Silicone rod extraction of pharmaceuticals from water

Silicone elastomer (in the form of a flexible rod) is one of the materials currently tested for use in analytical extraction techniques and passive sampling devices. We investigated the applicability of this material for the enrichment of selected polar pharmaceuticals (antipyrine, carbamazepine, diclofenac, ibuprofen, bezafibrate) from water. Time-resolved batch extraction tests (up to five weeks in duration) were performed in stirred water samples ( approximately 0.5 L) with 2-cm-long silicone rod pieces. After re-extraction of trapped compounds with methanol, analysis was performed using liquid chromatography coupled with mass spectrometry. Distribution equilibrium was reached after a test duration of seven days. The silicone rod/water partition coefficients of the investigated pharmaceuticals range from 4 (antipyrine) to 1250 (diclofenac), and are related to the hydrophobicity of the compound. Enrichment of these pharmaceuticals in the silicone rod is lower than for other compound classes (chlorinated and polycyclic hydrocarbons).     

Headspace sorptive extraction using silicone tubes for the determination of chlorobenzenes in water

A new approach for headspace sorptive extraction is presented and demonstrated for the determination of 12 chlorobenzenes in water samples. It consists of a silicone tube (15-mm length) arranged around a stainless steel rod. This device is fixed on a septum cap and exposed to the headspace of 50 mL of a salt-saturated water sample. After extraction (60-min optimized extraction time), thermodesorption is carried out by direct insertion of the silicone tube into the thermodesorption-gas chromatography-mass spectrometry system. Desorption of the analytes is performed at 250 °C for 5 min with a gas flow of 50 mL/min. Repeatability (relative standard deviation 5–10%), extraction yields (9–46%), enrichment factors (129–657), and detection limits (0.002–0.012 μg/L) were determined and four real water samples were analyzed with the headspace tube extraction. The results were verified by standard addition. A comparison of headspace tube extraction with other headspace enrichment techniques underlined the high extraction capacity of the proposed method. A big advantage of tube extraction is the low cost of the silicone material. The tubes can be discarded after single use, avoiding carryover problems and cross-contamination. Figure Scheme of the HS-tube extraction and thermodesorption system     

Characterization of silicone phases by alkaline hydrolysis and CGC analysis

A simple way to elucidate the functional group substitution on silicone chains is presented. The polymer is decomposed into its monomers by alkaline hydrolysis. These monomers are converted into trimethylsilyl derivatives, which are then analyzed and identified by capillary gas chromatography/mass spectrometry.     

A simple and inexpensive "solvent in silicone tube extraction" approach and its evaluation in the gas chromatographic analysis of pesticides in fruits and vegetables

A novel, simple, and inexpensive approach to sorptive extraction, which we call solvent in silicone tube extraction (SiSTEx), was applied to pesticide residue analysis and its effectiveness and efficiency were evaluated. In SiSTEx, which is a form of open tubular sorptive extraction, a piece of silicone tubing (4 cm long, 1.47 mm ID, 1.96 mm OD in this study) is attached to the cap of a 20 mL glass vial that contains the aqueous sample. The tubing is plugged at the end dangling in the sample solution, and MeCN (e.g., 40 microL) added by syringe to the inner tube volume through a septum in the cap. A stir-bar is used to mix the sample for a certain time (e.g., 60 min), which allows chemicals to partition into the tubing where they diffuse across the silicone and partition into the MeCN. The final MeCN extract is then analyzed for the concentrated analytes. In this study, the SiSTEx approach was evaluated for the analysis of organophosphorus (OP) and organochlorine (OC) pesticides in fruits and vegetables using GC/pulsed flame photometric (PFPD) and halogen specific (XSD) detectors for analysis. The produced samples were initially extracted by a rapid MeCN procedure, and 5 mL of the initial extract was diluted four-fold with water to undergo sorptive extraction for 60 min. The final extract was analyzed by GC/PFPD + XSD for 14 OP and 22 OC pesticides. This simple approach was able to detect 26 of the 36 pesticides at 10 ng/g or less original equivalent sample concentration with average reproducibility of 11% RSD. For those 26 pesticides, a 44-fold lower detection limit on average was achieved in matrix extracts using SiSTEx despite the four-fold dilution with water.     

