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[Display omitted] • A geometry study to enhance the enrichment in chips is proposed. • A new SLM with 1:1 DHE:TBP for simultaneous extraction of basic compounds of different polarity is presented. • The versatile semi-continuous device offers high sensitivity and good enrichments. • Good recoveries and excellent clean-up were obtained from human urine samples. Liquid-phase microextraction (LPME) in microfluidic devices involves extraction of acids or bases by diffusion in a pH gradient, from aqueous sample, through a supported liquid membrane (SLM), and into aqueous acceptor phase. The SLM is an integrated part of the device, and separates the donor (sample) and acceptor phase channels. In this work, the geometry of the donor and acceptor phase channels were studied and optimized. With optimal channel geometry (12 mm length, 2 mm width, 0.12 mm depth), metoprolol, haloperidol, nortriptyline, and loperamide were extracted from 900 μL urine and into 25 μL stagnant 10 mM HCl using a mixture of dihexyl ether and tributyl phosphate 1:1 v/v as the SLM. During 30 min of extraction, where the sample was pumped into the system at 30 μL min−1 and the acceptor phase was stagnant, recoveries exceeded 75 % and enrichment factors up to 28 were obtained. Evaluation of the analytical performance supported the reliability of the device in combination with HPLC-UV detection. Implementation of LPME in microfluidic devices is expected to increase in the future and the current paper provides experimental support for the importance of the careful design of the donor and acceptor channels. [ABSTRACT FROM AUTHOR]

• A fully green microfluidic method based LPME is developed for the extraction of parabens. • A new ecological supported liquid membrane based on Ca:Ty 2:1 is proposed for the first time. • This system based on natural and biodegradable materials have proven to be an attractive alternative in sample treatment. • The microfluidic method is efficient and successfully applied in biological samples with excellent clean-up. Development of green approaches have emerged as a challenge that highlight the pressing need for nontoxic solvents, miniaturized method and bio-degradable materials. In this regard, an environmentally-friendly microfluidic system based on natural deep eutectic solvents (DESs) immobilized in agarose membranes was developed to extract parabens from urine samples for the first time. A comprehensive study of the support liquid membrane showed that only 3 µL of camphor and thymol (2:1 molar ratio) was an interesting option as a substitute for conventional (toxic) solvents used to date. Other experimental conditions were optimized and pH 4 (HCl) and 12 (NaOH) were selected as sample and acceptor solution, respectively. Both solutions (sample and acceptor) were fixed at 1 µL min−1 as flow rate. The proposed green microfluidic device was successfully applied for the determination of parabens in urine samples with relative recoveries between 86 and 100% for all analytes. Detection limits and quantitation limits were between 0.011–0.093 and 0.31–0.38 µg mL−1, respectively. Relative standard deviation was below 7% for all analytes. Furthermore, the environmentally-friendly solvent (Ca:Ty 2:1) used as SLM offered the same advantages in terms of membrane stability allowing consecutive extractions. Results were compared with experiments previously conducted using conventional (polypropylene) membranes, observing that highly green microextraction systems based on natural and biodegradable materials have proven to be an attractive alternative in microfluidic systems. [ABSTRACT FROM AUTHOR]

In liquid-phase microextraction (LPME), the sample and the acceptor are separated by a synthetic organic solvent, which is immobilized in a porous polymeric membrane of polypropylene or polyvinylidene fluoride. The organic solvent serves as extraction phase, while the polymeric membrane serves as support membrane. The combination of extraction phase and support membrane is termed supported liquid membrane (SLM). In this paper, we developed for the first time fully green and biodegradable supported SLMs, based on natural deep eutectic solvents as extraction phase and agarose as support membrane. This highly green approach was developed and studied with sulfonamide pharmaceuticals as model analytes, and performance was compared with LPME using conventional SLMs. All experiments were conducted in a microfluidic device. Model analytes were extracted from acidic sample (pH1.0) and into alkaline acceptor (pH12.0). Both sample and acceptor were pumped at 1 μL min−1 into the microfluidic device, and the optimal SLM was based on 3 µL of coumarin and thymol (1:2 molar ratio) as the extraction phase. The proposed green microfluidic device was successfully applied for the determination of sulfonamides in urine samples with spiking recoveries in the range of 77–100%. LPME with deep eutectic solvent immobilized in agarose showed similar performance as with conventional SLMs. Thus, the data presented in this paper demonstrate that highly green microextraction systems may be developed in the future, based on natural solvents and biodegradable materials. [ABSTRACT FROM AUTHOR]

