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 μg 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 μg l-1

Synthesis and Evaluation of Four Novel Stationary Phases in High Pressure Liquid Chromatography

High pressure liquid chromatography is one of the most frequently used methods for the separation of mixtures. Chemically modified silica hydride stationary phases, due to their unique selectivity and versatility, have been the focus of an increasing number of studies in the past several years. The objective of fabricating stationary phases with dual properties is to achieve separation of both polar and non-polar components in a single analysis. Due to an increasing demand in the fields of drug discovery, proteomics, and metabolomics to analyze numerous samples with a wide range of polarities, there is a need for more versatile stationary phases for a wide range of applications. In order to meet the above objective, in this research four novel silica hydride-based columns were synthesized using a hydrosilation procedure. The characterization of each column was done using a series of polar and nonpolar compounds by studying their aqueous normal phase and reversed-phase chromatographic behavior. Under these conditions, it turned out that two columns showed both RP and ANP behaviors. Of the remaining columns, one exhibited ANP behavior only and the other performed only in the reversed-phase mode

Vapor Sensing Characteristics of Nanoelectromechanical Chemical Sensors Functionalized Using Surface-Initiated Polymerization

Surface-initiated polymerization has been used to grow thick, uniform poly(methyl methacrylate) films on nanocantilever sensors. Cantilevers with these coatings yielded significantly greater sensitivity relative to bare devices as well as relative to devices that had been coated with drop-cast polymer films. The devices with surface-initiated polymer films also demonstrated high selectivity toward polar analytes. Surface-initiated polymerization can therefore provide a straightforward, reproducible method for large-scale functionalization of nanosensors

Evaluation of a Silica Hydride Based Diol Stationary Phase For High Pressue Liquid Chromatogrphy

The impact of chromatography across many scientific fields and applications is limitless. It is a vital everyday separation, characterization, and purification tool for many scientists worldwide. Innovations in high performance liquid chromatography (HPLC) stationary phases have led to more diverse separations essential to many fields including the pharmaceutical industry and research. Silica hydride based stationary phases have been shown to display both reverse phase (RP) and aqueous normal phase (ANP) chromatographic behavior. This is a result of both the silica hydride surface and the bonded phase. The goal of this work was to characterize silica hydride based diol stationary phases for HPLC. A wide range of compounds with varying polarities were analyzed. Retention was observed under ANP and RP conditions. Two representative silica hydride based diol stationary phases were compared to demonstrate the effect that the length of the bonded phase has on the separation capabilities of the column. The diol bonded phase with a longer carbon chain retained analytes with more hydrophobic (or non-polar) characteristics longer than analytes with more hydrophilic properties. As part of a larger study the effect of buffer concentration on the ANP retention of model compounds was investigated. Retention dramatically decreased when the concentration of some buffers was increased. This trend is opposite of what has been observed in hydrophilic interaction liquid chromatography (HILLIC), indicating a clear distinction in the retention mecahism for HILLIC and ANP

ATR-FTIR Spectroscopic Analysis of Sorption of Aqueous Analytes into Polymer Coatings Used with Guided SH-SAW Sensors

Attenuated total internal reflectance Fourier transform infrared (ATR-FTIR) spectroscopy was used for the investigation of sorption of aqueous solutions of analytes into polymer coatings. A series of simple model polymers, such as poly(dimethylsiloxane), poly(epichlorhydrin), and poly(isobutylene), and films and analytes, such as aqueous solutions of ethylbenzene, xylenes, toluene, and nitrobenzene, were used to evaluate the use of ATR-FTIR spectroscopy as a screening tool for sensor development. The ratios of integrated infrared absorption bands provided a simple and efficient method for predicting trends in partition coefficients. Responses of polymer-coated guided shear horizontal surface acoustic wave (SH-SAW) sensor platforms to the series of analytes, using polymer coatings with similar viscoelastic properties, were consistent with ATR-FTIR predictions. Guided SH-SAW sensor responses were linear in all cases with respect to analyte concentration in the tested range. Comparison of ATR-FTIR data with guided SH-SAW sensor data identifies cases where mass loading is not the dominant contribution to the response of the acoustic wave sensor. ATR-FTIR spectra of nitrobenzene, coupled with computational chemistry, provided additional insight into analyte/polymer interactions

A rapid and versatile microfluidic method for the simultaneous extraction of polar and non-polar basic pharmaceuticals from human urine

