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Analytical Signal (analytical + signal)
Selected AbstractsA Contactless Impedance Probe for Simple and Rapid Determination of the Ratio of Liquids with Different Permittivities in Binary MixturesELECTROANALYSIS, Issue 1 2009Franti, ek Opekar Abstract Simple contactless cells with planar or tubular electrodes have been designed for measurement of the permittivity of solutions. The cells, connected to an integrated circuit of astable multivibrator, respond primarily to the capacitance component of the cell impedance, the multivibrator frequency depends in a defined manner on the solution permittivity and is readily used as the analytical signal in determinations of the ratios of components in binary liquid mixtures; water solution of methanol, ethanol and dioxane have been tested. The response of the cell with planar electrodes satisfies well the simple theoretical model and both the cells provide results with a sufficient sensitivity, a low LOD value (units of %vol) and a good precision (around 1%rel). The cell simplicity, small dimensions, long-term stability and the possibility of powering them from a battery make them suitable for hand-held meters. As an example of application in practice, the content of ethanol was determined in the car fuel petrol. [source] Voltammetric Detection of Free Sulfhydryl Compounds in Food FloursELECTROANALYSIS, Issue 1 2007Matteo Scampicchio Abstract Cyclic voltammetry has been applied to the rapid measurement of free SH-compounds in food flours samples. The protocol is based on the electrochemical adaptation of the Ellman's test, where the DTNB reacts with SH-compounds present in food flour extracts, resulting in the equimolar production of the electroactive compound TNBA which, in turns, reacts with phenylendiamine. The reaction is found to provide an analytical signal from which to quantify indirectly free sulfhydryl compounds in flours extracts. [source] Determination of Platinum with Thiosemicarbazide by Catalytic Adsorptive Stripping Voltammetry (AdSV)ELECTROANALYSIS, Issue 4 2005Sylwester Huszal Abstract This work describes a very sensitive and selective voltammetric procedure for the determination of platinum. Instead of commonly used hydrazine, thiosemicarbazide as a component of supporting electrolyte was applied. The method is based on adsorption of platinum-thiosemicarbazone complex, formed in situ in voltammetric cell from thiosemicarbazide and formaldehyde, coupled with a hydrogen catalytic reaction at a hanging mercury drop electrode. The linear relation between platinum concentration and height of analytical signal was observed up to 1.5×10,9,mol,L,1 with the detection limit calculated as 1.5×10,13,mol,L,1 (3,s of the blank) after 50,s of accumulation time. The effect of various interferences from other ions was studied. Described method was applied for platinum determination in hydroponically cultivated plants after microwave decomposition. [source] Adsorptive Stripping Voltammetry of Rifamycins at Unmodified and Surfactant-Modified Carbon Paste ElectrodesELECTROANALYSIS, Issue 20 2004Sonia Gutiérrez-Fernández Abstract The electrochemical behavior of the antibiotics rifampicin and rifamycin SV is investigated by cyclic voltammetry at carbon paste and in situ surfactant modified carbon paste electrodes. Both antibiotics adsorb on the unmodified electrodes and show a reversible redox process due to the oxidation of the 6,9-dihydroxynaphthalene moiety to the corresponding naphthoquinone. This process is used as analytical signal for developing adsorptive voltammetric methods for the determination of the antibiotics. Experimental parameters, such as pH of the supporting electrolyte, accumulation potential and time are optimized. After accumulation from acidic solutions (0.1,M KCl pH 2 or HCl 0.2,M) at ,0.1 or 0,V for 3,min, the differential pulse oxidation peak current changes linearly with the antibiotic concentration in the range 3.5×10,10,M ,5.4×10,9,M or 5×10,11,M ,1.0×10,9,M for rifampicin and rifamycin SV, respectively. Rifamycin SV is not accumulated on carbon paste electrodes modified in situ with the anionic surfactant sodium dodecyl sulfate, whereas rifampicin is readily accumulated on this modified electrodes resulting in a signal enhancement and allowing rifampicin determinations without interference from rifamycin SV. On the other hand, selective determination of rifamycin SV in the presence of rifampicin is achieved by using carbon