Evaluation of measuring range and interferences for gas-sensing potentiometric probes

The experimental limit of detection and the interferences for any assembled gas sensor are the analytical features of greatest interest. Theoretical and practical studies of CO₂ and SO₂ gas sensors are reported. In the measurement of CO₂, the sample should not be buffered at too acidic a value, although the rate of diffusion at e.g. pH 6.8, may be slower than at low pH. Choice of sample pH can also be used to limit interfering effects. The conditions must be selected on the basis of the required rate of analysis and the selectivity attainable.     

Flow injection potentiometric determination of paraquat in formulations and biological samples

A flow injection potentiometric method for the rapid determination of paraquat in herbicide formulations and biological samples is described. It is based on the utilization of a flow-through potentiometric detector containing polyvinyl chloride-immobilised octamethylcyclotetrasiloxane, a lipophilic plasticizer (tetra-n-undecyl 3,3′,4,4′-benzophenone tetracarboxylate) and membrane additive potassium tetrakis(4-chlorophenyl)borate. The detector was minimally interfered by the presence of constituents such as Na⁺, K⁺, Ca²⁺, Mg²⁺, glucose, urea, lactic and citric acids at physiological levels, respectively. Good correlation between results of the proposed method and HPLC for the formulation samples was found, while results for the determination of paraquat in biological samples such as urine, vomitus and stomach washout was less satisfactory.     

Array of potentiometric sensors for the analysis of creatinine in urine samples

The development of potentiometric biosensors for creatinine based on creatinine iminohydrolase (E.C. 3.5.4.21) immobilized on chitosan membranes coupled to a nonactin based ammonium ion selective electrode is described. The response characteristics of three types of biosensors with the enzyme immobilized by three different procedures were evaluated. The biosensors with better response characteristics were obtained by coupling the ammonium ion selective electrodes to chitosan membranes with the enzyme immobilized by adsorption. The linear response range of these biosensors to creatinine was 10(-4) to 10(-2) M, the response time was between 30 and 60 s, they showed an operational lifetime of 44 days and the slope of the response to creatinine in the first day varied between 50 and 52 mV decade-1. An array of six potentiometric sensors, constituted by two creatinine biosensors and four ion selective electrodes for potassium, sodium, ammonium and calcium was calibrated and a multivariate model based on PLS1 for the response to creatinine was obtained and validated. The array was used for the analysis of creatinine in urine samples and the results were compared with the results of a clinical analysis laboratory, based on the Jaffé reaction.     

Determination of lead and cadmium in biological samples by potentiometric stripping analysis

Summary The determination of lead and cadmium in biological materials was carried out by potentiometric stripping analysis. Supporting electrolyte was a mixture of NaCl and HCl. In the presence of 4% lumatom in methanol, oxidation potentials of –0.46 V for Pb and –0.68 V for Cd were found (vs. SCE). The method was applied to different standard reference materials (leaves, needles, hair) and was also compared with the differential pulse anodic stripping technique. The latter presented considerable difficulties, in particular by the interference of oxygen.

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Bestimmung von Blei und Cadmium in biologischem Material durch potentiometrische Stripping-Analyse

Zusammenfassung Als Trägerelektrolyt diente bei diesem Verfahren ein Gemisch von NaCl und HCl. In Gegenwart von 4% Lumatom in Methanol wurden Oxidationspotentiale von –0,46 V für Pb und –0,68 V für Cd (gegen SKE) erhalten. Die Methode wurde auf verschiedene Referenzmaterialien (Laub, Nadeln, Haar) angewendet und auch mit der Differentialpuls-Anodic Stripping-Analyse verglichen. Bei der letzteren ergaben sich größere Schwierigkeiten, hauptsächlich durch störenden Sauerstoff.

