A biamperometric method for the determination of sulfate

A biamperometric method for the determination of sulfate has been developed. Its application to the determination of sulfate content in rubidium uranium trisulfate is discussed. Sulfate is determined by titration with lead nitrate in aqueous ethanolic medium using ferrocyanide-ferricyanide redox system as biamperometric indicator. Initially, the method has been tested for standard. K₂SO₄ solutions. In case of Rb₂ U(SO₄)₃, since uranium interferes, it is precipitated as ammonium diuranate and excess ammonia is removed prior to the titration. Precision of better than 0.3% was achieved with no significant bias.     

流动注射双安培法测定橙皮甙

基于橙皮甙的不可逆氧化和氧化铂的不可逆还原体系构成了双安培法直接检测橙皮甙的新方法。在外加电压为0.2 V时,通过偶合橙皮甙在一支电极上的氧化和氧化铂在另一支电极上的还原两个不可逆电极过程,构成流动注射双安培检测体系。在pH 8.95的B-R缓冲溶液中,测得橙皮甙的氧化电流与其浓度在6.0×10-6~8.0×10-4mol/L范围内呈良好的线性关系(r=0.9997,n=11),检出限为1.0×10-6mol/L。连续30次测定6.0×10-4mol/L橙皮甙,其峰电流相对标准偏差(RSD)为3.2%,常用药物赋形剂和无机离子均不干扰橙皮甙的测定。方法已用于江中健胃消食片中橙皮甙含量的测定。     

Indirect determination of nitroglycerine by biamperometric titrimetry

A procedure is described for the determination of nitroglycerine in propellant samples by biamperometric titrimetry. The method is simple, avoids the use of expensive instruments, and is free from interferences other than those occurring in the classical techniques. The accuracy and precision are equal to those of existing methods. The reduction and titration steps are performed in the specially designed flask.     

Indirect biamperometric determination of o-phenylenediamine in lab-on-valve format using reversible indicating redox system

The miniaturized lab-on-valve (LOV) manifold well hyphenated with indirect biamperometry is presented for automated determination of trace level concentrations of organic environmental pollutants by programmable flow. The experimental procedure was carried out by means of taking o-phenylenediamine (OPDA) as a model analyte, relying on the Fe(iii)/Fe(ii) couple that served as an indicating redox system. The miniaturized electrochemical flow cell (EFC) designed and processed was integrated into the LOV module which is assembled with two identical polarized platinum electrodes between which a small potential difference (ΔE) was applied, to implement automated on-line analysis in a closed system. Factors affecting analytical performance are discussed, including indicating redox systems, concentration of indicating system, the acidity, the potential difference, and flow variables in the LOV. The calibration curve showed an excellent linearity in the concentration range of 5.0 × 10(-7) to 1.0 × 10(-4) mol L(-1) (R(2) = 0.9993). The limits of detection (LOD) and quantitation (LOQ) for OPDA were found to be 1.1 × 10(-7) and 3.7 × 10(-7) mol L(-1), respectively. A sampling frequency of 40 h(-1) was obtained along with an R.S.D. of 2.8% at 1.0 × 10(-6) mol L(-1) OPDA (n = 11). The proposed procedure was successfully applied to the assay of OPDA in industrial waste water.     

A flow-injection biamperometric method for determination of pantoprazole in pharmaceutical tablets

A flow-injection biamperometric method for determination of pantoprazole (PTZ) in pharmaceutical tablets is reported for the first time. The reversible redox couples Fe3+/Fe2+, Fe(CN)6(3-)/Fe(CN)6(4-), Ce4+/Ce3+, VO3(-)NO2+, and I2/I- were tested as indicating redox systems for biamperometric determination of PTZ in a flow-injection assembly with optimized flow parameters. The best results were obtained using V03(-)NO2+, which showed to be a selective and sensitive biamperometric indicating system for PTZ even in the presence of excipients and antioxidants that typically are found in drugs. The analytical graph was linear (r = 0.99945) in the range from 10 to 100 mg/L using 25 mmol/L VO3(-) as the reagent and water as the carrier stream and applying 100 mV between the 2 platinum wire electrodes. The limits of detection and quantitation were 200 and 667 microg/L, respectively, with a sensibility of calibration of 22.6 mV/mg/L. The proposed method was successfully applied to determine PTZ in commercial pharmaceutical tablets with a mean relative error of 1.60% (n = 5) and mean relative standard deviation of 3.10%. Recoveries close to 100% showed good agreement between the expected amount of PTZ in tablets (40 mg) and the results found by the application of the proposed method and demonstrated that the formulations used in the tablet compositions do not interfere in the PTZ analysis. The system had good stability, with a relative standard deviation of 3.80% for 9 sequential injections of a 60 mg/L PTZ solution. A sampling rate of about 100 samples/h was obtained.     

