A comprehensive study of a new versatile microchip device based liquid phase microextraction for stopped-flow and double-flow conditions.

A new geometry for a versatile microfluidic-chip device based liquid phase microextraction was developed in order to enhance the preconcentration in microfluidic chips and also to enable double-flow and stopped-flow working modes. The microchip device was combined with a HPLC procedure for the simultaneous determination of two different families as model analytes, which were parabens and non-steroidal anti-inflammatories (NSAIDs): Ethyl 4-hydroxybenzoate (Et-P), Propyl 4-hydroxybenzoate (Pr-P), Butyl 4-hydroxybenzoate (Bu-P), IsoButyl 4-hydroxybenzoate (iBu-P), salycilic acid (SAC), ketoprofen (KET), naproxen (NAX), diclofenac (DIC) and ibuprofen (IBU) in urine samples. The new miniaturized microchip proposed in this work allows not only the possibility of working in double-flow conditions, but also under stagnant conditions (stopped-flow) (SF-µLPME). The sample (pH 1.5) was delivered to the SF-µLPME at 20 µL min-1 while keeping the acceptor phase (pH 11.75) under stagnant conditions during 20 min. The highest enrichment factors (between 16 and 47) were obtained under stopped-flow conditions at 20 µL min-1 (sample flow rate) after 20 min extraction; whereas the extraction efficiencies were within the range of 27-81% for all compounds. The procedure provided very low detection limits between 0.7 and 8.5 µg L-1 with a sample volume consumption of 400 µL. Parabens and NSAIDs have successfully been extracted from urine samples with excellent clean up and recoveries over 90% for all compounds. In parallel, the new device was also tested under double flow conditions, obtaining good but lower enrichment factors (between 9 and 20) and higher extraction efficiencies (between 45 and 95) after 7 min extraction, consuming a volume sample of 140 µL. The versatile device offered very high extraction efficiencies and good enrichment factor for double flow and stopped-flow conditions, respectively. In addition, this new miniaturized SF-µLPME device significantly reduced costs compared to the existing analytical techniques for sample preparation since this microchip require few microliters of sample and reagents and it is reusable.

Electromembrane extraction (EME) and HPLC determination of non-steroidal anti-inflammatory drugs (NSAIDs) in wastewater samples.

In this paper, an electromembrane extraction (EME) combined with a HPLC procedure using diode array (DAD) and fluorescence detection (FLD) has been developed for the determination of six widely used non-steroidal anti-inflammatory drugs (NSAIDs): salicylic acid (SAC), ketorolac (KTR), ketoprofen (KTP), naproxen (NAX), diclofenac (DIC) and ibuprofen (IBU). The drugs were extracted from basic aqueous sample solutions, through a supported liquid membrane (SLM) consisting of 1-octanol impregnated in the walls of a S6/2 Accurel(®) polypropylene hollow fiber, and into a basic aqueous acceptor solution resent inside the lumen of the hollow fiber with a potential difference of 10 V applied over the SLM. Extractions that were carried out in 10 min using a potential of 10 V from pH 12 NaOH aqueous solutions shown concentration enrichments factors of 28-49 in a pH 12 NaOH aqueous acceptor solution. The proposed method was successfully applied to urban wastewaters. Excellent selectivity was demonstrated as no interfering peaks were detected. The procedure allows very low detection and quantitation limits of 0.0009-9.0 and 0.003-11.1 µg L(-1), respectively.

Rapid flow injection method for the determination of sulfite in wine using the permanganate-luminol luminescence system.

A simple, rapid and sensitive chemiluminescence method for the determination of sulfite has been developed by combining flow-injection analysis and its sensitizing effect on the known chemiluminescence emission produced by the oxidation of luminol in alkaline medium; in this work permanganate has been proposed as oxidizing reactive. The optimum conditions for the chemiluminescence emission were established. The chemiluminescence was proportional to the sulfite concentration over the range 1.6 × 10(-5) and 4.0 × 10(-4)mol L(-1). The detection limit was 4.7 × 10(-6)mol L(-1) of sulfite. The method has been satisfactorily used for the determination of free and bound sulfite in wines.

Hollow fiber-based liquid-phase microextraction (HF-LPME) of ibuprofen followed by FIA-chemiluminescence determination using the acidic permanganate-sulfite system.

Hollow fiber-based liquid-phase microextraction (HF-LPME) is a relatively new technique employed in analytical chemistry for sample pretreatment which offers more selectivity and sensitivity than any traditional extraction technique. This paper describes a three-phase HF-LPME method for ibuprofen using a polypropylene membrane supporting dihexyl ether followed by a chemiluminescence (CL) determination using the CL enhancement on the acidic permanganate-sulfite system in a FIA configuration which is the first time that both techniques have been combined for analytical purposes. The CL intensity (peak area) was proportional to the log of ibuprofen concentration in the donor phase over the range 0.1-20 microg mL(-1). The detection limit was 0.03 microg mL(-1) of ibuprofen in the donor phase. The method was satisfactory reproducible and has been applied to the ibuprofen determination in pharmaceuticals and in real human urine samples.