     

Dynamic mechanical relaxation behavior of block copolymers at high temperatures

We carried out dynamic mechanical measurements to investigate three different examples of block copolymers: styrene–isoprene diblock copolymers and styrene–butadiene–styrene and styrene–(styrene butadiene)–styrene triblock copolymers. Isochronal and isothermal measurements of the real and imaginary parts of the complex shear modulus were performed over wide ranges of temperature and frequency. The measurements showed the presence of an additional relaxation process appearing at temperatures higher than those of the glass relaxation of the polystyrene phase, which has been misinterpreted by some authors as an order–disorder transition. The frequency dependence revealed that this process was a relaxation process and did not belong to a first‐order transition. Moreover, the influence of crosslinking via dicumylperoxide was measured, and we constructed complete master curves to confirm the presence of two relaxation processes. The high‐temperature relaxation process was strongly suppressed by crosslinking. Therefore, it was possible to detect the glass relaxation process of the polystyrene phase in a precise manner. The results were compared with those of homopolymers. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2198–2206, 2001     

The potentiometric behavior of polymer-supported metallophthalocyanines used as anion-selective electrodes

Liquid polymer membrane electrodes based on nickel and manganese phthalocyanines were examined for use as anion-selective electrodes. The electrodes were prepared by incorporating the ionophores into plasticized poly(vinyl chloride) membranes, which were directly coated onto the surfaces of graphite electrodes. The resulting electrodes demonstrate near-Nernstian responses over a wide linear range of perchlorate anion (5 × 10⁻⁷ to 1 × 10⁻¹ M). The electrodes have a fast response time, submicromolar detection limits (5 × 10⁻⁷ M perchlorate), and could be used over a wide pH range of 3.5–10. The influences of lipophilic cationic and anionic additives on the response properties of the electrodes were investigated. The proposed sensors revealed high selectivity for perchlorate over a number of common inorganic and organic anions. The highest selectivity was observed for the electrode based on manganese phthalocyanine in the presence of the lipophilic anionic additive sodium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate. Application of the electrodes to determine perchlorate in tap water and human urine is also reported.      

Flow-injection potentiometric applications of solid state Li+ selective electrode in biological and pharmaceutical samples

A solid state polyvinyl chloride (PVC) membrane Li⁺-selective electrode was prepared and used as a detector in a low-dead volume flow through cell for the determination of Li⁺ in pharmaceutical formulations and human serum samples. The potentiometric performance characteristics of the electrode were calculated under the optimized flow conditions. The electrode had near-Nernstian behavior in the concentration range of 0.1–100 mM (R ² = 0.9981) with a slope of 61.34 mV decade⁻¹ and detection limit of 0.080 mM. The relative standard deviation of the electrode response for eight replicate measurements of 100, 10, and 1 mM Li⁺ was 0.43%, 0.45%, and 0.99%, respectively. The designed flow-through cell detector system revealed sampling rates of approximately 70 injections per hour. Flow injection potentiometry (FIP) results obtained for the pharmaceutical formulations were in good harmony with the atomic emission spectrophotometry results. However, the electrode could not be used successfully for the direct analysis of real serum samples in FIP.     

Flow injection determination of anisidine value in palm oil samples using a triiodide potentiometric detector

A flow injection analysis (FIA) procedure for the determination of anisidine value (AV) in palm olein using a triiodide detector is described. Undiluted oil sample and chloramine-T reagent were added to a reaction chamber, and reaction was accelerated by applying a short vortex action (typically for 30 s). After allowing the emulsified oil phase to be separated from the aqueous phase (bottom layer), an aliquot of the aqueous phase (containing unreacted chloramine-T) was aspirated into a carrier stream that contained I⁻ where the chloramine-T oxidized the I⁻ to form I₃⁻ which was finally detected by a flow-through triiodide potentiometric detector. Variables that affect the FIA signals such as size of the reaction chamber, oil and reagent flow rates, chloramine-T concentration, vortex time, time for phase separation, carrier stream pH and injected volume were studied. The optimized FIA procedure is linear over 1.0-23.0 AV. The method exhibits good repeatabililty (R.S.D. of ±3.16% (n = 4) for the determination of 5.0 AV) and a sampling rate of 40 samples per hour was achieved. Good correlation (r² = 0.996 (n = 4)) between the proposed method and the manual American Oil Chemists’ Society procedure was found when applied to the determination of twenty different types of palm olein samples.     

