A Fast and Validated High Throughput Bar Adsorptive Microextraction (HT-BAµE) Method for the Determination of Ketamine and Norketamine in Urine Samples.

We developed, optimized and validated a fast analytical cycle using high throughput bar adsorptive microextraction and microliquid desorption (HT-BAµE-µLD) for the extraction and desorption of ketamine and norketamine in up to 100 urine samples simultaneously, resulting in an assay time of only 0.45 min/sample. The identification and quantification were carried out using large volume injection-gas chromatography-mass spectrometry operating in the selected ion monitoring mode (LVI-GC-MS(SIM)). Several parameters that could influencing HT-BAµE were assayed and optimized in order to maximize the recovery yields of ketamine and norketamine from aqueous media. These included sorbent selectivity, desorption solvent and time, as well as shaking rate, microextraction time, matrix pH, ionic strength and polarity. Under optimized experimental conditions, suitable sensitivity (1.0 µg L-1), accuracy (85.5-112.1%), precision (≤15%) and recovery yields (84.9-105.0%) were achieved. Compared to existing methods, the herein described analytical cycle is much faster, environmentally friendly and cost-effective for the quantification of ketamine and norketamine in urine samples. To our knowledge, this is the first work that employs a high throughput based microextraction approach for the simultaneous extraction and subsequent desorption of ketamine and norketamine in up to 100 urine samples simultaneously.

Bar Adsorptive Microextraction Coated with Carbon-based Phase Mixtures for Performance-Enhancement to Monitor Selected Benzotriazoles, Benzothiazoles, and Benzenesulfonamides in Environmental Water Matrices.

: In the present work we propose, for the first time, bar adsorptive microextraction coated with carbon-based phase mixtures, followed by microliquid desorption and high performance liquid chromatography-diode array detection (BAµE-µLD/HPLC-DAD) analysis, to enhance the performance of the determination of traces of benzotriazoles (BTRs), benzothiazoles (BTs), and benzenesulfonamide derivatives (BSDs) in environmental water matrices. Assessing six carbon-based sorbents (CA1, CN1, B test EUR, SX PLUS, SX 1, and R) with different selectivity properties allowed us to tailor the best phase mixture (R, 12.5%/CN1, 87.5%) that has convenient porosity, texture, and surface chemistry (pHPZC,mix ~6.5) for trace analysis of benzenesulfonamide, 1-hydroxybenzotriazole, 1H-benzotriazole, 5-methyl-1H-benzotriazole, benzothiazole, and 1,3-benzothiazol-2-ol chemicals in aqueous media. Optimized experimental conditions provided average recoveries ranging from 37.9% to 59.2%, appropriate linear dynamic ranges (5.0 to 120.0 µg L-1; r2 ≥ 0.9964), limits of detection between 1.0 and 1.4 µg L-1, and good precisions (relative standard deviation (RSD) ≤ 9.3%). The proposed methodology (BAµE(R, 12.5%/CN1, 87.5%)-µLD/HPLC-DAD) also proved to be a suitable sorption-based static microextraction alternative to monitor traces of BTRs, BTs, and BSDs in rain, waste, tap, and estuarine water samples. From the data obtained, the proposed approach showed that the BAµE technique with the addition of lab-made devices allows users to adapt the technique to use sorbents or mixtures of sorbents with the best selectivity characteristics whenever distinct classes of target analytes occur simultaneously in the same application.

Application of a bar adsorptive microextraction based methodology for doping control of alkylamine stimulants in urine matrices.