In sample preparation, simultaneous extraction of analytes of very different polarity from biological matrixes represents a challenge. In this work, verapamil hydrochloride (VRP), amitriptyline (AMP), tyramine (TYR), atenolol (ATN), metopropol (MTP) and nortriptyline (NRP) were used as basic model analytes and simultaneously extracted from urine samples by liquid-phase microextraction (LPME) in a microfluidic device. The model analytes (target compounds) were pharmaceuticals with 0.4 < log P < 5. Different organic solvents and mixtures of them were investigated as supported liquid membrane (SLM), and a mixture of 2:1 (v/v) tributyl phosphate (TBP) and dihexyl ether (DHE) was found to be highly efficient for the simultaneous extraction of the non-polar and polar model analytes. TBP reduced the intrinsic hydrophobicity of the SLM and facilitated extraction of polar analytes, while DHE served to minimize trapping of non-polar analytes. Sample and acceptor phase composition were adjusted to pH 12 and pH 1.5, respectively. Urine samples were pumped into the microfluidic system at 1 μL min-1 and the extraction was completed in 7 min. Recoveries exceeded 78% for the target analytes, and the relative standard deviation (n = 4) was below 7% in all cases. Using five microliters of SLM, the microfluidic extraction system showed good long-term stability, and the same SLM was used for more than 18 consecutive extractions.Agencia de Gestió d'Ajusts Universitaris i the Recerca 2017-SGR-329Ministerio de Ciencia e Innovación PGC2018-096608-B-C2

Sorbent coatings for solid-phase microextraction targeted towards the analysis of death-related polar analytes coupled to comprehensive two-dimensional gas chromatography: comparison of zwitterionic polymeric ionic liquids versus commercial coatings

Decomposition of bodies generates several types of polar volatile organic compounds (VOCs), whose types, patterns and ratios change during the various stages of decomposition and, therefore, their determination has huge potential to provide useful information to disclose events related to the time of death, or body surrounding environment. As sample preparation is a mandatory key-point in a method development, this research aims to develop a simple, accurate and rapid approach to study death-related polar VOCs based on headspace solid-phase microextraction (HS-SPME) combined with comprehensive two-dimensional gas chromatography-time of flight mass spectrometry (GC × GC-ToFMS) analysis. The performance of zwitterionic PIL-based fibers (containing a [VIm+C9COO−] monomer and a [(VIm)2C122+]-2Br− crosslinker), tailored for polar compounds, was evaluated for a set of 19 analytes associated with the unique odour created by decomposing bodies, and it was compared to the commercially-available fibers: divinylbenzene/carboxen/poly(dimethylsiloxane) – DVB/CAR/PDMS, poly(dimethylsiloxane)/divinylbenzene – PDMS/DVB and polyacrylate (PA). Fibers with absorptive-type mechanism, such as PA and PIL, showed the best results in the balance of the parameters studied, being able to detect analytes at ng level and providing a profile representative of the headspace composition, thus they may represent a useful tool to respond to current challenges in forensic taphonomy. The reproducibility (with relative standard deviation lower than 18%, depending on the analyte) and relative recoveries (higher than 99.1%) were similar and acceptable for both fibers. The zwitterionic PIL, with ca. 4 times smaller film thickness than PA, still has potential to have the best performance, supported by the efforts to obtain thicker sorbent coatings.publishe

Response and Discrimination Performance of Arrays of Organothiol-Capped Au Nanoparticle Chemiresistive Vapor Sensors

The response and discrimination performance of an array that consisted of 20 different organothiol-capped Au nanoparticle chemiresistive vapor sensors was evaluated during exposure to 13 different organic vapors. The passivating organothiol ligand library consisted of collections of straight-chain alkanethiols, branched alkanethiols, and aromatic thiols. A fourth collection of sensors was formed from composites of 2-phenylethanethiol-capped Au nanoparticles and nonpolymeric aromatic materials that were coembedded in a sensor film. The organic vapors consisted of six hydrocarbons (n-hexane, n-heptane, n-octane, isooctane, cyclohexane, and toluene), three polar aprotic vapors (chloroform, tetrahydrofuran, and ethyl acetate), and four alcohols (methanol, ethanol, isopropanol, and 1-butanol). Trends in the resistance response of the sensors were consistent with expected trends in sorption due to the properties of the test vapor and the molecular structure of the passivating ligands in the sensor films. Classification algorithms including principal components analysis and Fisher’s linear discriminant were used to evaluate the discrimination performance of an array of such sensors. Each collection of sensors produced accurate classification of most vapors, with misclassification occurring primarily for vapors that had mutually similar polarity. The classification performance for an array that contained all of the sensor collections produced nearly perfect discrimination for all vapors studied. The dependence of the array size (i.e., the number of sensors) and the array chemical diversity on the discrimination performance indicated that, for an array of 20 sensors, an array size of 13 sensors or more produced the maximum discrimination performance