paste electrodes in situ modified with the cationic surfactant cetyltrimethylammonium chloride. [source] Catalytic Effect on Silver Electrodeposition of Gold Deposited on Carbon ElectrodesELECTROANALYSIS, Issue 19 2004Alfredo de, Escosura-Muñiz Abstract A new methodology, based on silver electrocatalytic deposition and designed to quantify gold deposited onto carbon paste electrode (CPE) and glassy carbon electrode (GCE), has been developed in this work. Silver (prepared in 1.0,M NH3) electrodeposition at ,0.13,V occurs only when gold is previously deposited at an adequate potential on the electrode surface for a fixed period of time. When a CPE is used as working electrode, an adequate oxidation of gold is necessary. This oxidation is carried out in both 0.1,M NaOH and 0.1,M H2SO4 at oxidation potentials. When a GCE is used as working electrode, the oxidation steps are not necessary. Moreover, a cleaning step in KCN, which removes gold from electrode surface, is included. To obtain reproducibility in the analytical signal, the surface of the electrodes must be suitably pretreated; this electrodic pretreatment depends on the kind of electrode used as working electrode. Low detection limits (5.0×10,10,M) for short gold deposition times (10,min for CPE and 5,min for GCE) were achieved with this novel methodology. Finally, sodium aurothiomalate can be quantified using silver electrocatalytic deposition and GCE as working electrode. Good linear relationship between silver anodic stripping peak and aurothiomalate concentration was found from 5.0×10,10,M to 1.0×10,8,M. [source] Catalytic Voltammetric Determination of Cladribine in Biological SamplesELECTROANALYSIS, Issue 5-6 2003Noemí de-los-Santos-Álvarez Abstract An electrochemical method for the citotoxic prodrug cladribine determination is proposed. Graphite electrodes modified with cladribine showed a redox process with a formal potential of 0.173,V at pH 6, after the oxidation of the adenine moiety of the drug, whose current can be employed as analytical signal with a detection limit of 75,nM by square-wave voltammetry. As these oxidation products exhibit great electrocatalytic activity toward the electro-oxidation of NADH at low potentials, the analytical response can further be amplified. As a result, the detection limit was improved up to 1,nM using differential pulse voltammetry. The method was applied to the determination of cladribine in serum and urine samples after solid-phase extraction. No electroactive interferences were found in both fluids. The method allows the selective detection of the drug in the presence of the main metabolite, 2-chloroadenosine, which is not able to electrocatalize the NADH oxidation. [source] New supported liquid membrane-capillary electrophoresis in-line arrangement for direct selective analysis of complex samplesELECTROPHORESIS, Issue 15 2006Leonor Nozal Abstract An in-line coupling of a micro-membrane extraction unit, based on supported liquid membrane, with commercially available capillary electrophoresis equipment is described. A main characteristic of this micro-membrane device, made from a simple Eppendorf tube, is that it permits the application of voltage in the acceptor solution to be applied during the extraction process. This has been shown as an alternative to enhance sensitivity, as the analytical signal achieved by applying 10,kV for 20,min was similar to that obtained without the application of voltage and with extraction time of 60,min. In addition, the design has been made permitting both in-line hydrodynamic and electrokinetic sample introduction into the electrophoretic capillary. The analytical potential of the proposed system has been demonstrated by the direct determination of nitroimidazoles from pig liver tissue. The high efficiency of the proposed system allowed the extraction and the determination of the analytes to be performed from a simple tissue homogenate obtained in water. The precision of the analysis of spiked samples, expressed in terms of relative standard deviation, was better than 4.8%. [source] Underpotential Deposition Study and Determination of Bismuth on Gold Electrode by Using VoltammetryCHINESE JOURNAL OF CHEMISTRY, Issue 6 2002Yong-Ling Du Abstract The cyclic voltammetry (CV) and the semidifferential anodic stripping voltammetry (SdASV) were used for investigation of bismuth(III) underpotential deposition (UPD) on gold electrode. Based on the excellent electrochemical properties of Au/ Bi UPD system, a