Lanthanide complexes as luminogenic probes to measure sulfide levels in industrial samples

A series of lanthanide-based, azide-appended complexes were investigated as hydrogen sulfide-sensitive probes. Europium complex 1 and Tb complex 3 both displayed a sulfide-dependent increase in luminescence, while Tb complex 2 displayed a decrease in luminescence upon exposure to NaHS. The utility of the complexes for monitoring sulfide levels in industrial oil and water samples was investigated. Complex 3 provided a sensitive measure of sulfide levels in petrochemical water samples (detection limit ∼ 250 nM), while complex 1 was capable of monitoring μM levels of sulfide in partially refined crude oil.     

Determination of fluoxetine in pharmaceutical preparations and biological samples using potentiometric sensors based on polymeric membranes

The construction and general performance of four novel potentiometric membrane sensors for the determination of fluoxetine have been described. The sensors are based on the formation of the ion association complex of fluoxetine with sodium tetraphenylborate and phosphotungstic acid as electroactive materialles, dispersed in a PVC matrix with dibuthyl sebacate (or diethyl sebacate) as a plasticizer. These sensors exhibit fast, stable and near-Nernstian response for the monocharged fluoxetine cation over wide concentration range from 3.0 × 10^?6 to 1.2 × 10^?2 M and pH 4.0–7.5. No interferences are caused by many inorganic and organic species. Direct potentiometric determinations of 5–100 μg/mL of fluoxetine in drug and urine samples show good recovery of fluoxetine. The developed membrane electrodes have been used as an end point indicator electrode; the potentiometric titration of fluoxetine with sodium tetraphenylborate as a titrant has been monitored.     

Dynamic behavior in diplatinum metalloreceptors

Diplatinum metalloreceptors anti-4a and anti-4b exhibit dynamic behavior in solution that is modified by anion binding. An X-ray crystal structure determination of anti-4a supports its proposed solution structure.     

Influence of decyl alcohol on the potentiometric behavior of three p-alkylbenzenesulfonate ion-selective electrodes

The influence of decyl alcohol on the potentiometric response of three para-alkylbenzenesulfonate (p-RBS) electrodes is analyzed. The results are clearly dependent on the membrane surface polarity due to the presence of the alcohol. The ionophore was the complex trioctylmethylammonium-p-RBS, (TOMA+)-p-RBS-, with R=H, CH3, and C2H5. The nature of the complex plays a fundamental role on the potentiometric behavior of the electrode showing that the more hydrophobic the complex, the better the potentiometric responses. Moreover, the electrodes selectivities for several hydrophilic and hydrophobic interfering anions were determined. The potentiometric results with interfering anions were coherent with the Pearson's hard and soft acid-base character of these anions.     

Thermal behavior of selected Czech marble samples

The definition as well as prediction of rock thermal behavior seems to be a quite difficult problem significantly effected by rock composition and structure. Temperature increase causes various changes of rock material (such as decomposition, oxidation, phase and polymorphic transformation, etc.). These changes are connected to thermal expansion with following appearance of tensions and cracks in minerals and rock structure. After consequential temperature decrease, developed tensions and cracks still influence the process. This study presents the application of thermogravimetric analysis, differential thermal analysis and thermomechanical analysis in characterization of selected marble thermal behavior. The texture and morphological orientation of calcite grains for marble samples was determined by optical microscopy. FTIR spectroscopy application along with X-ray diffraction (XRD) extended data about mineralogical composition. According to optical microscopy, the calcite grains show marked morphological anisotropy in one direction for some samples. Therefore, the thermal expansion had to be measured in three different (perpendicular to each other) directions. It is evident, that the effect of temperature on the final marble properties depends not only on mineralogical composition, but also on structure, texture and morphological orientation of grains. All these facts significantly influence the interpretation of differences in various marble thermal behavior.     

ESR lineshapes and kinetic behavior of nitroxide spin probes in micellar solutions

The ESR spectrum of the nitroxide radical 2,2,6,6-tetramethylpiperidine-N-oxide (TEMPO) has been investigated in aqueous solutions of the following surfactants:n-octylammonium bromide, sodiumn-octylsulfonate,n-decylammonium bromide,n-docecyltrimethylammonium bromide, and sodiumn-dodecylsulfate. The spectra were recorded at 25° C as function of surfactant concentration in the ranges 0–0.5m for the C₁₀ and C₁₂ compounds and 0–1.0m for the others. Analysis of the spectra using computer simulation methods yields the hyperfine coupling constanta _H and the widthW _H of the partially resolved lines in the proton hyperfine structure. Changes in these variables with surfactant concentration are interpreted from medium effects on the magnetic properties of the radical, kinetics of radical-micelle interactions, and rotational dynamics of the nitroxide probe in these solutions.     

