Solid supports and supported liquid membranes for different liquid phase microextraction and electromembrane extraction configurations. A review.

Liquid phase microextraction (LPME) and electromembrane microextraction (EME) can be considered as two of the most popular techniques in sample treatment today. Both techniques can be configurated as membrane-assisted techniques to carry out the extraction. These supports provide the required geometry and stability on the contact surface between two phases (donor and acceptor) and improve the reproducibility of sample treatment techniques. These solid support pore space, once is filled with organic solvents, act as a selective barrier acting as a supported liquid membrane (SLM). The SLM nature is a fundamental parameter, and its selection is critical to carry out successful extractions. There are numerous SLMs that have been successfully employed in a wide variety of application fields. The latter is due to the specificity of the selected organic solvents, which allows the extraction of compounds of a very different nature. In the last decade, solid supports and SLM have evolved towards "green" and environmentally friendly materials and solvents. In this review, solid supports implemented in LPME and EME will be discussed and summarized, as well as their applications. Moreover, the advances and modifications of the solid supports and the SLMs to improve the extraction efficiencies, recoveries and enrichment factors are discussed. Hollow fiber and flat membranes, including microfluidic systems, will be considered depending on the technique, configuration, or device used.

A Method for the Determination of Veterinary Drugs from Different Therapeutic Classes in Animal Urine.

A rapid, precise and robust HPLC separation procedure has been developed and optimized for the determination of a series of drugs of different therapeutic classes: chlortetracycline, oxitetracycline, cefoperazone, diclofenac, tiamphenicol, marbofloxacin, ciprofloxacin, danofloxacin, enrofloxacin and flumequine. The chromatographic method used a monolithic C18 column and both diode array and fluorescence detection. This procedure was validated for the analysis of drugs in cow urine, using a simple and fast procedure with methanol/acetonitrile, allowing the simultaneous and efficient extraction of most of the studied drugs. The proposed method was successfully applied to the determination of enrofloxacin in cow urine, collected after the administration of this antibiotic.

New developments in microextraction techniques in bioanalysis. A review.

In recent years, the interest in new extraction methods with lower sample volume requirements, simpler equipment and handling, and lower reagent consumption, has led to the development of a series of microextraction methods based on extraction phases in the microliter order. Nowadays, many references can be found for several of these methods, which imply a wide range of applications referred to both the analyte and the sample nature. In this paper, recent developments in both well-established microextraction techniques (solid phase microextraction, hollow-fiber liquid phase microextraction, dispersive liquid-liquid microextraction, etc.) and recently appeared microextraction procedures (nanoextraction systems, microchip devices, etc.) for the clinical analysis of biological samples will be reviewed and discussed.

New developments in the extraction and determination of parabens in cosmetics and environmental samples. A review.

Parabens are a family of synthetic esters of p-hydroxibenzoic acid widely used as preservatives in cosmetics and health-care products, among other daily-use commodities. Recently, their potential endocrine disrupting effects have raised concerns about their safety and their potential effects as emerging pollutants, leading to the regulation of the presence of parabens in commercial products by national and trans-national organizations. Also, this has led to an interest in developing sensible and reliable methods for their determination in environmental samples, cosmetics and health-care products. This paper is a comprehensive up-to-date review of the literature concerning the determination of parabens in environmental samples and cosmetic and health-care products. A brief revision of the literature concerning the traditional determination of parabens (1980-2003) is included, followed by an in-depth revision of the recent developments in both measurement and extraction methods for parabens in the last years (2003-2013). Finally, possible future perspectives in this field are proposed.

Agar films containing silver nanoparticles as new supports for electromembrane extraction.

A new support containing silver nanoparticles to assist electromembrane extraction (EME) procedures is proposed. For the first time, synthesized agar films containing silver nanoparticles (AgNPs) have been used as a support for liquid membranes in EME. Agarose films of 20 µm thickness containing 107.9 mg Ag/g agar were synthesized and characterized by transmission electron microscopy (TEM) and atomic force microscopy (AFM), showing isolated spherical silver nanoparticles of 20-30 nm diameter with homogeneous distribution. Nanometallic films were cut and glued to narrow bore glass tubes and used as supports for a dihexyl ether liquid membrane for use in an EME procedure. EME conditions were optimized and applied to the extraction of selected non-steroidal anti-inflammatory drugs (NSAIDs). The results were compared to those using polypropylene membranes (450 µm and 100 µm thickness), achieving 10- to 70-fold higher extraction efficiency. This article opens a new line of research into electrically assisted microextraction systems by combining other possible kinds of nanometallic films, including different metals, film functionalization through metallic NPs, and the use of low polarity solvents. Also, very low currents are obtained during the extraction process, which lead to high electromigration of the analytes.

Hollow-fiber liquid-phase microextraction for the direct determination of flumequine in urban wastewaters by flow-injection analysis with terbium-sensitized chemiluminescence.

A flow-injection analysis chemiluminescence method based on the enhancement effect of the flumequine-Tb(III) complex on the weak native emission of the Ce(IV)-Na2SO3 system has been developed for the determination of flumequine. The method includes a cleanup and preconcentration stage (750-fold) of the sample by hollow-fiber liquid-phase microextraction using an Accurel(®) Q 3/2 polypropylene hollow fiber impregnated with 1-octanol as the supported liquid membrane. The obtained 50 µL acceptor phase was injected in a 1 mM Tb(III) + 4 mM Ce(IV) in 5% v/v H2 SO4 stream and mixed with a 2 mM Na2 SO3 stream before its introduction into the flow cell. The chemiluminescence signal was linear in the 0.3-15 ng/mL range, with detection and quantitation limits of 0.1 and 0.3 ng/mL, respectively. The method allows the selective extraction and determination of flumequine in wastewater samples, using simpler and lower-cost instrumentation and with shorter extraction and analysis times than traditional high-performance liquid chromatography analysis.

Application of chemiluminescence in the analysis of wastewaters - a review.

The toxicological effects of diverse pollutants typically found on wastewaters of diverse origin (industrial, urban, etc.) have led to regulation of their emission by national and trans-national organizations, and an increasing interest in the development of fast and reliable methods for their analysis. This paper is an up-to-date comprehensive review on the analytical applications of chemiluminescence technique (characterized by high sensitivity, wide dynamic ranges and simple instrumentation) to the analysis of wastewaters, emphasizing the different kinds of pollutants that have been studied with these methods and discussing the different approaches followed by the authors as CL reactions, devices and coupled methods.