Chemiluminometric determination of ascorbic acid in pharmaceutical formulations exploiting photo-activation of GSH-capped CdTe quantum dots.

An automated multi-pumping flow system is proposed for the chemiluminometric determination of ascorbic acid in pharmaceutical formulations, relying on the ability of semiconductor nanocrystals to generate short-lived reactive species upon photo-irradiation. A photo-unit based on visible-light-emitting diodes is used to photo-excite cadmium telluride (CdTe) quantum dots capped with glutathione, leading to the generation of radicals that react with luminol under alkaline conditions, yielding the chemiluminescence. Ascorbic acid acts as a radical scavenger, preventing the oxidation of luminol, thus ensuring a concentration-dependent chemiluminescence quenching. After system optimization, a linear working range of 5.0 × 10(-7) to 5.0 × 10(-6) mol/L ascorbic acid (r = 0.9967, n = 5) was attained, with a detection limit of 3.05 × 10(-7) mol/L and a sampling rate of 200/h. The flow system was applied to the analysis of pharmaceutical formulations and the results were in good agreement with those obtained by the reference titrimetric procedure (RD < ± 4.3%, n = 7).

Zone trapping/merging zones in flow analysis: a novel approach for rapid assays involving relatively slow chemical reactions.

A novel strategy for accomplishing zone trapping in flow analysis is proposed. The sample and the reagent solutions are simultaneously inserted into convergent carrier streams and the established zones merge together before reaching the detector, where the most concentrated portion of the entire sample zone is trapped. The main characteristics, potentialities and limitations of the strategy were critically evaluated in relation to an analogous flow system with zone stopping. When applied to the spectrophotometric determination of nitrite in river waters, the main figures of merit were maintained, exception made for the sampling frequency which was calculated as 189 h(-1), about 32% higher relatively to the analogous system with zone stopping. The sample inserted volume can be increased up to 1.0 mL without affecting sampling frequency and no problems with pump heating or malfunctions were noted after 8-h operation of the system. In contrast to zone stopping, only a small portion of the sample zone is halted with zone trapping, leading to these beneficial effects.

Molecularly imprinted polymer as a solid phase extractor in flow analysis.

Molecularly imprinted polymers (MIPs) are novel alternative materials for solid phase extraction. Applications in flow analysis are recent and enhanced in-line separation/concentration procedures have been proposed. Use of flow systems is very important in the context. The aim of this review is then to highlight the implementation of MIP as solid phase extractor in flow analysis, emphasizing potentialities, limitations and applications.

Multi-task flow system for potentiometric analysis: its application to the determination of vitamin B6 in pharmaceuticals.

A flow set-up based on the sequential injection analysis concept was designed, aiming at increased automation and robustness of procedures related with potentiometric detection in pharmaceutical control. In this sense, programmable set-up calibration, ion-selective electrode characterization, standard addition techniques and titration procedures could be carried out without any stock solutions conventional handling or modification on the physical structure of the flow system. Evaluation of a flow-through vitamin B6 selective electrode and its application to routine analysis of pharmaceuticals were selected as models to demonstrate the system potentialities. The system ability to generate in-line calibrating solutions was verified by comparing the results with those obtained with solutions prepared by the manual procedure. The vitamin B6 determination in pharmaceutical products was carried out and in-line performed recoveries gave values within 97.4-103.5%. The system ability to perform titrations was ascertained using the precipitation reaction of vitamin B6 with tetraphenylborate. Other profitable features such as lower reagent consumption with a low effluent generation volume were also achieved.

Individual sample conditioning in flow analysis. Determination of N-total in plant materials.

