Bioavailability of flumequine and diclofenac in mice exposed to a metal-drug chemical cocktail. Evaluation of the protective role of selenium.

Background And Purpose: Organisms, including humans, are subjected to the simultaneous action of a wide variety of pollutants, the effects of which should not be considered in isolation, as many synergies and antagonisms have been found between many of them. Therefore, this work proposes an in vivo study to evaluate the effect of certain metal contaminants on the bioavailability and metabolism of pharmacologically active compounds. Because the most frequent entry vector is through ingestion, the influence of the gut microbiota and the possible protective effects of selenium has been additionally evaluated.

An improved microfluidic device to enhance the enrichment factors in liquid phase microextraction: application to the simultaneous extraction of polar and non-polar acids in biological samples.

A new microfluidic device to enhance the enrichment factor in miniaturized systems is proposed. The microfluidic system was design for liquid phase microextractions, and it was applied to the simultaneous extraction of acidic compounds of a wide range of polarity (0.5 < log P < 3).

Bioaccumulation and biochemical responses in the peppery furrow shell Scrobicularia plana exposed to a pharmaceutical cocktail at sub-lethal concentrations.

Pharmaceutical drugs in the aquatic medium may pose significant risk to non-target organisms. In this study, the potential toxicity of a mixture of three compounds commonly detected in marine waters (ibuprofen, ciprofloxacin and flumequine) was assessed, by studying bioaccumulation, oxidative stress and neurotoxicity parameters (catalase CAT, superoxide dismutase SOD, glutathione reductase GR, glutathione S-transferase GST, lipid peroxidation LPO, glutathione peroxidase GPX, metallothionein MT and acetylcholinesterase AChE) in the clam Scrobicularia plana. Temporal evolution of selected endpoints was evaluated throughout an exposure period (1, 7 and 21 days) followed by a depuration phase.

Monitoring of pharmaceuticals in aquatic biota (Procambarus clarkii) of the Doñana National Park (Spain).

In this work the presence of different pharmaceuticals at Doñana National Park (Spain) and their main entry sources (input source or entry points) have been stated over the 2011-2016 years period. Twenty-three selected pharmaceuticals (corresponding to eight therapeutic families) were evaluated in crayfish and water samples from Doñana National Park (Spain) (six sampling points selected in order to cover different possible pollution sources into and surrounding the Park). The multiresidue determination was carried out using enzymatic-microwave assisted extraction prior to high performance liquid chromatography mass spectrometry detection.

Assessment of pharmaceutical mixture (ibuprofen, ciprofloxacin and flumequine) effects to the crayfish Procambarus clarkii: A multilevel analysis (biochemical, transcriptional and proteomic approaches).

The knowledge about the effects of pharmaceuticals on aquatic organisms has been increasing in the last decade. However, due to the variety of compounds presents in the aquatic medium, exposure scenarios and exposed organisms, there are still many gaps in the knowledge on how mixtures of such bioactive compounds affect exposed non target organisms. The crayfish Procambarus clarkii was used to analyze the toxicity effects of mixtures of ciprofloxacin, flumequine and ibuprofen at low and high concentrations (10 and 100 μg/L) over 21 days of exposure and to assess the recovery capacity of the organism after a depuration phase following exposure during additional 7 days in clean water.

Uptake study in Juncus sp. and Salicornia europaea of six pharmaceuticals by liquid chromatography quadrupole time-of-flight mass spectrometry.

In this work, eight plants of Juncus sp. and ten of Salicornia europaea were used for an uptake assay of pharmaceuticals (flumequine, cirpofloxacin, enrofloxacin, carbamazepine, diclofenac and ibuprofen) by irrigation at three concentration levels: 10 ng mL (low level); 700 ng mL (medium level) and 10 μg mL (high level). Two plants irrigated with pharmaceutical-free water were set up as controls.

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.

Direct capillary electrophoresis analysis of basic and acidic drugs from microliter volume of human body fluids after liquid-phase microextraction through nano-fibrous membrane.