A flow injection method for biamperometric determination of dipyrone in pharmaceuticals

A flow-injection method for determination of dipyrone (novalgin, metamizol) in pharmaceutical tablets with biamperometric detection is described. Flow-parameters such as flow rate, coil length and sample injection volume were optimized. The calibration graph was linear (r=0.9997) within the range of 10-50 mg l⁻¹ in a 1-mmol l⁻¹ HCl carrier solution for an applied potential of 100 mV between the two platinum wire electrodes. Two indicating redox systems were studied, namely Fe(III)/Fe(II) and I₂/I⁻. The former proved to be well suited as a selective and sensitive biamperometric indicating system for dipyrone in the presence of ingredients commonly accompanying the drug. The developed method was successfully applied to the determination of dipyrone in several commercial pharmaceutical preparations. The sampling rate was 71 samples per hour with a rsd of 1.6% (eight injections of a 14-mg l⁻¹ dipyrone solution). Recoveries close to 100% demonstrated the reliability of the proposed method.     

A novel biamperometric biosensor for urinary oxalate determination using flow-injection analysis

A biosensor for determination of oxalate concentration in urine has been developed by immobilisation of oxalate oxidase and peroxidase on the surface of an interdigitated gold electrode. Enzyme immobilisation was performed using BSA and glutaraldehyde. Biamperometric measurements were made in flow conditions both in aqueous oxalate solutions (tested concentration range between 50 μM and 10 mM) and in real urine samples (tested measuring range between 5 and 100 μM). Optimal working conditions were examined for flow-injection analysis, and good correlation was achieved between added oxalate quantity and the one measured by biosensor in urine matrix (R² = 0.9983). The influence of some interferences (ascorbic acid, uric acid, paracetamol, acetylsalicylic acid) was also studied using biamperometric measurement mode.     

Robust flow-batch coulometric/biamperometric titration system: determination of bromine index and bromine number of petrochemicals

A flow–batch system was constructed and evaluated to perform coulometric titrations with biamperometric end point detection. The flow section of the system is employed for sampling by injecting a sample volume (50–300 μL) in a flow injection-like system. About 1.5 mL of a suitable carrier solution is delivered by a peristaltic pump in order to quantitatively transfer the sample to the system titration cell (2.0 mL total inner volume). The carrier contains the coulometric precursor for the titrant species. The cell contains two pairs of platinum electrodes used for coulometric generation of reagent and biamperometric detection and is actively stirred. The titrant species is generated and the titration is performed by the usual batch procedure with the excess of titrant being detected by biamperometry following the analysis of the titration curve. System operation is computer controlled and all operations are automated, including titration curve analysis and cell cleaning after the titration is ended. The system is characterized by its robustness because its operation does not depend on flow rates, and the work using coulometric methods which generate gases at the counter-electrode is not troublesome. The flow–batch system has been evaluated for determination of bromine index and bromine number (relative to the total reactive olefin content) in petrochemicals according to an ASTM procedure. Typical precision (R.S.D.) is between 0.5 and 6% for different petrochemicals whose bromine number/index vary from 1000 to 10 mg of bromine per 100 g of sample, respectively. Recoveries for standard additions are between 92 and 123% for 10 mg of Br₂ per 100 g increments and 98 to 101% for 100 mg per 100 g increments. Accuracy of the proposed system was evaluated against results obtained by the standard ASTM with no significant difference detected at 95% confidence level.     