To comply with 'World Anti-Doping Agency' (WADA) guidelines, doping control laboratories must continuously adjust their analytical procedures. Therefore, sample preparation continues to play a critical step in modern analytical strategies, namely by replacing the tedious, time and solvent consuming commonly employed (e.g. liquid-liquid extraction). The present contribution proposes, for the first time in doping control, bar adsorptive microextraction (BAµE) as an alternative analytical technique for the qualitative determination of six alkyl amine stimulants (AAs; 1,3-dimethylbutylamine, 1,4-dimethylpentylamine, heptaminol, isometheptene, octodrine and tuaminoheptane) in urine matrices followed by derivatization prior to gas chromatography coupled to mass spectrometry, operating in the selected ion monitoring mode acquisition (GC-MS(SIM)). After selecting the most selective coating phase, i.e., a mixed-mode reversed phase/strong anion exchange sorbent (P2), assays performed under optimized experimental conditions [microextraction - BAµE(P2), 1 h (1,000 rpm), pH 11, 10 % NaCl; back-extraction - methanol (150 µL), 30 min, under sonication], allowed remarkable recoveries ranging from 48.7 % (heptaminol, 200 ng/mL) to 83.1 % (1,4-dimethylpentylamine, 200 ng/mL). The validation assessment assays of the proposed methodology showed suitable limits of identification (5.0-35.0 ng/mL), appropriate linear dynamic ranges (5.0-200.0 ng/mL) and good determination coefficients (r2 > 0.9937), as well as excellent selectivity, robustness, accuracy and precision. To check whether the methodology is fit-for-purpose, four previously analysed proficiency urine samples were successfully tested, in which were unequivocally detected and identified some of the target AAs. The present methodology showed to be a remarkable alternative in comparison to other dedicated analytical approaches to screen AAs in urine matrices, since it is cost-effective, user- and eco-friendly, requiring low volume of urine sample (1 mL). The great potential of this analytical technology in doping control lies in a very effective microextraction combined with the minimization of potential interferents, presenting itself as an added value to be applied to other types of substances and complex matrices.

Development of a bar adsorptive micro-extraction-large-volume injection-gas chromatography-mass spectrometric method for pharmaceuticals and personal care products in environmental water matrices.

The combination of bar adsorptive micro-extraction using activated carbon (AC) and polystyrene-divinylbenzene copolymer (PS-DVB) sorbent phases, followed by liquid desorption and large-volume injection gas chromatography coupled to mass spectrometry, under selected ion monitoring mode acquisition, was developed for the first time to monitor pharmaceutical and personal care products (PPCPs) in environmental water matrices. Assays performed on 25 mL water samples spiked (100 ng L(-1)) with caffeine, gemfibrozil, triclosan, propranolol, carbamazepine and diazepam, selected as model compounds, yielded recoveries ranging from 74% to 99% under optimised experimental conditions (equilibrium time, 16 h (1,000 rpm); matrix characteristics: pH 5, 5% NaCl for AC phase; LD: methanol/acetonitrile (1:1), 45 min). The analytical performance showed good precision (RSD < 18%), convenient detection limits (5-20 ng L(-1)) and excellent linear dynamic range (20-800 ng L(-1)) with remarkable determination coefficients (r(2) > 0.99), where the PS-DVB sorbent phase showed a much better efficiency. By using the standard addition methodology, the application of the present analytical approach on tap, ground, sea, estuary and wastewater samples allowed very good performance at the trace level. The proposed method proved to be a suitable sorption-based micro-extraction alternative for the analysis of priority pollutants with medium-polar to polar characteristics, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor PPCPs in water matrices.

Stir-bar-sorptive extraction and liquid desorption combined with large-volume injection gas chromatography-mass spectrometry for ultra-trace analysis of musk compounds in environmental water matrices.

