Milton K. Sasaki

Pulsed flows in flow analysis: Potentialities, limitations and applications.

In flow analysis, use of a steady and pulseless flow was considered essential for ensuring a reproducible handling of the flowing sample. To this end, peristaltic and syringe pumps have been the propelling device in the vast majority of the flow analysers. Recently, the number of applications involving pulsed flow has been increasing. Most of them refer to use of solenoid pumps, the essence of the so-called multi-pumping flow systems. This review critically discusses the characteristics, potentialities and limitations of the pulsed flow systems, emphasizing the main advantageous characteristics of the streams involved, such as high radial mass transference and good mixing of the fluids. Diverse contributions ranging from instrumentation development to analytical applications are presented.

Evidences of turbulent mixing in multi-pumping flow systems

Multi-pumping flow systems exploit pulsed flows delivered by solenoid pumps. Their improved performance rely on the enhanced radial mass transport inherent to the pulsed flow, which is a consequence of the establishment of vortices thus a tendency towards turbulent mixing. This paper presents several evidences of turbulent mixing in relation to pulsed flows, such as recorded peak shape, establishment of fluidized beds, exploitation of flow reversal, implementation of relatively slow chemical reactions and/or heating of the reaction medium. In addition, Reynolds number associated with the GO period of a pulsed flow is estimated and photographic images of dispersing samples flowing under laminar regime and pulsed flow conditions are presented.

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.

A flow system with zone merging and zone trapping in the main reactor applied to spectrophotometric catalytic determination of cobalt in grasses

A flow system with zone merging and zone trapping in the main reactor was proposed. The sample and reagent inserted aliquots merge together and the resulting zone is directed towards a displaceable reactor inside which its most concentrated portion is trapped. After the pre-set TRAP period, the handled sample is released towards detection. A comparison with an analogous flow system exploiting zone stopping revealed the superior characteristics of sampling rate and system operation; moreover, the sample inserted volume plays little influence on sampling rate. The system was applied to the spectrophotometric determination of cobalt in pastures, and enhanced figures of merit (sampling rate=18 h(-1); peak height r.s.d.=0.7%, detection limit=0.046 μg L(-1) Co; reagent consumption=330 μg of Tiron per measurement; 98%

Flow Systems with MnO2-coated Open Tubular Reactors for Spectrophotometric Determination of Ascorbic Acid in Pharmaceutical Products

ABSTRACT A novel strategy for preparing polyethylene open tubular reactors coated with MnO2(s) was pioneered for flow analysis in order to minimize the inherent drawbacks of packed solid reagents. As an application, the determination of ascorbic acid in pharmaceuticals was selected. The method involved reduction of Mn(IV) by ascorbic acid, release of the formed Mn2+ ion, reaction with formaldoxime, and spectrophotometric monitoring. The influence of flow pattern was investigated by using two similar flow systems relying on constant or pulsed flow delivered by peristaltic or solenoid pumps. With pulsed flow, system versatility and ruggedness were improved, and the analytical sensitivity (0.01143 L mg−1 ascorbic acid), detection limit (0.6 mg L−1 ascorbic acid), and sampling rate (60 h−1) evaluated compared to constant flow were improved by 2.1%, 40.0%, and 6.5%, respectively. At the same time, the reagent consumption (2.8 mg per determination) and analytical precision (relative standard deviation of approximately 2.5%) were maintained. One can conclude that the mixing conditions did not limit the analyte/reagent interaction. The results were in agreement with the British Pharmacopoeia method.

Flow-based food analysis: an overview of recent contributions

Analysis of food and beverages (e.g. determination of nutrients, additives, and contaminants) is benefited by the advantages provided by flow systems such as high precision and sampling rate, as well as low reagent consumption and waste generation. Flow manifolds have been based on several detection techniques (e.g. luminescence, spectrophotometry, electroanalysis, and mass spectrometry), and have been employed for sample handling and chemical derivatization also coupled to separation techniques. Time-consuming steps such as sample preparation and calibration, including exploitation of the standard addition method have been performed on-line in a faster and cleaner way. In addition, flow systems are advantageous for the use of modified electrodes, biosensors, and optosensors. This review is focused on the critical evaluation of the potential of selected flow-based analytical systems for food analysis, highlighting the applications after 2012.

Tracer-monitored flow titrations

The feasibility of implementing tracer-monitored titrations in a flow system is demonstrated. A dye tracer is used to estimate the instant sample and titrant volumetric fractions without the need for volume, mass or peak width measurements. The approach was applied to spectrophotometric flow titrations involving variations of sample and titrant flow-rates (i.e. triangle programmed technique) or concentration gradients established along the sample zone (i.e. flow injection system). Both strategies required simultaneous monitoring of two absorbing species, namely the titration indicator and the dye tracer. Mixing conditions were improved by placing a chamber with mechanical stirring in the analytical path aiming at to minimize diffusional effects. Unlike most of flow-based titrations, the innovation is considered as a true titration, as it does not require a calibration curve thus complying with IUPAC definition. As an application, acidity evaluation in vinegars involving titration with sodium hydroxide was selected. Phenolphthalein and brilliant blue FCF were used as indicator and dye tracer, respectively. Effects of sample volume, titrand/titrant concentrations and flow rates were investigated aiming at improved accuracy and precision. Results were reliable and in agreement with those obtained by a reference titration procedure.

Spectrophotometric flow-injection determination of sulfate in rainwater

A flow-injection system is proposed for the spectrophotometric determination of low concentrations of sulfate in rainwater using barium dimethylsulfonazo(III) (Ba-DMSA). Selectivity is enhanced by including a Dowex 1-X8 anionic resin mini-column into the manifold, aiming at sulfate in-line concentration and separation from potential interfering chemical species. The proposed system is robust and provides precise results (r.s.d. < 5.0%) at an analytical frequency of 40 h−1. About 0.09 mg DMSA is consumed per determination. The analytical curve is linear up to 2.0 mg L−1 SO42− and the detection and quantification limits were estimated as 0.01 and 0.04 mg L−1 SO42−, respectively. Results are in agreement with those obtained by ion chromatography at the 95% confidence level.

Dual thermostating in flow analysis

An advanced strategy involving concentric tubes is proposed for fast and controlled heating (or cooling) of the reaction medium in flow analysis. Different temperatures are set by sequentially circulating two thermostated water streams through the outer larged bore (2.0mm i.d.) silicone tube, which acted as a water-jacket of the inner (0.8mm i.d.) PTFE tube, and directing the sample zone to flow through it. Each end of the outer tube is connected to a three-way valve that selects the stream to flow inside it. For 25-85cm tube lengths and a 12.0mLmin-1 flow rate, the time interval required for temperature attainment, and the uniformity of temperature along the tube were evaluated. For the 85-cm tube, low differences in temperatures along the coil (1.1-8.7°C) and between programmed and attained values (2.3-13.4°C) were noted within a wide range of pre-set temperatures (15-75°C). The feasibility of the innovation in flow analysis was demonstrated in a model system relying on the iodide-nitrite reaction. The strategy allows fast (15-120s) thermostating of the reaction medium in a versatile and simple way, and is especially attractive when two controlled temperatures are set during the analytical course. Potentialities and limitations of the innovation are discussed.