In the present work, a disposable microextraction device with a polyamide 6 nano-fibrous supported liquid membrane (SLM) is employed for the pretreatment of minute volumes of biological fluids. The device is placed in a sample vial for an at-line coupling to a commercial capillary electrophoresis instrument with UV-Vis detection (CE-UV) and injections are performed fully automatically from the free acceptor solution above the SLM with no contact between the capillary and the membrane. Up to 4-fold enrichment of model basic (nortriptyline, haloperidol, loperamide, and papaverine) and acidic (ibuprofen, naproxen, ketoprofen, and diclofenac) drugs is achieved by optimizing the ratio of the donor to the acceptor solution volumes (16 to 4 μL, respectively).

Quick Analysis of Organic Amendments via Portable X-ray Fluorescence Spectrometry.

The determination of heavy metals in soils and organic amendments, such as compost, manure, biofertilizer, and sludge, generally involves the digestion of samples with , and the determination of those in the solution using various techniques. Portable X-ray fluorescence (PXRF) has many advantages in relation to traditional analytical techniques. However, PXRF determines the total elemental content and, until now, its use for the analysis of organic amendments has been limited.

Chitosan tailor-made membranes as biopolymeric support for electromembrane extraction.

A chitosan membrane composed by 60% (w/w) chitosan and 40% (w/w) Aliquat®336 has been proposed as a new biopolymeric support for electromembrane extraction. The new support has been characterized by Scanning Electron Microscopy, resulting a 30-35 µm thickness. Amoxicillin, nicotinic acid, hippuric acid, salicylic acid, anthranilic acid, ketoprofen, naproxen and ibuprofen have been successfully extracted using the proposed support.

Simultaneous determination of metformin and glimepiride in human serum by ultra high performance liquid chromatography quadrupole time of flight mass spectrometry detection.

This work proposes a simple method for the simultaneous determination of two antidiabetic compounds, metformin and glimepiride, by ultra-high performance liquid chromatography using quadrupole time of flight mass spectrometry detection with electrospray ionization. The method was validated and shown to be linear, selective, accurate and precise. The chromatographic separation was performed using a BEH C18 column (50 mm x 2.

A New Microchip Design. A Versatile Combination of Electromembrane Extraction and Liquid-Phase Microextraction in a Single Chip Device.

For the first time, a novel and versatile microfluidic device was developed to achieve the possibility of combining different extraction principles using a miniaturized approach for the extraction of different classes of analytes. This novel microchip is composed of a sandwich of three poly(methyl methacrylate) (PMMA) layers. Four channels allowed the combination of electromembrane extraction (EME) and liquid-phase microextraction (LPME) in three different ways: (I) EME and LPME, (II) EME and EME, or (III) LPME and LPME.

Multiresidue determination of 21 pharmaceuticals in crayfish (Procambarus clarkii) using enzymatic microwave-assisted liquid extraction and ultrahigh-performance liquid chromatography-triple quadrupole mass spectrometry analysis.

In this paper, a multiresidue enzymatic-microwave assisted extraction prior to ultrahigh performance liquid chromatography and triple quadrupole mass spectrometry analysis has been developed for the determination of 21 pharmaceuticals in crayfish (Procambarus Clarkii) samples. The analysed compounds corresponding to 6 therapeutic families were: fluoroquinolones (ciprofloxacin, danofloxacin, enrofloxacin, flumequine, gatifloxacin, grepafloxacin, marbofloxacin and norfloxacin); tetracyclines (chlortetracycline and oxytetracycline); sulphonamides (sulfamethoxazole, sulfadiazine, sulfamethazine, sulfamerazine); penicillins (amoxicillin); anfenicols (chloramphenicol, thiamphenicol and florfenicol); non-steroidal anti-inflammatory drugs (ibuprofen and salicylic acid) and trimethoprim an antibiotic that is frequently co-administered with sulfamethoxazole. The main factors affecting the extraction efficiency were optimized for 0.