Stir-bar-sorptive extraction with liquid desorption followed by large-volume injection and capillary gas chromatography coupled to mass spectrometry in selected ion monitoring acquisition mode (SBSE-LD/LVI-GC-MS(SIM)) has been developed to monitor ultra-traces of four musks (celestolide (ADBI), galaxolide (HHCB), tonalide (AHTN) and musk ketone (MK)) in environmental water matrices. Instrumental calibration (LVI-GC-MS(SIM)) and experimental conditions that could affect the SBSE-LD efficiency are discussed. Assays performed on 30-mL water samples spiked at 200 ng L(-1) under optimized experimental conditions yielded recoveries ranging from 83.7 ± 8.1% (MK) to 107.6 ± 10.8% (HHCB). Furthermore, the experimental data were in very good agreement with predicted theoretical equilibria described by octanol-water partition coefficients (K (PDMS/W) ≈ K (O/W)). The methodology also showed excellent linear dynamic ranges for the four musks studied, with correlation coefficients higher than 0.9961, limits of detection and quantification between 12 and 19 ng L(-1) and between 41 and 62 ng L(-1), respectively, and suitable precision (< 20%). Application of this method for analysis of the musks in real water matrices such as tap, river, sea, and urban wastewater samples resulted in convenient selectivity, high sensitivity and accuracy using the standard addition methodology. The proposed method (SBSE-LD/LVI-GC-MS(SIM)) was shown to be feasible and sensitive, with a low-sample volume requirement, for determination of musk compounds in environmental water matrices at the ultra-trace level, overcoming several disadvantages presented by other sample-preparation techniques.

Determination of short-chain carbonyl compounds in drinking water matrices by bar adsorptive micro-extraction (BAµE) with in situ derivatization.

In this contribution, bar adsorptive micro-extraction using polystyrene-divinylbenzene sorbent phase and in situ derivatization with pentafluorophenyl hydrazine, followed by liquid desorption and high-performance liquid chromatography-diode array detection (BAµE(PS-DVB)(PFPH in situ)-LD/HPLC-DAD), was developed for the determination of six short-chain carbonyl compounds (formaldehyde, acetaldehyde, propanal, acetone, butanone, and 2-hexenal) in drinking water matrices. PFPH presented very good specificity as an in situ derivatization agent for short-chain ketones and aldehydes in aqueous media, allowing the formation of adducts with remarkable sensitivity, selectivity and the absence of photodegradation. Assays performed on 30-mL water samples spiked at the 25.0 µg L(-1) levels, under optimized experimental conditions, yielded recoveries ranging from 47.4 ± 3.8% to 85.2 ± 3.8%, in which the PS-DVB proved to be a convenient sorbent phase. The analytical performance showed good accuracy, suitable precision (RSD < 13.0%), detection limits in between 47 and 132 ng L(-1) and remarkable linear dynamic ranges (r(2) > 0.9907) from 1.0 to 80.0 µg L(-1). By using the standard addition methodology, the application of the present method to drinking water samples treated with different disinfectants, namely, chloride, ozone and both, allowed very good performances to monitor these priority compounds at the trace level. The proposed methodology proved to be a feasible alternative for polar compound analysis, showing to be easy to implement, reliable, sensitive and requiring a low sample volume to monitor short-chain aldehydes and ketones in drinking water matrices.

High throughput bar adsorptive microextraction: A simple and effective analytical approach for the determination of nicotine and cotinine in urine samples.

A simple, effective, convenient and environmentally friendly methodology using high throughput bar adsorptive microextraction (HT-BAµE) with microliquid desorption in combination with large volume injection-gas chromatography-mass spectrometry operating in the selected-ion monitoring acquisition mode (LVI-GC-MS(SIM)) was applied for the determination of nicotine and cotinine in urine samples. Under optimized experimental conditions, the developed methodology allowed for linear dynamic ranges between 20.0 and 2000.0 µg L-1 with determination coefficients of 0.9991 and 0.9992, as well as average recovery yields of 61.7-67.5% and 53.9-57.8% for nicotine and cotine, respectively. The developed methodology was applied to monitor urine samples from 86 volunteers having different smoking habits, where nicotine and cotinine were quantified in the range from 23.6 to 2612.6 µg L-1. The target compounds were extracted in a HT-BAµE apparatus, which allows for simultaneous microextraction and subsequent back-extraction of up to 100 samples. This is a major improvement over other microextraction techniques. The data from the proposed methodology were satisfactory and in line with current green analytical chemistry guidelines, and proved to be an effective sample preparation alternative with substantial potential for high throughput bioanalysis.