Ion-selective electrode for the determination of prenalterol

A new prenalterol (Pr) ion-selective PVC membrane electrode based on the ion-pair complex of Pr with sodium tetraphenylborate was prepared and its performance characteristics were studied. The electrode exhibited a linear response with a good Nernstian slope over a relatively wide range of concentration. The electrode whose membrane was made of 8.0% (w/w) of ion pair, 49.5% (w/w) of dioctyl phthalate (DOP) and 43.5% (w/w) of PVC showed characteristics higher than those obtained with the other ones, namely, slope of 56.3 mV per concentration decade, at 25 °C; usable concentration range 1.2×10⁻⁵–3.2×10⁻² M prenalterol; response time ≤20 s. Up to 24 h continuous soaking, the calibration graph slope was constant at 56.0 mV per concentration decade, at 25 °C, then it decreased gradually as the time of soaking increases reaching 41 mV per decade after 11 days. The changes in pH did not affect the electrode performance within the range 2.2–7.5. The standard electrode potentials were determined at different temperatures and used to calculate the isothermal coefficient of the electrode. The electrode showed very good selectivity for Pr with respect to a large number of inorganic and organic cations. The standard addition method and potentiometric titration were used to determine Pr in pure solutions and in pharmaceutical formulations. The relative standard deviations (R.S.D.) of the three methods used for the determination of prenalterol in pharmaceutical formulations were 0.8, 2.1 and 1.9% of the extrapolation, standard addition and potentiometric methods, respectively.     

Enzyme electrode for the determination of salicylate

Salicylate hydorxylase is used with a carbon dioxide sensor for the determination of salicylate in aqueous solution and pooled serum. The enzyme is physically entrapped with a dialysis membrance at the sensing tip of the carbon dioxide electrode. The enzyme catalyses the stoichiometric formation of catechol and carbon dioxide from salicylate and reduced pyridine nucleotide in the presence of flavin adenine dinucleotide as a specific cofactor. The carbon dioxide is detected by the sensor and related to the concentration of salicylate via a calibration curve. The method compares favorably with the spectrophotometric method for assay of salicylate. Although suitable for salicylate concentrations in the range of 5–300 μg ml^?1, its response below 5 μg ml^?1 is limited by the detection limit of the carbon dioxide sensor.     

加碘食盐中微量碘的离子选择性电极测定

在加碘食盐中加入还原剂将KIO3中的IO3^-还原为I^-,使用碘离子选择性电极技术,采用标准曲线法直接测定了溶液中的I-量.并引入表面活性剂作为增敏剂,降低了检测下限,提高了检测的灵敏度.实际测定3种食盐样品,取得了较好的效果.     

A polarographic cell system with a novel temperature-controlled reference electrode for the determination of kinetic parameters of electrode reactions

An improved experimental arrangement for the determination of kinetic data relating to polarographic reductions is described. The significant feature is the constant-temperature reference electrode; its construction and use in this context are described. A comparison is made of the more realistic results obtained by these means, with those obtained with a more conventional cell where the temperature of the reference electrode is varied with that of the working solution.     

Application of ion-exchange chromatography with an ion-selective electrode detector to iodine determination in natural waters

A system is described which uses a selective electrode for potentiometric detection of anions in natural waters after ion-exchange separation. With an iodide-selective electrode in the flow cell, a linear relationship exists between iodide concentration and potential in the sub-Nernstian range (0–100 μM). The limit of detection is 0.015 μM for an injection of 125 μl of sample. For optimum electrode performance, a constant iodide background of about 0.5 μM is required in the column effluent passing through the detector. This background is added uniformly through a short section of hollow-fibre dialysis tubing in a concentric-flow diffusion cell. The detector also responds to other anions which affect the solubility of silver ion. This can be used to advantage if chromatographic separation is sufficient. Preconcentration of iodide in fresh waters on an anion guard cartridge allows determination down to 1 nM concentrations. For sea-water samples, simple chemical pretreatment permits quantitation of different iodine species.     

Ion-selective electrode for the determination of dimethylbenzylammonium ions

A sensor is proposed for the direct potentiometric determination of dimethylbenzylammonium in acid and neutral aqueous solutions. The sensor membrane is made of a polymeric composition on the basis of polyvinylchloride containing an ion associate and a solvent as a plasticizer. Salts of the tetraphenylborate anion and its derivatives served as ionophores. Basic electroanalytical parameters of the developed potentiometric sensors are studied and the pH range of their possible application is determined. The developed sensor is used as a reference electrode in the potentiometric titration of dimethylbenzylammonium with tetraphenylborate anions.     

Indirect coulometric determination of platinum based on the ascorbic acid—iodine system

Platinum(IV) can be determined by addition of an excess of ascorbic acid solution and back-titration with anodically generated iodine to a biamperometric end-point. Conditions have been established for quantitative reduction of platinum(IV) and elimination of oxidation of piatinum(II) by the generated iodine. The determination is carried out at pH 5, and the accuracy and precision are better than 0.5% for platinum in the range 5–20 nag.