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).

Use of Polymer Inclusion Membranes (PIMs) as support for electromembrane extraction of non-steroidal anti-inflammatory drugs and highly polar acidic drugs.

The use of polymer inclusion membranes (PIMs) as support of 1-octanol liquid membrane in electromembrane extraction (EME) procedure is proposed. Synthesis of PIMs were optimized to a composition of 29% (w/w) of cellulose triacetate as base polymer and 71% (w/w) of Aliquat®336 as cationic carrier. Flat PIMs of 25µm thickness and 6mm diameter were used.

Liquid chromatography quadrupole time-of-flight mass spectrometry determination of six pharmaceuticals in vegetal biota. Uptake study in Lavandula dentata.

A procedure based on microwave assisted extraction for the determination of 6 pharmaceuticals in samples of Lavandula dentata, Salicornia ramosissima and Juncus sp. by liquid chromatography-quadrupole time of flight mass spectrometry (LC-QTOF/MS) was optimized and validated. Best results were obtained using microwave assisted extraction of 1.

Recent trends in capillary electrophoresis for complex samples analysis: A review.

CE has been a continuously evolving analytical methodology since its first introduction in the 1980s of the last century. The development of new CE separation procedures, the coupling of these systems to more sensitive and versatile detection systems, and the advances in miniaturization technology have allowed the application of CE to the resolution of new and complex analytical problems, overcoming the traditional disadvantages associated with this method. In the present work, different recent trends in CE and their application to the determination of high complexity samples (as biological fluids, individual cells, etc.

Recent advances in sample pre-treatment for emerging methods in proteomic analysis.

The objective of proteomics is the study of proteins (including their structure elucidation, the characterization of their role in biochemical process, the detection and identification of anomalous modifications in their structures and behavior, etc.) from both a qualitative and quantitative point of view. These studies have to face several difficulties as (a) the intrinsic complexity of protein molecules, (b) the low concentrations of the studied proteins, (c) the complexity of the biological samples (which could lead to interferences from the components of these matrixes), etc.

Easy, fast and environmental friendly method for the simultaneous extraction of the 16 EPA PAHs using magnetic molecular imprinted polymers (mag-MIPs).

An easy and environmental friendly method, based on the use of magnetic molecular imprinted polymers (mag-MIPs) is proposed for the simultaneous extraction of the 16 U.S. EPA polycyclic aromatic hydrocarbons (PAHs) priority pollutants.

New nanostructured support for carrier-mediated electromembrane extraction of high polar compounds.

A new support has been proposed to be used for carrier-mediated electromembrane extraction purposes. The new support (Tiss®-OH) is a 100µm thickness sheet nanofiber membrane manufactured by electrospinning and composed by acrylic nanofibers. It has been used in an electromembrane extraction (EME) combined with a HPLC procedure using diode array detection.

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.

Electromembrane extraction for the determination of parabens in water samples.

To our knowledge, for the first time an electromembrane extraction combined with a high-performance liquid chromatography procedure using diode-array detection has been developed for the determination of five of the most widely used parabens: ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, and benzyl 4-hydroxybenzoate. Parabens were extracted from pH 4 aqueous sample solutions with use of an Accurel® S6/2 polypropylene hollow fiber that supports a liquid membrane of 1-octanol to a pH 12 aqueous acceptor solution placed inside the lumen of the hollow fiber. An electric current of 30 V was applied over the supported liquid membrane by means of platinum wires placed in the donor and acceptor phases.

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.

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.

A novel approach for electromembrane extraction based on the use of silver nanometallic-decorated hollow fibers.

A novel approach based on the use of nanometallic-decorated hollow fibers to assist electromembrane extraction is proposed. Microporous polypropylene hollow fibers, on which nanometallic silver was deposited, have been used for the first time as liquid membrane support in electromembrane extraction (EME). Different methods for the generation/deposition of silver nanoparticles (AgNPs) were studied.