Simultaneous analysis of parabens in cosmetic products by stir bar sorptive extraction and liquid chromatography

A sensitive and precise stir bar sorptive extraction (SBSE) combined with LC (SBSE/LC) analysis is described for simultaneous determination of methyl, ethyl, propyl, and butyl parabens in commercial cosmetic products in agreement with the European Union Cosmetics Directive 76/768/EEC. Important factors in the optimization of SBSE efficiency are discussed, such as time and temperature of extraction, pH, and ionic strength of the sample, matrix effects, and liquid desorption conditions by different modes (magnetic stirring, ultrasonic). The LOQs of the SBSE/LC method ranged from 30 to 200 ng/mg, with linear response over a dynamic range, from the LOQ to 2.5 μg/mg, with a coefficient of determination higher than 0.993. The interday precision of the SBSE/LC method presented a coefficient of variation lower than 5%. The effectiveness of the proposed method was proven for analysis of commercial cosmetic products such as body creams, antiperspirant creams, and sunscreens.     

Development of natural sorbent based micro-solid-phase extraction for determination of phthalate esters in milk samples

In the present study, a natural sorbent based micro-solid phase extraction (μ-SPE) was developed for determination of phthalate esters in milk samples. For the first time, an efficient and cost effective natural material (seed powder of Moringa oleifera) was employed as sorbent in μ-SPE. The sorbent was found to be naturally enriched with variety of functional groups and having a network of interconnected fibers. This method of extraction integrates different steps such as removal of proteins and fatty stuff, extraction and pre-concentration of target analytes into a single step. Thirteen phthalate esters were selected as target compounds for the development and evaluation of method. Some key parameters affecting the extraction efficiency were optimized, including selection of membrane, selection and amount of sorbent, extraction time, desorption solvent, volume of desorption solvent, desorption time and effect of salt addition. Under the optimum conditions, very good linearity was achieved for all the analytes with coefficient of determinations (R²) ranging between 0.9768 and 0.9977. The limits of detection ranged from 0.01 to 1.2 μg L⁻¹. Proposed method showed satisfactory reproducibility with relative standard deviations ranging from 3.6% to 10.2% (n = 7). Finally, the developed method was applied to tetra pack and bottled milk samples for the determination of phthalate esters. The performance of natural sorbent based μ-SPE was better or comparable to the methods reported in the literature.     

Gas purge-microsyringe extraction: A rapid and exhaustive direct microextraction technique of polycyclic aromatic hydrocarbons from plants

Gas purge-microsyringe extraction (GP-MSE) is a rapid and exhaustive microextraction technique for volatile and semivolatile compounds. In this study, a theoretical system of GP-MSE was established by directly extracting and analyzing 16 kinds of polycyclic aromatic hydrocarbons (PAHs) from plant samples. On the basis of theoretical consideration, a full factorial experimental design was first used to evaluate the main effects and interactions of the experimental parameters affecting the extraction efficiency. Further experiments were carried out to determine the extraction kinetics and desorption temperature-dependent. The results indicated that three factors, namely desorption temperature (temperature of sample phase) T_d, extraction time t, and gas flow rate u, had a significantly positive effect on the extraction efficiency of GP-MSE for PAHs. Extraction processes of PAHs in plant samples followed by first-order kinetics (relative coefficient R² of simulation curves were 0.731–1.000, with an average of 0.958 and 4.06% relative standard deviation), and obviously depended on the desorption temperature. Furthermore, the effect of the matrix was determined from the difference in E_app,d. Finally, satisfactory recoveries of 16 PAHs were obtained using optimal parameters. The study demonstrated that GP-MSE could provide a rapid and exhaustive means of direct extraction of PAHs from plant samples. The extraction kinetics were similar that of the inverse process of the desorption kinetics of the sample phase.     

