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EN
The potentiometric response characteristics of a diclofenac selective electrode, based on ion association in different plasticizers, were compared. The sensitivity, working range, detection limit and selectivity of membrane sensors demonstrated significant dependence on the type of plasticizers. The potentiometric unit presented a linear response toward diclofenac concentrations between 1 × 10−5 − 5 × 10−2 mol L−1, with slopes of approximately 60 mV dec−1, and exhibited a response time of 3 s. The potentiometric analysis of sodium diclofenac in pharmaceutical formulations was perfomed by the membrane electrode proposed and compared with the results of potentiometric titration given by the Pharmacopoeia of Ukraine. [...]
EN
The analytical properties of an ion-selective electrode sensitive to labetalol with a liquid membrane, based on ion-pair complexes with sodium tetraphenylborate (TPB-Na+) are described. The studied electrode can be used for the determination of labetalol hydrochloride as a protonated form of labetalol in pharmaceuticals. The calibration curve, e.g. EMF=f(pCLabHCl) is linear in the range from 10−5 to 10−2 mol L−1 with a correlation coefficient of 0.9992 and slope of 61.13 mV/decade, which is close to the Nernstian slope. The detection limit of the examined electrode is 7.20×10−6 mol L−1. The influence of pH of the tested solutions on the formulation of the electrode is not as considerable since the electrode works correctly in the pH range 3.0–8.0. The main attributes of the developed electrode are: stability, good reproducibility of EMF and short response time, close to 30 seconds depending on labetalol concentration in the solution. The electrode shows good selectivity for many inorganic ions. The selectivity for drug cations is weaker due to the structural similarity of the interfering cations to labetalol. The results of labetalol determination using direct potentiometry in drugs such as Pressocard (Polpharma) and Trandate (GlaxoWellcome) were compatible with the quantity of labetalol declared by the manufacturer, and with parallel UV spectrophotometric and HPLC determinations.
EN
A potentiometric procedure for cysteine thiol group concentration monitoring in media generating free radicals was developed using a thiol specific silver-mercury electrode. Electrolytic deposition of mercury on a silver wire and treatment with 20 mM cysteine in 0.5 M NaOH were used to produce the electrode. A silver-chloride electrode in saturated KCl was the reference. A glass capillary with 1 M KNO3 in 1% agarose gel was the liquid junction. The electrode responded to cysteine concentration in the range from 0.01 to 20 mM yielding a perfect linear relationship for the dependence of log [cysteine] versus electrode potential [mV], with b0 (constant) = -373.43 [mV], b1 (slope) = -53.82 and correlation coefficient r2 = 0.97. The electrode potential change per decade of cysteine concentration was 57 mV. The minimal measurable signal response was at a cysteine concentration of 0.01 mM. The signal CV amounted to 4-6% for cysteine concentrations of 0.01 to 0.05 mM and to less than 1% for cysteine concentrations of 0.5 to 20 mM. The response time ranged from about 100 s for cysteine concentrations of 0.01 to 0.1 mM to 30 s at higher cysteine concentrations. The standard curve reproducibility was the best at cysteine concentrations from 0.1 to 20 mM. In a reaction medium containing cysteine and copper(II)-histidine complex ([His-Cu]2+) solution in 55 mM phosphate buffer pH 7.4 the electrode adequately responded to changes in cysteine concentration. Beside cysteine, the silver-mercury electrode responded also to thiol groups of homocysteine and glutathione, however, the Nernst equation slope was about half of that for cysteine.
EN
Carbon nanomaterials have been very popular in the scientific community in recent years, because of their unusual physical and chemical properties. Their high electrocatalytic activity, very good electrical conductivity and mechanical resistance mean that scientists are constantly looking for new technological solutions to take advantage of the opportunities offered by nanomaterials in many areas of human activity. One of such area are potentiometric sensors. There are many publications in which scientists describe methods of construction, analytical parameters and practical applications of new sensors obtained using carbon nanomaterials, and often also describe methods of synthesis of new original nanomaterials. The purpose of this work was to characterize carbon-based nanomaterials and their application in the construction of ion-selective electrodes.
EN
Backround: The present review focuses on electrochemical methods for antioxidant capacity and its main contributors assessment. The main reactive oxygen species, responsible for low density lipoprotein oxidation, and their reactivity are reminded. The role of antioxidants in counteracting the factors leading to oxidative stress-related degenerative diseases occurence, is then discussed. Antioxidants can scavenge free radicals, can chelate pro-oxidative metal ions, or quench singlet oxygen. When endogenous factors (uric acid, bilirubin, albumin, metallothioneins, superoxide dismutase, catalase, glutathione peroxidase, glutathione reductase, glutathione-S-transferase) cannot accomplish their protective role against reactive oxygen species, the intervention of exogenous antioxidants (vitamin C, tocopherols, flavonoids, carotenoids etc) is required, as intake from food, as nutritional supplements or as pharmaceutical products. Literature study: The main advantages of electrochemical methods with respect to traditional, more laborious instrumental techniques are described: sensitivity, rapidity, simplicity of the applied analytical procedure which does not require complicated sample pre-treatment etc. The paper reviews minutiously the voltammetric, amperometric, biamperometric, potentiometric and coulometric methods for total antioxidant capacity estimation. For each method presented, the electroactivity and the mechanism of electro-oxidation of antioxidant molecules at various electrodes, as well as the influences on the electroactive properties are discussed. The characteristics of the developed methods are viewed from the perspective of the antioxidant molecule structure influence, as well as from the importance of electrode material and/or surface groups standpoint. The antioxidant molecule-electrode surface interaction, the detection system chosen, the use of modifiers, as well as the nature of the analysed matrix are the factors discussed, which influence the performances of the studied electrochemical techniques. Conclusions: The electrochemical methods reviewed in this paper allow the successful determination of the total antioxidant capacity and of its main contributors in various media: foodstuffs and beverages, biological fluids, pharmaceuticals. The advantages and disadvantages of the electrochemical methods applied to antioxidant content and antioxidant activity assay are treated and interpreted, in the case of various analysed matrixes. Combining advanced materials with classical electrode construction, provides viable results and can constitute an alternative for the future.
EN
The electrochemical behavior of some sulpha drug-Schiff bases at a mercury electrode was examined in the Britton-Robinson universal buffer of various pH values (2.5–11.7) containing 20% v/v) of ethanol using DC-polarography, cyclic voltammetry and controlled-potential electrolysis. The DC-polarograms and cyclic voltammograms of the examined compounds exhibited a single, 2-electron, irreversible, diffusion-controlled cathodic step within the entire pH range which is attributed to the reduction of the azomethine group-CH=N- to -CH2-NH-. The symmetry transfer coefficient (α) of the electrode reaction and the diffusion coefficient (D 0) of the reactant species were determined. The electrode reaction pathway of the compounds at the mercury electrode was suggested to follow the sequence: H+, e−, e−, H+. The dissociation constant of the sulpha drug-Schiff bases, the stability constant and stoichiometry of their complexes with various divalent transition metal ions (Mn2+, Co2+, Ni2+, Cu2+ and Zn2+) were determined potentiometrically at room temperature. [...]
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