A flow-batch system allowing in-line individual sample matrix matching is proposed for analysis of sample lots with high variability in acidity. The feasibility of the approach is demonstrated in the spectrophotometric determination of total nitrogen in Kjeldahl digests, using a column with a slightly soluble reagent (AgCl). The solutions are sequentially injected by means of an 8-port selecting valve and processed in a mixing chamber that is also used as a monitoring unit. The system yields reproducible results (r.s.d. usually < 2.5%) and the sampling rate is 14 samples/h. The analytical curve is linear within 1.00 and 6.00% N (dry basis), and the regression coefficient is > 0.999 (n = 6). Results are in agreement with certified values of standard reference materials and with results obtained by conductometry.

An improved leaping detector for flow analysis applied to iron speciation in drugs.

A low inner volume (ca. 64 ml) probe was built up in an injector-commutator in order to behave as a photometric leaping detector in flow analysis. It comprises a bicolour light-emitting diode (BLED), as a source of pulsed radiation in the red and green visible region, and two phototransistors as transducers. Sample injection, detector relocation, analytical signal recording, data treatment and definition of the spectral working range were computer-controlled. The feasibility of the system was initially demonstrated in the flow-injection speciation of iron, and the overall standard deviation of results was estimated as +/- 1.6 and +/- 1.4% for 1.6-4.0 mg l(-1) Fe(II) or total iron after eightfold processing of synthetic samples. The system was further applied to drug analysis: the mean deviations of results for typical samples were estimated as +/- 5.2 and +/- 3.3%, and the relative standard deviation as +/- 1.6 and +/- 1.3% for Fe(II) and total iron, respectively. Results were compared with those obtained by a conventional spectrophotometric procedure and no statistic differences at the 95% confidence level were found. In relation to an earlier system with multi-site detection, the proposed system is more stable, presenting low drift with a relative standard deviation of 0.026% and 0.039% for measurements (n=120 during 4 h of observation) with green and red emission. It is also faster with a sampling rate of 133 h(-1) and carryover problems are not found. The possibility of compensating the Schlieren noise by dual-wavelength spectrophotometry is discussed.

Correction of iron interface in the spectrophotometric flow injection catalytic determination of molybdenum in plants.

Iron interference in the spectrophotometric catalytic determination of molybdenum based on the iodide-hydrogen peroxide reaction can be corrected by using sulphosalicylic acid as masking and color-forming reagent. The catalytic influence of iron ions is circumvented to the extent of about 90% and correction of any remaining iron ions is possible by monitoring the colored iron(III)-salicylate complex at 490 nm. In this way, iron is also determined. With the proposed system, molybdenum can be determined in plant and food digests within the 0-100 mug Mo 1(-1) range in the presence of up to 25 mg Fe 1(-1), at a sampling rate of about 50 determinations h(-1). The relative standard deviation of 10 consecutive measurements was estimated as < 2%. Results for samples were comparable with those obtained by graphite furnace atomic absorption spectrometry. In addition, recoveries within the range 94-100% were calculated.

Development of a tubular periodate electrode for flow-injection determination of glycerol.

Periodate electrodes without inner reference solution based on tetraoctylammonium periodate plus solvent mediator (dibutyl phthalate or 2-nitrophenyl octylether) were constructed. Linear dynamic range, practical detection limit, slope, stability, selectivity coefficients, pH dependence, response time and lifetime were evaluated. A tubular version was further developed and coupled to a flow-injection system for glycerol determination in samples relevant to the industrial production of soaps, detergents and similar. The method involves glycerol oxidation by periodate with potentiometric evaluation of its consumption. The influence of oxidizing agent concentration (10(-5)-10(-2)M NalO(4)), ionic strength (0.0-1.0M Na(2)SO(4)) and mean resident time were investigated and the feasibility of using a single-fine manifold was discussed. The proposed system handles about 40 samples/hr, is very stable and suitable to industrial control. Results within the 1000 and 5000 mg/l range glycerol are precise (r.s.d. <0.005) and in fair agreement with conventional procedures. Baseline drift or noise is not observed and a thermostat water bath is not required. A noteworthy feature is the almost linear relationship between glycerol concentration and recorded peak height which is a consequence of combined effects of reaction kinetics and electrode Nernstian response.