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Supported imidazolium ionic liquid phases: A new material for solid-phase extraction

This study reports a material that is based on the concept of ionic liquid analogue: a slightly crosslinked polymer-supported imidazolium trifluoroacetate salt (IL-CF(3)COO(-)) that favorably combines the properties of ionic liquids (ILs) and the advantages of a solid support. The ionic liquid-supported material was evaluated for the first time as a solid-phase extraction (SPE) sorbent for selectively and quantitatively extracting pharmaceuticals from aqueous samples. The novel IL-CF(3)COO(-) was evaluated under reversed-phase (RP), weak anion exchange (WAX), strong anion exchange (SAX) and strong cation exchange (SCX) SPE procedures, and we found that SAX conditions are the most suitable for investigating the behaviour of the IL-CF(3)COO(-) material. Under SAX conditions, the IL-CF(3)COO(-) material was capable of selectively and quantitatively extracting a group of acidic compounds from aqueous samples, while washing basic analytes that were also present in the sample. The SPE method using IL-CF(3)COO(-) material was used to analyse 1000 ml of different aqueous samples (ultrapure, tap and river) with complete recovery of the acidic compounds studied. Moreover, the method provided clean chromatogram and high recoveries when percolating complex real samples, such as 1000 ml of river water and 250 ml of effluent wastewater from a sewage treatment plant spiked at low levels with the analytes studied.

Novel coatings for stir bar sorptive extraction to determine pharmaceuticals and personal care products in environmental waters by liquid chromatography and tandem mass spectrometry

Two new commercially available polar coatings for stir bar sorptive extraction (SBSE), consisting of polyacrylate (PA) with a proportion of polyethyleneglycol (PEG) (Acrylate Twister(®)) and PEG modified silicone (EG Silicone Twister(®)), were evaluated and compared with the classic coating based on polydimethylsiloxane (PDMS Twister(®)) for the extraction of a group of pharmaceuticals and personal care products (PPCPs) from wastewater samples. The SBSE parameters, such as sample pH, agitation speed, extraction temperature, extraction time, desorption solvent and time, were optimised in order to achieve suitable sorption of the target analytes. The EG Silicone coating enabled more efficient extraction of some polar compounds as well as improving the sorption of apolar compounds, in comparison with the other two coatings. Finally, the method of SBSE followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) using the EG Silicone coating was validated achieving good linearity (r(2)>0.994, except for CBZ (r(2)>0.989)), precision (%RSD<17%) and low limits of quantification (LOQs) (20-40 ng L(-1)). The SBSE/LC-MS/MS methodology was applied for the determination of PPCPs in wastewater samples.

Development and application of a polar coating for stir bar sorptive extraction of emerging pollutants from environmental water samples.

In the present study, a stir bar coated with hydrophilic polymer based on poly(N-vinylpyrrolidone-co-divinylbenzene) was prepared for the sorptive extraction of polar compounds. The main parameters affecting the polymerisation of the coating were investigated. The new stir bar was applied successfully in stir bar sorptive extraction with liquid desorption followed by liquid chromatography-mass spectrometry in tandem with a triple quadrupole for the determination of a group of polar pharmaceuticals and personal care products (PPCPs) in environmental water matrices. Different variables affecting extraction and desorption such as agitation speed, temperature, ionic strength and extraction time were optimised. The results showed that the stir bar is able to enrich the selected analytes effectively. The developed method was applied to determine a group of PPCPs in different complex environmental samples, including river, effluent and influent waste water.

Hydrophilic hypercrosslinked polymeric sorbents for the solid-phase extraction of polar contaminants from water.

Three new hypercrosslinked polymers with hydrophilic character arising from hydroxyl moieties in their skeletons have been prepared in microsphere format and applied to the off-line solid-phase extraction (SPE) of polar compounds from water samples. For sample volumes of 1000 ml, the recoveries of various polar pesticides, such as oxamyl, methomyl, selected phenolic compounds, as well as some pharmaceuticals, were close to 90%. The HXLPP-polar polymer with the best performance characteristics was applied to real samples. Its performance was also compared to commercially available sorbents, such as LiChrolut EN (hydrophobic, hypercrosslinked), Oasis HLB (hydrophilic, macroporous) and Isolute ENV+ (hydrophilic, hypercrosslinked); the new sorbent out-performed the commercially available sorbents. The polymer was applied successfully in off-line SPE of river water samples followed by liquid chromatography and ultraviolet detection, providing a good linear range and detection limits of 0.2 microg l(-1) for the majority of the compounds, with the exception of oxamyl, methomyl, guaiacol and salicylic acid where the detection limit was 0.5 microg l(-1).

Hypercrosslinked polymer microspheres with weak anion-exchange character : preparation of the microspheres and their applications in pH-tuneable, selective extractions of analytes from complex environmental samples

In the present study, we describe the preparation of two high-specific-surface area hypercrosslinked polymer resins (HXLPPs) in the form of monodisperse microspheres with average diameters around 6 microm, modified subsequently with two amine moieties: 1,2-ethylenediamine (EDA) and piperazine. The two resins were evaluated subsequently as weak anion-exchange (WAX) sorbents in solid-phase extraction (SPE), with the aim being to extract a group of acidic compounds from complex environmental samples and thereby free them from basic compounds, including interferences. The new hypercrosslinked sorbents with WAX capacity (HXLPP-WAX) were benchmarked against commercial, macroporous sorbents, namely Oasis-WAX and Strata-X-AW, and to the corresponding neutral sorbents, namely the HXLPP precursor, Oasis-HLB and Strata-X, with promising results. The off-line SPE method developed using the WAX sorbents was applied to Ebre river water samples and led to high recoveries of all the analytes when 500 ml of sample was applied to the cartridges, whereas lower recoveries were obtained with the neutral sorbents. The HXLPP-WAX resin modified with the EDA moiety displayed the most attractive overall performance characteristics; it was tested further with 1,000 ml of Ebre river water samples, spiked at lower levels of the analyte mixture, and with effluent waste water from a treatment plant. In both cases, the resin provided good recoveries and net chromatogram, due to the ion-exchange moieties which enable the selective extraction of target compounds.