Simultaneous liquid–liquid microextraction and polypropylene microporous membrane solid-phase extraction of organochlorine pesticides in water,tomato and strawberry samples

A procedure involving the simultaneous performance of liquid–liquid microextraction and polypropylene microporous membrane solid-phase extraction was carried out. The applicability of the proposed procedure was evaluated through extraction of several organochlorine pesticides from river water, tomato and strawberry samples. The parameters affecting the extraction efficiency were optimized by multivariable designs, and the analytical features were estimated. Under optimized conditions, analytes were concentrated onto 1.5 cm long microporous membranes placed directly into the sample containing 15 mL of water with 20 μL of 1-octanol. The best extraction conditions were achieved at 59 °C, with 60 min of extraction time and 2.91 g of sodium chloride. The desorption of the analytes was carried out using 30 μL of a mixture of toluene and hexane in the proportion of 60:40% (v/v) for 10 min. Detection limits in the range of 2.7–20.0 ng L⁻¹, 0.50–1.15 μg kg⁻¹, and 1.53–12.77 μg kg⁻¹ were obtained for river water, strawberry and tomato samples, respectively. Good repeatability was obtained for all three sample types. The results suggest that the proposed procedure represents a very simple and low-cost microextraction alternative rendering adequate limits of quantification for the determination of organochlorine pesticides in environmental and food samples.     

Silicone glue coated stainless steel wire for solid phase microextraction

A new solid phase microextraction (SPME) fiber based on high-temperature silicone glue coated on a stainless steel wire is presented. The fiber coating can be prepared easily in a few minutes, it is mechanically stable and exhibits relatively high thermal stability (up to 260 °C). The extraction properties of the fiber to benzene, toluene, ethylbenzene, and xylenes (BTEX) were examined using both direct and headspace SPME modes coupled to gas chromatography-flame ionization detection. The effects of the extraction and desorption parameters including extraction and desorption time, sampling and desorption temperature, and ionic strength on the extraction/desorption efficiency have been studied. For both headspace and direct SPME the calibration graphs were linear in the concentration range from 0.5 μg L⁻¹ to 10 mg L⁻¹ (R² > 0.996) and detection limits ranged from 0.07 to 0.24 μg L⁻¹. Single fiber repeatability and fiber-to-fiber reproducibility were less than 6.8 and 21.5%, respectively. Finally, headspace SPME was applied to determine BTEX in petrol station waste waters with spiked recoveries in the range of 89.7-105.2%.     

Approaches for on-line coupling of extraction and chromatography

This review provides an overview of the approaches available in order to perform on-line coupling of various extraction techniques with liquid and gas chromatography, for the analysis of semivolatile and nonvolatile analytes in liquid and solid samples. The main focus is on the instrumental set-up of these techniques. Selected real applications are described by way of illustration. The extraction methods suitable for on-line coupling covered in this review are: liquid-liquid extraction, solid-phase extraction, membrane-based techniques, pressurised liquid extraction, supercritical fluid extraction, and microwave- and sonication-assisted extractions. The following systems are not covered in this review: on-line coupled solid-phase extraction-liquid chromatography, purge-and-trap-GC, and membrane extraction with a sorbent interface-GC.Abbreviations DMAE Dynamic microwave-assisted extraction - DSAE Dynamic sonication-assisted extraction - FIA Flow injection analysis - FID Flame ionisation detection - GC Gas chromatography - HGAAS Hydride generation atomic absorption spectroscopy - IC Ion chromatography - IPLC Ion pair liquid chromatography - LC Column liquid chromatography - LLE Liquid-liquid extraction - LVI Large-volume injection - MAE Microwave-assisted extraction - MESI Membrane extraction with a sorbent interface - MMLLE Microporous membrane liquid-liquid extraction - MS Mass spectrometry - NP Normal-phase - OTT Open-tubular trapping - OTTTD Open-tubular trapping with thermal desorption - PAH Polycyclic aromatic hydrocarbon - PHWE Pressurised hot water extraction - PCB Polychlorinated biphenyl - PLE Pressurised liquid extraction - PTV Programmed-temperature vaporizer - RP Reversed-phase - RSD Relative standard deviation - SAE Sonication-assisted extraction - SFE Supercritical fluid extraction - SIM Selective ion monitoring - SLM Supported liquid membrane - SPE Solid-phase extraction - SPE-TD Solid-phase extraction-thermal desorption - SVE Solvent vapour exit - TD Thermal desorption     

