Development of a long-term stable organic membrane-based thin-film microsensor using new-type substrate surface treatment

A novel long lifetime organic membrane-based thin-film Cu(II) microsensor has been elaborated. The advantages of the suggested microsensor include: excellent stability, long lifetime, and reasonable good selectivity. The significant improvements of the lifetime (>4 months) of the organic membrane-based thin-film microsensors have been realized for the first time using new-type electrodeposition treatment of the solid-state substrate surface in combination with a new nebulization method for applying the organic membrane coating mixture on the thin-film gold substrate. The electrochemical behavior of the thin-film microsensor in terms of ionic sensitivity, limit of detection, the effect of the pH, dynamic response time, Nernstian response interval, selectivity coefficients and lifetime has been evaluated. The results are compared to those obtained with the conventional ion-selective and coated graphite rod macroelectrodes prepared with the same ionophore. The reliability of the suggested thin-film microsensor with the low cost of its microfabrication makes it promising for the miniaturized application.     

Dissolution Testing and Potentiometric Assay of Sertraline Hydrochloride in Batch and FIA Conditions

An electrochemical polyvinyl chloride membrane sensor for sertraline (Ser) was prepared based on the ion associate of sertraline with phosphotungstic acid. The sensor was fully characterized in terms of its membrane composition, life span, effect of soaking, pH, interferences, and temperature and exhibited an average Nernestian response (61.6 ± 0.9 mV/decade) in the concentration range of 1.0 × 10^?2 –5.0 × 10^?5 M. Sertraline was assayed potentiometrically in its pure solutions and pharmaceutical preparations using the developed electrode under batch and flow injection conditions and the recovery values ranged from 93.44–101.12%, with a relative standard deviation of 0.53–1.27%.

The sensor was successfully applied to the determination of the dissolution profile study of (Ser) tablets and the results were validated by comparison with spectrophotometric assays according to the quality control unit of the tablets pharmaceutical company producers. The results obtained from the proposed electrode were statistically analyzed and compared to a reported method. No significant difference was observed regarding both accuracy and precision.     

Novel Sensors for Batch and Flow Injection Analysis of Histamine Based on Crown Ethers

Six types of histamine potentiometric sensors are developed. They are based on using dibenzo‐30‐crown‐10 (DB30C10) with potassium tetrakis(p‐chlorophenyl)borate lipophilic additive (Type I), dibenzo‐30‐crown‐10 without additive (Type II), dibenzo‐24‐crown‐8 (DB24C8) with the same additive (Type III), dibenzo‐24‐crown‐8 without additive (Type IV), dibenzo‐18‐crown‐6 with the additive (Type V) and dibenzo‐18‐crown‐6 without additive (Type VI) as neutral carriers for histamine. Sensors based on dibenzo‐30‐crown‐10 with (PTp‐C1PB) lipophilic additive (Type I) and dibenzo‐30‐crown‐10 without additive (Type II) show good response. The other sensors Types III–VI show poor response in terms of calibration range and slope.     

Application of a new potentiometric method for determination of phosphate based on a surfactant-modified zeolite carbon-paste electrode (SMZ-CPE)

A phosphate-selective electrode based on surfactant-modified zeolite (SMZ) particles into carbon-paste has been proposed (SMZ-CPE). The electrode was fully characterized in terms of composition, response time, ionic strength, thermal stability and usable pH range. The electrode containing 20% SMZ exhibited linear response range to phosphate species in the range of 1.58 × 10⁻⁵ to 1.00 × 10⁻² M with a detection limit of 1.28 × 10⁻⁵ M and a Nernstian slope of 29.9 ± 0.9 mV per decade of phosphate concentration. The electrode response to phosphate remains constant in the pH range of 4-12 and in the presence of 1 × 10⁻⁴ to 4 × 10⁻³ M NaNO₃. The response of the electrode reaches equilibrium within several seconds after immersing the electrode in phosphate solution. Common anions such as Cl⁻, Br⁻, I⁻, NO₃⁻, SO₄²⁻ and Cr₂O₇²⁻ have little effect on the determination of phosphate but AsO₄³⁻ shows some interference. A successful application of the electrode for determination of phosphate in a fertilizer, using direct potentiometry, is presented. The electrode was also used for the potentiometric titration of phosphate. The validation of the obtained results in each case was proved by statistical methods.     

A novel uranyl membrane sensor with potentiometric anionic response

A novel potentiometric uranyl membrane sensor with a divalent anionic response is developed, characterized and used for determination of uranyl ion. The sensor incorporates triethylenetetramine (TETA) as an ionophore in poly(vinyl chloride) matrix membrane (PVC) plasticized with o-nitrophenyloctyl ether (o-NPOE). In strong sulphate test solutions, UO₂²⁺ ion forms a highly stable [UO₂(SO₄)₂]²⁻ anion, extractable in TETA as {(2TETAH)²⁺ [UO₂(SO₄)₂]²⁻} complex. Formation of the complex is confirmed and characterized by elemental analysis, mass spectrometry and infrared spectrometry. Sensor based on this system displays at pH 2.5-3.8 a linear response over the concentration range of 1.0 × 10⁻¹-3.5 × 10⁻⁵ mol l⁻¹ uranium with a near-Nernstian calibration slope of −26.5 ± 0.3 mV decade⁻¹. The lower limit of detection is ∼5 μg ml⁻¹, the lifetime is 12 weeks and negligible interferences are caused by most common cations. Validation of the assay method reveals excellent performance characteristics in terms of sensitivity, selectivity, fast response and potential stability. The sensor is used for the determination of 0.01-7.09 wt% uranium in naturally occurring and certified ore samples. The results show an average recovery of 97.6% and compare fairly well with data obtained using X-ray fluorescence technique.     