Wild vs cultivated halophytes: Nutritional and functional differences.

Some halophyte plants are currently used in gourmet cuisine due to their unique organoleptic properties. Moreover, they exhibit excellent nutritional and functional properties, being rich in polyphenolics and vitamins. These compounds are associated to strong antioxidant activity and enhanced health benefits. This work compared the nutritional properties and antioxidant potential of three species (Mesembryanthemum nodiflorum, Suaeda maritima and Sarcocornia fruticosa) collected in saltmarshes from Portugal and Spain with those of cultivated plants. The latter were generally more succulent and had higher contents of minerals than plants obtained from the wild and contained less fibre. All species assayed are a good source of proteins, fibres and minerals. Additionally, they are good sources of carotenoids and vitamins A, C and B6 and showed good antioxidant potential particularly S. maritima. Chromatographic analysis of the phenolic profile revealed that ferulic and caffeic acids as the most relevant phenolic compounds detected in the halophytes tested.

Plant extracts with anti-inflammatory properties--a new approach for characterization of their bioactive compounds and establishment of structure-antioxidant activity relationships.

Geranium robertianum L. (Geraniacea) and Uncaria tomentosa (Willd.) DC. (Rubiaceae) plant extracts, frequently used in traditional medicine for treatment of inflammatory and cancer diseases, were studied to identify potential bioactive compounds that may justify their therapeutic use and their underlying mechanisms of action. Since some of the pharmacological properties of these plant extracts may be linked to their antioxidant potential, the antioxidant activity, in relation to free radical scavenging, was measured by the ABTS/HRP and DPPH() assays, presenting U. tomentosa the higher activity. The antioxidant activity was also evaluated by scavenging of HOCl, the major strong oxidant produced by neutrophils and a potent pro-inflammatory agent. U. tomentosa was found to be a better protector against HOCl, which may justify its effectiveness against inflammatory diseases. SPE/LC-DAD was used for separation/purification purposes and ESI-MS/MS for identification/characterization of the major non-volatile components, mainly flavonoids and phenolic acids. The ESI-MS/MS methodology proposed can be used as a model procedure for identification/characterization of unknowns without the prerequisite for standard compounds analysis. The ESI-MS/MS data obtained were consistent with the antioxidant activity results and structure-activity relationships for the compounds identified were discussed.

High throughput bar adsorptive microextraction: A novel cost-effective tool for monitoring benzodiazepines in large number of biological samples.

In this work, we propose an innovative high throughput (HT) apparatus using the bar adsorptive microextraction (BAµE) technique, which enables the simultaneous enrichment of up to 100 samples. This novel configuration was combined with microliquid desorption and high-performance liquid chromatography-diode array detection to monitor trace levels of eight benzodiazepines (diazepam, prazepam, bromazepam, oxazepam, lorazepam, alprazolam, temazepam and loflazepate) in biological samples. The proposed methodology was fully developed, optimized and validated, resulting in suitable intraday and interday precision (RSD ≤ 15%), with recovery yields ranging from 33.0% to 104.5%. The lower limits of quantification were between 20.0 and 100.0 µg L-1, using 1.0 mL of urine and 0.5 mL of plasma or serum samples. The application of the proposed methodology to real matrices resulted in average sample preparation time of around 2 min per sample, demonstrating that it is user-friendly, cost-effective and a rapid decision-making tool, whenever large number of samples are involved.

Bar adsorptive microextraction coated with multi-walled carbon nanotube phases - Application for trace analysis of pharmaceuticals in environmental waters.

