Lead migration from toys by anodic stripping voltammetry using a bismuth film electrode.

Metals may be released from toys via saliva during mouthing, via sweat during dermal contact, or via gastric and intestinal fluids after partial or whole ingestion. In this study, we determined the lead migration from toys bought on the Portuguese market for children below 3 years of age. The lead migration was performed according to the European Committee for Standardization EN 71-3, which proposes a 2-hour migration test that simulates human gastric conditions. The voltammetric determination of migrated lead was performed by anodic stripping voltammetry (ASV) at a bismuth film electrode (BiFE). For all the analyzed toys, the values of migrated lead did not exceed the limits imposed by the European Committee for Standardization EN 71-3 (90 mg kg-1) and by the EU Directive 2009/48/EC (13.5 mg kg-1) on the safety of toys.

Ofloxacin determination in urine, serum and pharmaceuticals using an automatic flow potentiometric system.

An automatic system was developed to determine ofloxacin in biological fluids and pharmaceutical formulations. Drug detection was carried out by a potentiometric membrane sensor based on [bis(trifluoromethyl)phenyl]borate as molecular-recognition material. The tubular shaped detector system was solidly attached to the manifold, creating a high-throughput stable setup (50 samples per hour) appropriate for routine antibiotic assessment. Under the optimized flow conditions, the sensor displayed a mean detection limit of 1 × 10(-5) M, a linear response over the concentrations of 2 × 10(-5) to 5 × 10(-3) M (slope of 57.4 mV decade(-1)) and a wide working pH range (2.1 - 6.6). The procedure was successfully applied to ofloxacin analysis in pharmaceuticals (relative deviation lower than 6%) and biological fluids at levels usually found after drug administration of clinical doses (recoveries between 91 and 106%). No significant interference from common excipients found in commercial formulations and inorganic ions usually present in biological fluids was noticed.

Flow amperometric determination of pharmaceuticals with on-line electrode surface renewal.

In this article, a flow system developed for the amperometric determination of a great variety of pharmaceuticals that are known to lead the rapid poisoning of the working electrode surface is described. The referred system was made up of two parallel flow channels that shared the voltammetric detector of tubular configuration, whose movement in the manifold followed the concept of multi-site location of detector. In this way, after each measurement, the conditioning of the working electrode was possible through the passage by its surface of a regeneration solution without implying the alteration of the carrier that flowed in the analytical channel of the manifold. The methodology proposed was evaluated through the determination of two drugs belonging to two distinct therapeutic groups: an antihypertensive (diltiazem) and a non-steroid anti-inflammatory (nimesulide). The results obtained after evaluation of various pharmaceutical formulations on the Portuguese market were in the case of diltiazem compared with those supplied by the reference US Pharmacopoeia XXIV method, with no statistically significant differences having been observed for a confidence interval of 95%. In the case of nimesulide, since no official reference method exists, a series of recovery experiments were proceeded with and a mean value of 101.1% with a R.S.D. of 0.7% was obtained.

Sequential determination of salicylic and acetylsalicylic acids by amperometric multisite detection flow injection analysis.

An amperometric multisite detection flow injection analysis (FIA) system was developed for sequential determination of 2 analytes with a single sample injection and single detector. Tubular composite carbon electrodes with an inner diameter similar to that of the FIA manifold tubing were constructed so that measurements could be made without impairing the sample plug hydrodynamic characteristics. The electrochemical behavior of the tubular voltammetric cell in a low-dispersion FIA manifold and the behavior of the FIA system incorporating this type of voltammetric cell intended for multisite detection were evaluated by performing measurements with potassium hexacyanoferrate(II). Feasibility of the approach was demonstrated in the sequential determination of salicylic and acetylsalicylic acids in pharmaceutical products at a fixed potential of 0.98 V. The system allows sequential determination of salicylic acid concentrations ranging from 1.0 x 10(-5) to 5.0 x 10(-5) M and acetylsalicylic acid concentrations between 1.0 x 10(-3) and 5.0 x 10(-3) M with good precision on both detection sites and with relative standard deviations (RSDs) > or = 1.5% (n = 10) and 2.1% (n = 10), respectively. A comparison of these results with those of the U.S. Pharmacopeia procedure showed RSDs <5.0 and 1.0% for salicylic acid and acetylsalicylic acid, respectively. The proposed method enables 15 determinations per hour, which corresponds to the analysis of approximately 8 samples per hour. The detection limits of the methodology were approximately 3.5 x 10(-6) and 1.1 x 10(-5) M, respectively, for the first and second monitoring sites.