Flow injection potentiometric determination of clobutinol hydrochloride

New clobutinol (Clob) ion-selective polyvinyl chloride (PVC) membrane electrodes, based on the ion-associates of Clob with phosphotungstic acid or phosphomolybdic acid were prepared using dibutyl phthalate as plasticizing solvent. The electrodes were characterized in terms of membrane composition, temperature and pH. The sensors showed a near-Nernstian response over the concentration ranges (6.31 × 10⁻⁶)-(1.00 × 10⁻²) and (5.01 × 10⁻⁵)-(1.00 × 10⁻²) M in the case of clobutinol-phosphotungstate ((Clob)₃-PT) applying batch and flow injection (FI) analysis, respectively, and (1.58 × 10⁻⁵)-(1.00 × 10⁻²) and (5.01 × 10⁻⁵)-(1.00 × 10⁻²) M in case of clobutinol-phosphomolybdate ((Clob)₃-PM) for batch and FI analysis systems, respectively. The electrodes were successfully applied for the potentiometric determination of ClobCl in pharmaceutical preparation and urine in steady state and flow injection conditions. The electrodes exhibit good selectivity for Clob with respect to a large number of inorganic cations, sugars and amino acids.     

Cation-Coordinating Properties of Perfluoro-15-Crown-5

The coordinative properties of perfluoro-15-crown-5 with monocations were investigated using ¹⁹F NMR spectroscopy and ion-selective electrodes with perfluoro-15-crown-5 as the matrix of their sensor membranes and the fluorophilic tetrakis[3,5-bis(perfluorohexyl)phenyl]borate as ion exchanger site. The results show that perfluoro-15-crown-5 interacts weakly but significantly with Na⁺ and K⁺. Assuming 1:1 stoichiometry, the formal complexation constants were determined to be 5.5 and 1.7 M⁻¹, respectively. This weak binding is consistent with the strong electron withdrawing nature of the many fluorine atoms in the perfluorocrown ether. While perfluorinated crown ethers have been known to form host-guest complexes with the anions O₂⁻ and F⁻ in the gas-phase, this is the first study that quantitatively confirms cation binding to a perfluorocrown ether.     

Single interface flow system with potentiometric detection for the determination of nitrate in water and vegetables

In this work a single interface flow system (SIFA) with potentiometric detection was for the first time implemented and applied to the determination of nitrate in waters and plant extracts. The analytical potential of the SIFA system was exploited not only to transport the sample towards detection but also to carry out, in a reproducible and automated way, the tasks associated with sample pre-treatment, namely ionic strength, pH adjustment and interfering species suppression. The advantageous aspects of combining a SIFA system with potentiometry with enhanced simplicity, ease of implementation and automation were further discussed and emphasised.The obtained results showed relative deviations lower than 5%, for both types of samples, with sampling rates of about 40 h⁻¹.In addition, an innovative and straightforward process for constructing plastic membrane ion selective electrodes with a tubular configuration able to be coupled to flow-based analytical systems is also proposed. The developed approach, consisting of assembling the electrode inside a flow tubing connector is very simple to implement, robust, particularly adequate to be combined with flow methodologies and maintains all dynamic and analytical characteristics exhibited by previous assembling processes.     

Tetracycline Sensitive Membrane Electrodes Based on Poly (Vinyl Chloride) Matrices and their use in Drug Analysis

ABSTRACT

Tetracycline hydrochloride-selective electrodes of both the coated wire and the conventional polymer membrane types have been prepared. They are based on incorporating the tetracycline-phosphotungstate ion-associate in plasticized poly(vinyl chloride) film. A Nernstian response is shown by these electrodes within certain concentration ranges depending on the type of electrode. The effect of pH of the test solution and time of soaking on the electrodes' performance are studied. The electrodes are highly selective for tetracycline with respect to several inorganic cations, sugars and some amino-acids of significant importance in biological fluids and pharmaceutical preparations. The standard cell potentials, E°, were determined at different temperatures and used to calculate the isothermal temperature coefficient of the cell. Tetracycline is determined successfully in pure solutions and in pharmaceutical preparation using the standard additions method and potentiometric titration.     

Potentiometric measurement of ionic, acid-labile and covalently bound fluorine

Fluoride (F⁻) is the predominant chemical form of F in serum and bone, during administration of NaF as cariostatic agent or in the treatment of osteoporosis. In the treatment with sodium monofluorophosphate (MFP), F⁻, F bound to proteins by acid-labile linkage and non-volatile covalently bound F are detected. Only F⁻ is detectable with the ion-selective electrode. This paper describes a method for the measurement of non-volatile covalently bound F with the ion-selective electrode, which has a detection limit of 0.8 ± 0.6 nmol, within-run standard deviation of 7 nmol and a between-run standard deviation of 13 nmol at 100 nmol F and has a linear behaviour above 1 nmol. This paper also reports a methodology for the potentiometric measurement of F⁻, acid-labile F and covalently bound F in biological samples.