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Multi-signal calibrations have been recently exploited in molecular spectrochemical analysis alternatively to traditional calibration methods, improving analytical frequency and accuracy. The application of these strategies is simple and minimizes efficiently matrix effects by analyzing two calibration solutions comprising sample plus standard (S1), and sample plus blank (S2). The plot of the signals obtained with S1 and S2 at multiple settings (e.g. different wavelengths) yield a slope that can be related to the analyte concentration in the sample. Similarly, transient signals could also be related to the analyte concentration exploiting a similar strategy. Thus, in this work, two multi-signal approaches developed in flow-based systems are proposed, based on the responses at multiple wavelengths (online multi-energy calibration, OMEC), and on the dispersion profile of the samples, herein denominated multi-dispersion calibration (MDC). The calibrations were carried out with sample solutions after 2-fold dilution with a standard solution and with water. The feasibility of OMEC and MDC were demonstrated using KMnO4 solutions (without chemical reactions) under continuous and pulsed flow regimes. The applicability of this strategy was also demonstrated by the spectrophotometric determination of urea in milk and pet potty spray in a multi-pumping flow system, based on the color change of bromothymol blue after catalyzed hydrolysis by urease from jack beans (Canavalia ensiformis). MDC and OMEC were compared with external calibrations (EC) and classical standard addition. The limits of detection for urea were estimated at 13 mg L-1, 16 mg L-1, and 10 mg L-1 using MDC, MEC and EC, respectively. Recoveries from 93 to 101%, and the agreement of sample analyzes with the reference procedure demonstrated the good accuracy achieved by the proposed methods. Therefore, it was demonstrated the feasibility of MDC and OMEC for analytical purposes in a simple and efficient way with the advantages of flow-based manifolds.

RESUMEN

Biodiesel is an important alternative fuel produced from animal fats or vegetable oils. According to several world regulatory agencies, the acceptable threshold content for free glycerol in biodiesel is 200 mg kg-1. Exceeding concentrations may yield high amounts of acrolein after combustion. The analytical methods for glycerol determination are usually preceded by conventional liquid-liquid extraction that may affect precision and accuracy and impair analytical frequency. In this work, a multi-pumping flow system was proposed for the online dispersive liquid-liquid extraction of free glycerol from biodiesel followed by spectrophotometric determination. The analyte was transferred to the aqueous phase by mixing the sample and water under a pulsed flow regime. The emulsion was directed towards a retention column to remove the organic phase before chemical derivatization. Glycerol was oxidized by NaIO4 to generate formaldehyde, which reacted with acetylacetone in an ammonium acetate medium to yield 3,5-diacetyl-1,4-dihydrolutidine (λMAX = 412 nm). The optimization of the main parameters of the system was carried out by multivariate methods. The screening of variables was performed by fractional factorial design 24-1. The models for free glycerol determination and extraction were refined by central composite and full factorial 23, respectively. In both cases, the validation was carried out by analysis of variance, which yielded a satisfactory F-test value. After optimization, a linear range from 3.0 to 50.0 mg L-1 glycerol was observed. The detection limit, coefficient of variation and determination frequency were estimated to be 2.0 mg L-1 (n = 20; 99.7% confidence level), 4.2-6.0% (n = 20) and 16 h-1, respectively. The efficiency of the process was estimated to be 66%. After each extraction, the retention column (filled with 185 mg of glass microfiber) was washed with 50% ethanol solution to avoid carry-over effects. The comparative analyses of samples by the proposed and reference methods demonstrated the accuracy of the developed procedure at a 95% confidence level. Recoveries between 86 and 101% also indicated that the proposed procedure is accurate, suitable and reliable for online extraction and determination of free glycerol in biodiesel.

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RESUMEN

Drug quality assessment and stress testing are important to ensure both treatment efficacy and patient safety. High performance liquid chromatography may be considered a standard technique for pharmaceutical analysis, showing good precision and accuracy, but it also involves relatively high cost and low analytical frequency. Flow injection analysis presents high sample throughput, lower cost and might be used for selective drug analysis with an appropriate assay and/or detector. In this paper, for the first time, photoreactions promoted by UV radiation were employed for reagentless spectrophotometric determination of hydrochlorothiazide. Optimized parameters led to a linear range of 50 to 500 mg L-1, estimated limit of detection of 3.0 mg L-1 and 24 determinations per hour. The use of diluted NaOH solution as a carrier allowed solubilization of hydrochlorothiazide and analysis without organic solvents. The presence of the most common excipients was evaluated and no significant interferences were observed. The results from the analysis of samples by the proposed and by the reference procedures demonstrated accuracy and matching results. The proposed in-line photolysis of the pharmaceutical, performed in 5 min, is a promising alternative to the conventional hydrolytic forced degradation, which requires elevated temperature and prolonged time period. To evaluate the degree of photoconversion, a capillary zone electrophoresis method was developed, which performed well for separations manifesting good analytical frequency and reduced amount of waste. The combination of in-line photodegradation followed by separation by capillary electrophoresis is a promising approach for the stress test of hydrochlorothiazide in pharmaceutical formulations.

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