有序纳米线/棒/管阵列材料的研究进展

概述了有序纳米线/棒/管阵列的性质、应用及制备方法的研究进展,着重介绍了有序纳米线/棒/管阵列材料的制备方法如气相-液相-固相生长法、气相-固相生长法、模板法和溶剂热法,以及阵列材料在磁、场发射、激光、电化学、光电化学和催化方面所具有的独特性质与应用,展望了该领域的研究前景。     

Microextraction of volatile compounds from wine samples and their determination by GC-FID. The effect of the salts and extraction solvents used

Summary This study describes the optimization of microextraction as a method for extracting volatile compounds from wine. The study has been applied to twelve compounds present in wine: 3-methylbutyl acetate, 3-methyl-1-butanol, ethyl hexanoate, hexanol, ethyl octanoate, butanoic acid, ethyl decanoate, diethyl succinate, hexanoic acid, phenylethanol, octanoic acid, and decanoic acid. These compounds were selected from those identified by GC-MS analysis of a real wine sample. By means of a synthetic wine, the study investigated the influence on extraction yield of the solvents and salts used, the proportion of salts, and the agitation time. The determination was performed by GC with flame ionization detection and an internal standard was used for quantification. The method was applied to samples of white wine from La Rioja.     

Preparation and properties of surface modified ceramic membranes. Part II. Gas and liquid permeabilities of 5 nm alumina membranes modified by a monolayer of bound polydimethylsiloxane (PDMS) silicone oil

A new way to prepare hydrophobic membranes is reported. Polydimethylsiloxane oil (and any other silicone oil molecules) was grafted onto a porous alumina membrane (or any hydroxylated ceramic or glass) by heating, to 180°C, producing a covalently grafted monolayer of silicone oil, chemically and thermally stable, unaffected by organic solvents but susceptible to alkali attack (as is the silicone oil itself). The membrane is totally impermeable to pure water, and organic solvents may be extracted from water mixtures by pervaporation. Very high permeation fluxes were obtained, suggesting possible use of these silicone/ceramic membranes in extraction of volatile organic compounds (VOCs). This simple modification can be applied to macroporous membranes increasing hydrophobicity without pore blocking.     

Sorbent- and liquid-phase microextraction techniques and membrane-assisted extraction in combination with gas chromatographic analysis: A review

Approaches are described for on-line and off-line sample pretreatment of liquid samples utilising liquid- and adsorbent- and sorbent-phase microextraction methodologies with GC analysis. Solid-phase microextraction (SPME), stir-bar sorptive extraction (SBSE), on-line solid-phase extraction (SPE), liquid-phase microextraction (LPME) and membrane-assisted methods are critically evaluated and the applicability of each technique is demonstrated with examples.     

Stir rod sorptive extraction with monolithic polymer as coating and its application to the analysis of fluoroquinolones in honey sample

A stir rod sorptive extraction (SRSE) with monolithic polymer as coating was proposed to avoid the friction loss of coating during the stirring process. In our study, poly(2-acrylamide-2-methylpropanesulfonic acid-co-octadecyl methacrylate-co-ethylene glycol dimethacrylate) [poly(AMPS-co-OCMA-co-EDMA)] monolithic polymer was used as a coating of SRSE. The effect of concentration of porogen on SRSE performance was studied. Four fluoroquinolones (FQs) were selected as testing analytes to evaluate the extraction efficiency of SRSE. To achieve the optimum extraction conditions of SRSE towards FQs, several parameters, including extraction time, extraction temperature, stirring rate, sample solution pH and contents of inorganic salt in the sample solution were investigated. Under the optimized conditions of SRSE, a method for the determination of FQs in honey sample was proposed based on the combination of SRSE with liquid chromatography and electrospray ionization mass spectrometry (SRSE/LC/ESI-MS). The detection limits (LODs) of the proposed method for four FQs ranged from 0.06 to 0.14 ng/g and the recoveries were in the range of 70.3–122.6% at different concentrations for honey samples. Good method reproducibility was found as intra- and inter-day precisions, yielding the relative standard deviations less than 11.9% and 12.4%, respectively. The results show that SRSE with poly(AMPS-co-OCMA-co-EDMA) monolithic polymer as coating possessed good extraction capacity towards FQs in honey samples. Finally, the monolithic polymer coated stir rod was demonstrated to be reused at least 60 times.     