Bar adsorptive microextraction devices were modified with multi-walled carbon nanotubes for the first time. A bar adsorptive microextraction method followed by microliquid desorption and high-performance liquid chromatography with diode array detection was developed for the determination of trace levels of ketoprofen, diclofenac, gemfibrozil and mefenamic acid in water samples. The mean parameters affecting the bar adsorptive microextraction and microliquid desorption efficiency were studied and optimized using a univariate optimization strategy. The methodology was validated in terms of linearity, limits of detection and quantification, recovery, intra- and inter-day precision, accuracy, and matrix effect. The developed method showed lower limits of quantification of 0.35 µg L-1, calibration curves from 0.35 up to 1000.0 µg L-1 and determination coefficients higher than 0.9917. Recoveries in tap, surface, sea and waste water samples at three spiking levels were between 70.2 and 117.3% for all the pharmaceuticals. The coefficients of variation values for intra- (n = 6) and inter-day precisions (n = 18) were below 9.7%. The proposed analytical methodology allowed preconcentration factors up to 250 and proved to be cost-effective, easy to operate and environmentally friendly.

Advances in stir bar sorptive extraction for the determination of acidic pharmaceuticals in environmental water matrices Comparison between polyurethane and polydimethylsiloxane polymeric phases.

Stir bar sorptive extraction with polyurethane (PU) and polydimethylsiloxane (PDMS) polymeric phases followed by high-performance liquid chromatography with diode array detection [SBSE(PU or PDMS)/HPLC-DAD] was studied for the determination of six acidic pharmaceuticals [o-acetylsalicylic acid (ACA), ibuprofen (IBU), diclofenac sodium (DIC), naproxen (NAP), mefenamic acid (MEF) and gemfibrozil (GEM)], selected as non-steroidal acidic anti-inflammatory drugs and lipid regulators model compounds in environmental water matrices. The main parameters affecting the efficiency of the proposed methodology are fully discussed. Assays performed on 25 mL of water samples spiked at the 10 microg L(-1) level under optimized experimental conditions, yielded recoveries ranging from 45.3+/-9.0% (ACA) to 90.6+/-7.2% (IBU) by SBSE(PU) and 9.8+/-1.6% (NAP) to 73.4+/-5.0% (GEM) by SBSE(PDMS), where the former polymeric phase presented a better affinity to extract these target analytes from water matrices at the trace level. The methodology showed also excellent linear dynamic ranges for the six acidic pharmaceuticals studied, with correlation coefficients higher than 0.9976, limits of detection and quantification between 0.40-1.7 microg L(-1) and 1.5-5.8 microg L(-1), respectively, and suitable precision (RSD <15%). Moreover, the developed methodology was applied for the determination of these target analytes in several environmental matrices, including river, sea and wastewater samples, having achieved good performance and moderate matrix effects. In short, the PU foams demonstrated to be an excellent alternative for the enrichment of the more polar metabolites from water matrices by SBSE, overcoming the limitations of the conventional PDMS phase.

New-generation bar adsorptive microextraction (BAµE) devices for a better eco-user-friendly analytical approach-Application for the determination of antidepressant pharmaceuticals in biological fluids.

The present contribution aims to design new-generation bar adsorptive microextraction (BAµE) devices that promote an innovative and much better user-friendly analytical approach. The novel BAµE devices were lab-made prepared having smaller dimensions by using flexible nylon-based supports (7.5 × 1.0 mm) coated with convenient sorbents (≈ 0.5 mg). This novel advance allows effective microextraction and back-extraction ('only single liquid desorption step') stages as well as interfacing enhancement with the instrumental systems dedicated for routine analysis. To evaluate the achievements of these improvements, four antidepressant agents (bupropion, citalopram, amitriptyline and trazodone) were used as model compounds in aqueous media combined with liquid chromatography (LC) systems. By using an N-vinylpyrrolidone based-polymer phase good selectivity and efficiency were obtained. Assays performed on 25 mL spiked aqueous samples, yielded average recoveries in between 67.8 ±â€¯12.4% (bupropion) and 88.3 ±â€¯12.1% (citalopram), under optimized experimental conditions. The analytical performance also showed convenient precision (RSD < 12%) and detection limits (50 ng L-1), as well as linear dynamic ranges (160-2000 ng L-1) with suitable determination coefficients (r2 > 0.9820). The application of the proposed analytical approach on biological fluids showed negligible matrix effects by using the standard addition methodology. From the data obtained, the new-generation BAµE devices presented herein provide an innovative and robust analytical cycle, are simple to prepare, cost-effective, user-friendly and compatible with the current LC autosampler systems. Furthermore, the novel devices were designed to be disposable and used together with negligible amounts of organic solvents (100 µL) during back-extraction, in compliance with the green analytical chemistry principles. In short, the new-generation BAµE devices showed to be an eco-user-friendly approach for trace analysis of priority compounds in biological fluids and a versatile alternative over other well-stablished sorption-based microextraction techniques.