new method for determining bismuth (III) was established. A solution of 0.1 mol/L HNO3 was selected as the supporting electrolyte. Factors affecting the Bi(III) UPD and stripping steps were investigated and an optimized analytical procedure was developed. The calibration plots for Bi(III) concentration in the range 1.25 × 10,8 -1.0 × 10,7 mol/L were obtained. The detection limit, calculated as three times the standard deviation of the analytical signal of 8.3 × 10,8 mol/L for a 90 s electrodeposition at 0.00 V (while the solution magnetically stirred at a speed of 300 rpm), was 7.5 × 10,9 mol/ L. For 8 successive determinations of 1.25 × 10,7 mol/L Bi(III), the obtained RSD (relative standard deviation) was 0.4%. The developed method was applied to bismuth determining in medicine and urine samples. The analytical results were compared with that of atomic emission spectrometry (AES) method. [source] Acid decomposition of omeprazole in the absence of thiol: A differential pulse polarographic study at the static mercury drop electrode (SMDE)JOURNAL OF PHARMACEUTICAL SCIENCES, Issue 2 2006Ali M. Qaisi Abstract The reactions of omeprazole, a potent proton pump inhibitor (PPI), were investigated in the absence of a nucleophile. Reactions were monitored, using differential pulse polarography (DPP) at the static mercury drop electrode (SMDE), in solutions buffered to pH values ranging from 2.0 to 8.0. The fast, sensitive, and selective electrochemical technique facilitated to repeat recordings of successive voltammograms [peak current (nA) vs. peak potential (volts vs. Ag/AgCl saturated with 3.0 M KCl)]. The DPP signals of omeprazole and its degradation products, believed to be due to sulfur functional group (the principal site of electrode reaction), gave advantages over the previously employed UV detection technique. The latter primarily relied on pyridine and benzimidazole analytical signals, which are common reaction products of PPI in aqueous acidic solutions. After peak identification, the resulting current (nA)-time (s) profiles, demonstrated that omeprazole undergoes degradation to form two main stable compounds, the first is the cyclic sulfenamide (D+), previously believed to be the active inhibitor of the H+, K+ -ATPase, the second is omeprazole dimer. This degradation is highly dependant on pH. Unlike previous studies which reported that the lifetime of D+ is few seconds, the cyclic sulfenamide (D+) was found to be stable for up to 5,20 min. The results further indicated that omeprazole converts into the cyclic sulfenamide in an irreversible reaction, consequently, D+ and sulfenic acid (an intermediate which rapidly converts into D+) were not interconvertable. The present work suggested that the sulfenic acid is the active inhibitor in vivo. In addition, the omeprazole reactions, in the absence of the thiol, were not as complicated as were previously reported. © 2005 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 95:384,391, 2006 [source] Performance characteristics according to Commission Decision 2002/657/EC in the fluorimetric determination of tetracycline in the absence and in the presence of magnesiumLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 6 2007Noelia Rodríguez Abstract The fluorimetric determination of tetracycline is usually carried out in the presence of some metals that, through the formation of a complex with this antibiotic, enhance its fluorescence emission, giving more sensitive determination methods. It is well established that magnesium is one of these metals. However, it is possible that higher signals do not mean a real improvement in the quality of the analytical method. In this work, the univariate and multivariate fluorescence determination of tetracycline is performed in the presence and absence of Mg2+, comparing the quality of the analyses through some performance characteristics that, according to Commission Decision 2002/657/EC define the functional qualities of analytical methods. The methods with the best performance characteristics were multivariate determinations carried out in the absence of Mg2+, both when emission or excitation spectra were taken, the decision limits (CC,) being 13.1 and 20.1 µg/L and the detection capabilities (CC,) 25.3 and 38.5 µg/L, respectively. This study points out through a case study that higher analytical signals do not necessarily mean better performance characteristics of a method of analysis. Copyright © 2007 John Wiley & Sons, Ltd. [source] | ||||||||||