Stir bar sorptive extraction coupled to liquid chromatography for the analysis of strobilurin fungicides in fruit samples

A stir bar microextraction (SBSE) procedure for the determination of seven strobilurin fungicides in fruit samples using liquid chromatography (LC) and diode array detection (DAD) has been developed. The samples were sonicated in the presence of ethanol before submitting the extracts to SBSE. The incorporation of drazoxolon as an internal standard before SBSE allowed calibration without the need to use the standard additions method. Under the optimized conditions, detection limits were in the 0.3–2 ng g⁻¹ range, corresponding to trifloxystrobin and metominostrobin, respectively. The SBSE–LC–DAD procedure showed good repeatability (RSD below 11% in all cases) and provided recoveries of 80–105% from spiked samples. The method was applied to fifteen fruit samples, and low levels of pyraclostrobin and trifloxystrobin were found in two of them.     

Stir-bar sorptive extraction: A view on method optimisation,novel applications,limitations and potential solutions

Introduced in 1999 as a novel solventless sample preparation method, stir-bar sorptive extraction (SBSE) has become a popular analytical technique for the pre-concentration of organic compounds into a polydimethylsiloxane (PDMS)-coated stir-bar. In the last 10 years, hundreds of applications in the environmental, food and biomedical fields can be found in the literature. However, only PDMS-coated stir-bars are commercially available, which reduces the applicability of SBSE to the extraction of the non-polar compounds due to the poor extractability of more polar analytes. In this review, a view on method optimisation, limitations, potential solutions such as in-house coatings and derivatisation and novel applications in multi-residue analysis and passive sampling are revised.     

Speciation of methyltins by dispersive liquid–liquid microextraction and gas chromatography with mass spectrometry

Dispersive liquid–liquid microextraction in combination with an in situ derivatization is suggested for methyltin compound sampling and preconcentration from water solutions. The derivatization was carried out with sodium tetraethylborate at pH 3. The effects of extraction and disperser solvents type, volume, and extraction time on the extraction efficiency were investigated. 1,2‐Dichlorobenzene was used as an extraction solvent and ethanol was used as a disperser solvent. The calibration graphs for all the analytes were linear up to 2 μg (Sn) L^?1, correlation coefficients were 0.998–0.999, LODs were 0.13, 0.05, and 0.06 ng (Sn) L^?1 for trimethyltin, DMT, and monomethyltin, respectively. Repeatabilities of the results were acceptable with RSDs up to 12.1%. A possibility to apply the proposed method for methyltin compound determination in water samples was demonstrated.     

Gas chromatographic determination of some phenolic compounds in fuels and engine oil after simultaneous derivatization and microextraction

In this study, a simultaneous derivatization/air‐assisted liquid–liquid microextraction method has been developed for sample preparation of some phenolic compounds in fuels and engine oil. Analytes are transferred by back liquid–liquid extraction into NaOH solution and then are derivatized with butyl chloroformate and extracted simultaneously into carbon tetrachloride. The extracted derivatized analytes are analyzed using gas chromatography with flame ionization detection. The effect of extracting solvent type, derivatization agent and extraction solvent volumes, ionic strength of the aqueous solution, number of extraction cycles, etc., on the extraction efficiency is investigated. The calibration graphs are linear in the range of 3–10 000 μg/L. Enhancement factors, enrichment factors, and extraction recoveries are in the ranges of 497 to 1471, 571 to 991, and 60 to 109%, respectively. Detection limits are obtained in the range of 0.8 to 2.0 μg/L. Relative standard deviations for the extraction of each selected phenols are in the ranges of 2–4% for intraday (n = 6) and 3–6% (n = 5) for interday precisions for 200 μg/L. This technique is successfully applied for the extraction, preconcentration, and determination of the selected phenols in gasoline, kerosene, gas oil, and engine oil.