Use of experimental design in the optimization of stir bar sorptive extraction for the determination of polybrominated diphenyl ethers in environmental matrices.

Stir bar sorptive extraction and liquid desorption (LD) followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD-LVI-GC-MS), had been applied for the determination of ultra-traces of eleven polybrominated diphenylethers (PBDEs), from tetra to nona congeners (BDE-47, BDE-100, BDE-99, BDE-85, BDE-154, BDE-153, BDE-183, BDE-197, BDE-196, BDE-207 and BDE-206), in environmental matrices. Instrumental calibration under the selected-ion monitoring (SIM) mode acquisition and parameters that could affect the SBSE-LD efficiency are fully discussed. A complete randomized factorial design was established for the first time to optimize the main experimental parameters that affecting the SBSE-LD efficiency, including decisive interactions, which provides a more realistic picture of the sampling process. The analysis of variance (ANOVA) was the statistical method used to analyze data. From the data obtained, it can be emphasized that experimental parameters such as extraction time (240 min), agitation speed (1250 rpm), methanol content (40%) and desorption conditions (acetonitrile, 15 min), were the best analytical compromise for the simultaneous determination between tetra and nona congeners in aqueous media. A remarkable recovery (65.6-116.9%) and repeatability (<12.1%) were attained, whilst the experimental data allowed very good agreement with predict theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately = K(O/W)), with the exception of nona congeners since slightly lower yields were measured. Furthermore, excellent linear dynamic ranges from 0.01 to 14.0 microg/L (r2>0.9917) and low detection limits (0.3-203.4 ng/L) were also achieved for the eleven congeners studied. The proposed methodology was applied for the determination of ultra-trace levels of PBDEs in waste water, sediments and printed board circuit matrices by the standard addition approach, showing to be reliable, sensitive and having a low sample amount requirement in compliance with the international regulatory bodies.

Development, optimisation and application of polyurethane foams as new polymeric phases for stir bar sorptive extraction.

In this contribution, polyurethane foams are proposed as new polymeric phases for stir bar sorptive extraction (SBSE). Assays performed for polyurethane synthesis demonstrated that four series of formulations (P(1), P(2), P(3) and P(4)) present remarkable stability and excellent mechanical resistance to organic solvents. For polymer clean-up treatment, acetonitrile proved to be the best solvent under sonification, ensuring the reduction of the contamination and interferences. SBSE assays performed on these polyurethane polymers followed by liquid desorption and high-performance liquid chromatography-diode array detection (LD-HPLC-DAD) or large volume injection-capillary gas chromatography-mass spectrometry (LD-LVI-GC-MS), showed that P(2) presents the best recovery yields for atrazine, 2,3,4,5-tetrachlorophenol and fluorene, used as model compounds in water samples at a trace level. SBSE(P(2)) assays performed on this polymer mixed up with several adsorbent materials, i.e. activated carbon, a mesoporous material and a calixarene, did not bring any advantages in relation with the polymeric matrix alone. The comparison between assays performed by SBSE(P(2)) and by the conventional SBSE(PDMS) showed much better performance for the former phase on aqueous samples spiked with atrazine, 2,3,4,5-tetrachlorophenol and fluorene, in which the foremost two analytes present recovery values 3- and 10-fold higher, respectively. The polyurethanes proposed as new polymeric phases for SBSE provided powerful capabilities for the enrichment of organic compounds from aqueous matrices, showing to be indicated mainly in the case of the more polar analytes.

