussed in this review. The various sensing strategies are classified based on the electrochemical detection techniques used viz., potentiometry, voltammetry, amperometry, unconventional electrochemical methods etc., The enzymatic sensing of phosphate coupled with electrochemical detection is also included. Various electroanalytical methods available in the literature are assessed for their merits in terms of selectivity, simplicity, miniaturisation, adaptability and suitability for field measurements.     

Potentiometric detection of polyions based on functionalized magnetic nanoparticles

A novel potentiometric detection strategy based on functionalized magnetic nanoparticles has been developed for rapid and sensitive sensing of polyions. Highly dispersed magnetic nanoparticles coated with ion exchanger and plasticizer could promote an in situ cooperative ion-pairing interaction between the ion exchanger and the polyion analyte in sample solution by dramatically reducing the mass-transfer distance. With applying a magnetic field, the nanoparticles can be attached to the surface of ion exchanger free polymeric membrane. The observed potential signals are related to the polyion concentrations. The proposed polymeric membrane electrode exhibits a linear relationship between the greatest potential response slope (dE/dt) and the logarithm of protamine concentration in the range of 0.05−5 μg/mL with a lower detection limit of 0.033 μg/mL.     

Preparation of Iodide Selective Carbon Paste Electrode with Modified Carbon Nanotubes by Potentiometric Method and Effect of CuS‐NPs on Its Response

In this research, multiwalled carbon nanotubes (MWCNTs) was oxidized and chemically modified through reaction with 3‐(trimethoxysilyl)propan‐1‐amine (TMSPA) and their subsequent reaction with 2‐hydroxy‐3‐methoxy benzaldehyde. Subsequently, this material was metalized by reaction with copper acetate that lead to formation and impergeation of 2‐methoxy‐6‐((3‐(trimethoxysilyl)propylimino)methyl)phenol MMSPIMP? MWCNT‐Cu. This novel material was identified with different techniques such as SEM and FT‐IR analysis. In this work, the reported material are exhibited high accurate and repeatable monitoring of iodide due to its high surface area with various reactive centre. It exhibited selectivity for iodide over the wide linear dynamic range between 1.8×10^?6 and 1.15×10^?1 M, with a Nernstian slope of ?59.12±0.7 mV per decade of activity and detection limit of 1.8×10^?6 M. Copper sulfide nanoparticles were prepared and their effect on the electrode response was investigated. The results were improved in the presence of nanoparticles with fast and stable response, good reproducibility, long‐term stability, high selectivity over the presence of common organic and inorganic anions, high detection limit and dynamic range. The proposed sensor has been applied as potentiometric determination of some iodine species over a pH range of 2.5–10.     

Potentiometric detection of citrate in beverages using a graphite carbon electrode

The development, evaluation and application of a simple and low-cost graphite carbon electrode for the direct determination of citrate in food samples are described here. The electrode exhibits a linear response with a slope of −29.0 ± 1.0 mV decade⁻¹ in a concentration range of 0.07-7.0 mmol L⁻¹ in 0.1 mol L⁻¹ KCl/1.0 mmol L⁻¹ phosphate buffer solution with a limit of detection of 3.0 μmol L⁻¹. The electrode is easily constructed at a relatively low cost and has a fast time response (within 120 s) with no significant changes in its performance characteristics. The performance of the graphite sensor was tested to determine citrate in beverage samples (juices and an isotonic drink), and the results were validated against a reference procedure. The proposed method is quick, inexpensive, selective and sensitive, and is based entirely on conventional instrumentation.     

Unbiased Selectivity Coefficients of Potentiometric Sensors Using Thin Membrane Layers

Solid-contact ion-selective electrodes with thin membranes can more easily achieve complete ion exchange at the sample-membrane interface, giving unbiased selectivity coefficients. The calculated reconditioning rate corresponds well to experimental data. Alternatively, the redox state of the conducting polymer may be electrochemically switched resulting in primary ion expulsion from the membrane and interfering ion uptake from the sample. Both approaches were tested for tetrabutylammonium-selective electrodes. The approach's limitations are identified, which includes primary ions impurities in interfering ion salts and an interaction between primary ion and redox polymer. These limitations are visualized with ionophore-based sodium- and silver-selective electrodes.     

Potentiometric detection of organic acids in ion-exclusion chromatography using different types of liquid-membrane electrodes

Four different liquid-membrane electrodes were tested in a potentiometric flow-cell, in combination with an LC ion chromatography system (Aminex HPX-87H column). This setup was used for the determination of weak organic acids. The flow-through detector was of the wall-jet type. Conditions were established to achieve the best separation and detection characteristics. The sensitivity, selectivity and response time of the different electrodes were compared. Calibration curves and detection limits were measured for several organic acids, and compared with conductometric, and with low-wavelength UV detection. The detection limits were improved by inserting a post-column ion-suppressor system between the column and the detector. Several biological samples were analyzed to demonstrate the possibilities of the potentiometric detector.     

Potentiometric Determination of the Dissociation Constants of Glycylglycine in Various Aquo-Organic Media

The dissociation constant values of glycylglycine were determined at 25 ± 0.1 °C (I = 0.1 mol L^?1 KNO₃) with Potentiometric pH titration in pure water and various mixture of water and organic solvents. The organic solvents used were methanol, ethanol, N, N-dimethylformamide, dimethylsulfoxide, acetonitrile and dioxane. Initial estimates of the dissociation constants of glycylglycine were refined with ESAP2M computer program. The results obtained are discussed in terms of average macroscopic properties of the mixed solvents and the possible variation in microheterogeneity of the solvation shells around the solute.     

Potentiometric sensor for sensitive and selective detection of heparin

A polymeric membrane ion-selective electrode for determination of heparin is described in this paper.Protamine is incorporated into the organic membrane phase and functions as sensing element for selective recognition of heparin.The proposed membrane electrode exhibits high selectivity for heparin over lipophilic anions such as thiocyanide and salicylate.The potentiometric response to the concentration of heparin is Unear in the range of 0.01-0.4 U/mL and a lower detection limit of 0.005 U/mL can be achieved.     

Comparison of the Effects of Biofouling on Voltammetric and Potentiometric Measurements

Biofouling of sensors is a common problem when measuring biological samples. The adherence of proteins and biomolecules, called hemostasis, is the first of four steps that lead to biofouling and eventually a foreign body response. This typically occurs within the first hours after the exposure of the biosensor to a biological sample. The purpose of this study was to assess the effect of this initial step of biofouling on cyclic voltammetry and potentiometric measurements. The results show that biofouling occurred rapidly within minutes and strongly affected cyclic voltammetry measurements, while potentiometric measurements were minimally affected even after 24 hours.     

Polyaniline‐Based Sensor Material for Potentiometric Determination of Ascorbic Acid

Polyaniline (PANI)‐based sensor material for determination of ascorbic acid was synthesized by oxidative chemical polymerization of aniline on a screen‐printed carbon‐paste electrode. The influence of PANI chemical structure formed under various polymerization conditions on the sensor response was investigated. The presence of aniline dimer derivatives in PANI structure was found to induce significant improvement of the limit of detection and the linear dynamic range without a change in sensitivity. The sensor prepared by aniline polymerization in pH 7 buffer leading to the product containing mainly the aniline dimer‐based units showed the best detection limit of 0.1 µM. It was shown that the PANI‐based sensor could be used for ascorbic acid analysis in the presence of citrate and lactate as interfering ions. A quantitative determination of ascorbic acid concentration in beverages and vitamins was performed.