Flow injection potentiometric determination of pancuronium bromide in pharmaceutical preparation and urine samples using modified carbon paste electrodes

Carbon paste electrodes for pancuronium bromide was prepared based on ion association complexes of pancuronium bromide with sodium tetraphenylborate (NaTPB) or ammonium reineckate using dibutyl phthalate as solvent mediator and tetradodecylammonium tetrakis-(4-chlorophenyl)borate (ETH 500) as lipophilic additive. The sensors showed a near-Nernstian slope of 28.1 mV concentration decade(-1) at 25°C within the concentration range 6.31×10(-6)-1.00×10(-2) M in case of pancuronium-tetraphenylborate electrode and 26.6 mV concentration decade(-1) in the concentration range 5.66×10(-5)-1.00×10(-2) M in case of pancuronium-reineckate electrode. The sensors were successfully applied for the potentiometric determination of pancuronium bromide in pharmaceutical preparation and biological fluids in batch and flow injection conditions.     

Enantioanalysis of l-2-hydroxyglutaric acid in urine samples using enantioselective, potentiometric membrane electrodes based on maltodextrins

Quantitative assay of l-2-hydroxyglutaric acid (l-2-HGA) is important for the diagnosis of l-2-hydroxyglutaric aciduria. Three enantioselective, potentiometric membrane electrodes (EPMEs) based on maltodextrins with different dextrose equivalent (DE) (DE: 4.0-7.0 (I), 13.0-17.0 (II), 16.5-19.5 (III)), were designed for the enantioanalysis of l-2-HGA. The enantioselective, potentiometric membrane electrodes can be used reliably for enantiopurity assay of l-2-HGA using the direct potentiometric method in the ranges of 10⁻⁹-10⁻⁵, 10⁻⁶-10⁻³ and 10⁻⁸-10⁻⁵ mol L⁻¹ for the enantioselective, potentiometric membrane electrodes based on maltodextrins I, II and III, respectively, with very low detection limits. A high reliability was obtained when the electrodes were used for the assay of l-2-HGA in urine samples.     

Dynamic response characteristics of the potentiometric carbon dioxide sensor for the determination of aspartame

The dynamic response characteristics of a carbon dioxide gas sensor were studied to determine the potential for application of the device to the kinetic assay of substrate(s) under pseudo first-order kinetics. The dependence of the time constant on the concentration of carbon dioxide was determined by using convolution mathematics to analyse potentiometric changes caused by abrupt alterations of gas concentration. The operational conditions of the CO2 sensor were optimised for the development of enzyme electrodes, so that the mass-transport phenomena occurring during the course of the enzymic reactions were enhanced. As a result, the kinetic analysis of substrate(s) was performed more rapidly (2-6 min), with greater sensitivity and with an improved detection limit (10-5 M). A kinetic reaction-rate method for the determination of aspartame in dietary foodstuffs is proposed as a rapid and inexpensive alternative to a classical high-performance liquid chromatographic method.     

Dynamic sonication-assisted solvent extraction of organophosphate esters in air samples

A sensitive and selective method is presented for the determination of Zn-Bacitracin in adulterated animal feed by reversed-phase ion-pair high-performance liquid chromatography and post-column derivatization with o-phthalaldehyde prior to fluorescence detection. The calibration function was estimated to be between 8.0 and 65.0 mg l(-1) of Zn-BC. The detection and quantification limits of the chromatographic method were 2.5 and 7.5 mg 1(-1), respectively. Using the extraction procedure of Zn-Bacitracin from the feedstuff that we recently proposed and applying this new chromatographic method, it was possible to detect this antibiotic at levels below 5 mg kg(-1) in different kinds of feedstuffs with a standard deviation less than 6.0%.