Hypercrosslinked materials: preparation, characterisation and applications

This review article provides an overview of hypercrosslinking technology. In particular, it covers the preparation and characterisation of hypercrosslinked materials and their applications. The synthesis section examines the different monomers, precursor polymers and reagents used to prepare hypercrosslinked materials, but also the different synthetic approaches disclosed in the literature. The various chemical modification reactions relevant to this area are also reviewed. Several examples of applications for hypercrosslinked materials are described; these applications are grouped into thematic areas such as chromatography, gas storage and the trapping of organic contaminants.

Synthesis and application of hypercrosslinked polymers with weak cation-exchange character for the selective extraction of basic pharmaceuticals from complex environmental water samples

The synthesis of high specific surface area sorbents (HXLPP-WCX) in the form of hypercrosslinked polymer microspheres with narrow particle size distributions, average particle diameters around 6 microm, and weak cation-exchange (WCX) character, is described. The WCX character arises from carboxylic acid moieties in the polymers, derived from the comonomer methacrylic acid. A novel HXLPP-WCX sorbent with an attractive set of chemical and physical properties was then used in an off-line solid-phase extraction (SPE) protocol for the selective extraction of a group of basic compounds from complex environmental samples, a priority being the clean separation of the basic compounds of interest from acidic compounds and interferences. The separation power of the new sorbent for basic pharmaceuticals was compared to two commercially available, mixed-mode sorbents, namely Oasis WCX and Strata-X-CW. Under identical experimental conditions, HXLPP-WCX was found to deliver both higher capacity and better selectivity in SPE than either of the two commercially available materials. In an optimised SPE protocol, the HXLPP-WCX sorbent gave rise to quantitative and selective extractions of low microg l(-1) levels of basic pharmaceuticals present in 500 ml of river water and 250 ml of effluent waste water.

On-line solid-phase extraction coupled to hydrophilic interaction chromatography-mass spectrometry for the determination of polar drugs.

The present study describes the first fully automated method based on on-line solid-phase extraction (SPE) coupled to hydrophilic interaction chromatography-electrospray-mass spectrometry (HILIC-(ESI)MS) to determine a group of polar drugs that includes illicit drugs (such as cocaine, morphine, codeine and metabolites) and pharmaceuticals in environmental water samples. The SPE was performed using a highly retentive polymeric sorbent. The HILIC separation was optimised and the initial high organic content of the chromatographic mobile phase, was also suitable for the proper on-line elution of the analytes retained in the SPE column and for enhancing the ESI ionisation efficiency. This method allows the loading of samples of up to 250ml of ultrapure water or 10ml of environmental water samples spiked at low ngl(-1) levels of the analytes. The method yields near 100% recoveries for all the analytes. The method was also validated with environmental water samples with linear ranges from 5 to 1000ngl(-1) and limits of detection ≤2ngl(-1) for most of the compounds.

Preparation of a polar monolithic stir bar based on methacrylic acid and divinylbenzene for the sorptive extraction of polar pharmaceuticals from complex water samples.

A monolithic, hydrophilic stir bar coating based upon a copolymer of methacrylic acid and divinylbenzene [poly(MAA-co-DVB)] was synthesised and evaluated as a new polymeric phase for the stir bar sorptive extraction (SBSE) of polar compounds from complex environmental water samples. The experimental conditions for the extraction and liquid desorption in SBSE were optimised. Liquid chromatography-triple quadrupole mass spectrometry (LC-MS/MS) was used for the determination of a group of polar pharmaceuticals in environmental water matrices. The extraction performance of the poly(MAA-co-DVB) stir bar was compared to the extraction performance of a commercially available polydimethylsiloxane stir bar; it was found that the former gave rise to significantly higher extraction efficiency of polar analytes (% recovery values near to 100% for most of the studied analytes) than the commercial product. The developed method was applied to determine the studied analytes at low ng L⁻¹ in different complex environmental water samples.

Weak anion-exchange hypercrosslinked sorbent in on-line solid-phase extraction–liquid chromatography coupling to achieve automated determination with an effective clean-up☆

A mixed-mode polymeric sorbent was on-line coupled to liquid chromatography (LC) for the first time and applied to the selective solid-phase extract a group of pharmaceuticals in complex environmental water samples. The mixed-mode polymeric sorbent is a high-specific surface area hypercrosslinked polymer resin (HXLPP) in the form of monodisperse microspheres further modified with 1,2-ethylenediamine (EDA) moieties. These properties allow its application as a weak anion-exchange (WAX) sorbent in the on-line solid-phase extraction (SPE) coupling. The on-line SPE-LC method developed using the HXLPP-WAX sorbent was successfully applied to percolate a large volume of ultrapure (500 ml), river (250 ml) and effluent sewage (100 ml) water samples. In all the cases, the HXLPP-WAX resin provided near total recoveries of the most acidic compounds studied and clean chromatograms. This is because the ion-exchange interactions enable a washing step to be added to the SPE protocol that removes the compounds with weak acidic, neutral and basic properties from the sample matrix.