Determination of glyoxal and methylglyoxal in environmental and biological matrices by stir bar sorptive extraction with in-situ derivatization.

Stir bar sorptive extraction with in-situ derivatization using 2,3-diaminonaphthalene (DAN) followed by liquid desorption and high performance liquid chromatography with diode array detection (SBSE(DAN)in-situ-LD-HPLC-DAD) was developed for the determination of glyoxal (Gly) and methylglyoxal (MGly) in environmental and biological matrices. DAN proved very good specificity as in-situ derivatising agent for Gly and MGly in aqueous media, allowing the formation of adducts with remarkable sensitivity, selectivity and the absence of photodegradation. Assays performed on spiked (1.0 microg L(-1)) water samples, under convenient experimental conditions, yielded recoveries of 96.2+/-7.9% for Gly and 96.1+/-6.4% for MGly. The analytical performance showed good accuracy, suitable precision (<12.0%), low detection limits (15 ng L(-1) for Gly and 25 ng L(-1) for MGly adducts) and excellent linear dynamic ranges (r2>0.99) from 0.1 to 120.0 microg L(-1). By using the standard addition method, the application of the present method to tap and swimming-pool water, beer, yeast cells suspension and urine samples allowed very good performance at the trace level. The proposed methodology proved to be a feasible alternative for routine quality control analysis, showing to be easy to implement, reliable, sensitive and with a low sample volume requirement to monitor Gly and MGly in environmental and biological matrices.

Application of polyurethane-based devices as sorption-desorption phases for microextraction analysis - The all-in-one microextraction concept.

In this work, polyurethane-based (PU) devices having cylindrical geometry soaked with suitable organic solvents are proposed for microextraction analysis. This novel analytical approach (PU microextraction; PUµE) operates under the floating sampling technology for extraction, followed by mechanical compression using a manual syringe for back-extraction. To test the performance of the PUµE method, two series of priority contaminants were used as model compounds (group #1: metalaxyl-M, penconazole and tebuconazole; group #2: atrazine, terbuthylazine, alachlor and benzo[a]pyrene) and extracted from aqueous samples followed by gas chromatography-mass spectrometry (GC-MS) analysis. The preparation of the PUµE devices and the device handling procedures are described. Also, the optimization experiments as well as the application of the new method to real matrices are discussed. Assays performed on 25mL water samples spiked at trace levels yielded average recoveries ranging from (50.1±6.7) % to (93.3±1.6) %, under optimized experimental conditions. The analytical performance showed good detection limits (0.01-0.50µg/L) and linear dynamic ranges (0.1-50.0µg/L) with acceptable determination coefficients (r2>0.9937). Excellent repeatability was also achieved in both intraday (RSD<3.5%) and inter-day (RSD<7.0%) experiments. With standard addition quantification, the proposed analytical approach revealed good sensitivity and selectivity at trace levels with absence of matrix effects for environmental water and wine samples. The PUµE technique is simple, cost-effective and very easy to apply, using an all-in-one microextraction concept.

Profiling of antioxidant potential and phytoconstituents of Plantago coronopus.

The halophyte species Plantago coronopus has several described ethnomedicinal uses, but few reported biological activities. This work carried out for the first time a comparative analysis of P. coronopus organs in terms of phenolic composition and antioxidant activity of organic and water extracts from roots, leaves and flowers. The leaves contents in selected nutrients, namely amino acids and minerals, are also described. Roots (ethyl acetate and methanol extracts) had the highest radical scavenging activity (RSA) towards 1,1-diphenyl-2-picrylhydrazyl (DPPH) and 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) radicals, while leaves (hexane extract) had higher RSA on nitric oxide radical and iron chelating ability. High performance liquid chromatography (HPLC) analysis identified eighteen phenolics from which salicylic acid and epicatechin are here firstly described in Plantago species. Leaves had mineral levels similar to those of most vegetables, proving to be a good source for elements like calcium, sodium, iron and magnesium, and also for several of the essential amino acids justifying it use as food. Our results, especially those regarding the phenolics composition, can explain the main traditional uses given to this plantain and, altogether, emphasize the potential of P. coronopus as a source of bioactive molecules particularly useful for the prevention of oxidative stress-related diseases.