[Display omitted] • A microfluidic device is proposed for the simultaneous extraction of different nature compounds. • The microdevice is small, cheap, reusable and require only 15 µL of sample volume. • Monitoring of drugs and parabens is accomplished with good extraction efficiencies in 10 min. • The procedure is successfully applied in human urine samples with good recoveries. Frequent consumption of pharmaceuticals and personal care products (PPCPs) have emerged as a current problem that highlights the pressing need for new multi-residue analytical methods that allow their simultaneous determination to assess their overall effect on human health. In this regard and for the first time, a versatile microfluidic based- liquid phase microextraction (LPME) method was developed for simultaneous monitoring of ten compounds from six different classes: amoxicillin, sulfadiazine, sulfamerazine, tiamphenicol, ethyl 4-hydroxybenzoate, flumequine, propyl 4-hydroxybenzoate, 5-hydroxydiclofenac, 3-hydroxydiclofenac and diclofenac. The microfluidic device was combined with a HPLC-UV system for the separation and determination of the model analytes in the sample. Optimal conditions were reached using 2-nitrophenyl octyl ether as supported liquid membrane, pH 3.5 as donor phase, pH 11.5 as acceptor phase, 0.5 µL min−1 as donor flow rate and 1 µL min−1 as acceptor flow rate. Under optimal method conditions, the extraction efficiency was between 85 and 100% for most compounds after 10 min extraction, and it was successfully applied in non-diluted human urine, with recoveries between 70 and 100% for all analytes except for sulfamerazine (52% recovery). In addition, the extraction of metabolites (3-hydroxydiclofenac and 5-hydroxydiclofenac) was also demonstrated in microfluidic systems with recoveries between 71 and 100% in human urine. The proposed method allowed consecutive extraction and only requires 5 µL of organic solvent and less than 15 µL of sample volume. [ABSTRACT FROM AUTHOR]

• An efficient microfluidic device is proposed for the extraction of sulfonamides. • The developed system is fast and required very low sample consumption. • Tributyl phosphate is selected as supported liquid membrane for long-term membrane stability. • The procedure is successfully applied in urine samples with extraction efficiencies over 87%. Liquid phase microextraction (LPME) into a microfluidic has undergone great advances focused on downscaled and miniaturized devices. In this work, a microfluidic device was developed for the extraction of sulfonamides in order to accelerate the mass transfer and passive diffusion of the analytes from the donor phase to the acceptor phase. The subsequent analysis was carried out by high performance liquid chromatography with UV-DAD (HPLC-DAD). Several parameters affecting the extraction efficiency of the method such as the supported liquid membrane, composition of donor and acceptor phase and flow rate were investigated and optimized. Tributyl phosphate was found to be a good supported liquid membrane which confers not only great affinity for analytes but also long-term stability, allowing more than 20 consecutive extractions without carry over effect. Under optimum conditions, extraction efficiencies were over 96 % for all sulfonamides after 10 minutes extraction and only 10 µL of sample was required. Relative standard deviation was between 3-5 % for all compounds. Method detection limits were 45, 57, 54 and 33 ng mL−1 for sulfadiazine (SDI), sulfamerazine (SMR), sulfamethazine (SMT) and sulfamethoxazole (SMX), respectively. Quantitation limits were 0.15, 0.19, 0.18 and 0.11 µg mL−1 for SDI, SMR, SMT SMX, respectively. The proposed microfluidic device was successfully applied for the determination of sulfonamides in urine samples with extraction efficiencies within the range of 86-106 %. The proposed method improves the procedures proposed to date for the determination of sulfonamides in terms of efficiency, reduction of the sample volume and extraction time. [ABSTRACT FROM AUTHOR]