Considerations on ultra-trace analysis of phthalates in drinking water.

Stir bar sorptive extraction with liquid desorption followed by large volume injection and capillary gas chromatography coupled to mass spectrometry (SBSE-LD/LVI-GC-MS), had been applied for the determination of ultra-traces of seven-phthalates (dimethyl phthalate, diethyl phthalate, di-n-butyl phthalate, butyl benzyl phthalate, bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate) in drinking water samples, which are included in the priority lists set by several international regulatory organizations. Instrumental calibration under the selected-ion monitoring mode acquisition (LVI-GC-MS(SIM)), experimental parameters that could affect the SBSE-LD efficiency, as well as, the control of the contamination profile are fully discussed. Throughout systematic assays on 30 mL water samples spiked at the 0.40 microg/L level, it had been established that stir bars coated with 47 microL of polydimethylsiloxane, an equilibrium time of 60 min (1,000 rpm) and methanol as back extraction solvent, allowed the best analytical performance to monitor phthalates in water matrices. From the data obtained, good accuracy and a remarkable reproducibility (< 14.8%) were attained, providing experimental recovery data in agreement with the theoretical equilibrium described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)), with the exception of bis(2-ethylhexyl) adipate, bis(2-ethylhexyl) phthalate and bis(1-octyl) phthalate, for which lower yields were measured. Additionally, a remarkable linear dynamic range between 25 and 2,000 ng/L (r(2)>0.99) and low detection limits (3-40 ng/L) were also achieved for the seven-phthalates studied. The application of the present method to monitor phthalates in tap and bottled mineral water samples, allowed convenient selectivity and high sensitivity up to 1.0 microg/L level, using the standard addition methodology. The proposed method showed to be feasible and sensitive with a low sample volume requirement to monitor phthalates in drinking water matrices at the ultra-trace level, in compliance with international regulatory directives on water quality.

Determination of steroid sex hormones in water and urine matrices by stir bar sorptive extraction and liquid chromatography with diode array detection.

In this study, stir bar sorptive extraction and liquid desorption followed by high performance liquid chromatography with diode array detection (SBSE-LD-HPLC/DAD) were combined for the simultaneous determination of nine steroid sex hormones (estrone, 17alpha-estradiol, 17beta-estradiol, 17alpha-ethynylestradiol, diethylstilbestrol, mestranol, progesterone, 19-norethisterone and norgestrel) in water and urine matrices. During the method development, it has been demonstrated that equilibrium time, ionic strength and back extraction solvents are the most important parameters to control, for determining the nine-hormones in water matrices, in which stir bars coated with 126 microl of polydimethylsiloxane were used. Assays performed on 30 ml water samples spiked at 10 microg/l levels under optimised experimental conditions, yielded recoveries ranging from 11.1+/-4.9% (17beta-estradiol) to 100.2+/-10.4% (mestranol), showed that the methodology is well described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)) for the latter, while pronounced deviations to the theoretical efficiency (K(PDMS/W) not equal K(O/W)) were observed for the remaining hormones. From calibration studies, a good analytical performance for all hormones was attained, including a suitable precision (2.1-17.1%), low limits of detection (0.3-1.0 microg/l) and an excellent linear dynamic range (1.25-50.0 microg/l). Assays on environmental water and urine matrices showed recovery yields in worthy good agreement with the spiking level (10 microg/l), and suitability for profiling low microg/l levels of natural hormones in urine samples taken from pregnant women. The present methodology is easy, reliable and sensitive at the trace level, only requiring a low sample volume, showing to be a good analytical alternative to routine quality control for environmental and biomedical laboratories.