Utilization of solid-phase microextraction–high-performance liquid chromatography in the determination of aromatic analyte partitioning to imidazolium-based ionic liquid micelles

A solid-phase microextraction (SPME)–high-performance liquid chromatography (HPLC) approach is used, for the first time, to study the partitioning behavior of eight aromatic analytes to three imidazolium-based ionic liquid micelles, namely, 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br), 1-hexadecyl-3-butylimidazolium bromide (HDBIm-Br), and 1,3-didodecylimidazolium bromide (DDDDIm-Br). The model used to calculate the partition coefficients is improved by determining the accurate critical micelle concentration (CMC) value of the studied IL-micelles, which considers the nature and amount of organic modifier used in the experiments. Proper CMC values in the model improve the quality of the results and decrease the differences between theoretical and experimental intercepts. Surface tensiometry has been utilized to determine the CMC values for the micelles at different acetonitrile contents (1% and 1.5%, v/v). The calculated partition coefficient values for polycyclic aromatic hydrocarbons (PAHs) oscillate between 631 and 5980, whereas aromatic analytes with a lower number of fused rings in their structures suffer non-partitioning to any of the IL-micelles. The obtained partition coefficients to IL-micelles were highest with the DDDDIm-Br IL and were always higher than those obtained with the traditional surfactant cetyltrimethyl ammonium bromide (CTAB).     

Ion-exclusion chromatography with mixed micellar mobile phases

Mixed ionic-nonionic surfactant mobile phases for ion-exclusion chromatography of carboxylic acids permitted the analysis time to be reduced by partitioning the analytes could be determined without interference even when they eluted near the void volume. These advantages result from the formation of mixed micelles of the two surfactants. The partition behaviour of both neutral and charged analytes to a nonionic micellar phase was evaluated on the basis of a retention model that included dissociation equilibria of analytes. In addition, the partition coefficients to mixed micellar phases were also determined by using this model.     

Use of the three-phase model and headspace analysis for the facile determination of all partition/association constants for highly volatile solute–cyclodextrin–water systems

A versatile method for measuring the partition coefficients of volatile analytes with an aqueous pseudophase using headspace gas chromatography is reported. A “three-phase” model accounts for all equilibria present in the system, including the partitioning of the analyte in the gas and aqueous phases to the pseudophase. This method is applicable to a wide variety of volatile analytes and aqueous pseudophases, providing that sufficient pseudophase may be used to reduce the analyte partial pressure. Generally, the method offers good reproducibility and high sensitivity. The associations of five volatile analytes (hydrogen sulfide, methanethiol, dimethyl sulfide, dichloromethane, and ethyl ether) with various cyclodextrins were examined. All analytes were found to partition preferentially to the cyclodextrin pseudophase compared to the aqueous phase. In addition, several analyte–cyclodextrin combinations formed insoluble complexes in solution that enhanced the extraction of the analyte from the gas and aqueous phases. Derivatization of the cyclodextrins generally decreased the extent of analyte–cyclodextrin interaction.     

A hierarchical porous composite magnetic sorbent of reduced graphene oxide embedded in polyvinyl alcohol cryogel for solvent-assisted-solid phase extraction of polycyclic aromatic hydrocarbons

A hierarchical porouscomposite magnetic sorbent was fabricated and applied to the dispersive solvent-assisted solid-phase extraction of five polycyclic aromatic hydrocarbons. A sorbent was first prepared by incorporating graphene oxide, calcium carbonate, and magnetite nanoparticles into a polyvinyl alcohol cryogel. The graphene oxide was converted to reduced graphene oxide using ascorbic acid and a hierarchical porous structure was produced by reacting hydrochloric acid with incorporated calcium carbonate to generate carbon dioxide bubbles which created a second network. Before extracting the target analytes, the extraction solvent was introduced into the hierarchical pore network of the sorbent. The extraction was based on the partition between the analytes and introduced extraction solvent and the adsorption of analytes on reduced graphene oxide.The extraction efficiency was enhanced through π-π and hydrophobic interactions between polycyclic aromatic hydrocarbons and reduced graphene oxide and extraction solvent. The extracted polycyclic aromatic hydrocarbons were determined by using high-performance liquid chromatography coupled with a fluorescence detector. The developed method was applied to extract polycyclic aromatic hydrocarbons in disposable diaper, coffee, and tea samples and recoveries from 84.5 to 99.4% were achieved with relative standard deviations below 7%. The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.The developed sorbent exhibited good reproducibility and could be reused for 10 cycles.     

Determination of colloidally-associated polycyclic aromatic hydrocarbons (PAHs) in fresh water using C18 solid phase extraction disks

A new application of reversed-phase octadecyl (C₁₈) solid phase extraction disks has been developed to separate the colloidally-associated polycyclic aromatic hydrocarbons (PAHs) from those that were truly dissolved in the samples of fresh water. A correction for the retention of small amounts of colloidal material on the C₁₈ disks was required, which would have otherwise lead to minor underestimates in the degree of partitioning between the two phases. Using the humic substance Aldrich Humic Acid (AHA) as a model colloid and the 16 PAHs on the US Enrivonmental Protection Agency priority pollutant list, the partitioning coefficients of the PAHs between the colloidal and truly dissolved phases were shown to be proportional to the hydrophobicity of the PAHs, as measured by their octanol water partition coefficients (K_ow). The values for the partition coefficients obtained (cK_doc′) were similar to those previously reported in the literature using alternative methods, confirming that the technique was producing acceptable results. The technique allows the in situ partitioning of PAHs between the truly dissolved and colloidal phases in fresh water bodies to be determined. It will provide an invaluable cross-check of the laboratory-based methods which often require substantial manipulation of the sample and potentially alter the partitioning between the phases.     

Evaluation of tetraglyme for the enrichment and analysis of volatile organic compounds in air

A recently developed method for the sampling and analysis of volatile organic compounds in air has been evaluated. The system is based on the enrichment of analytes in tetraethylene glycol dimethyl ether or tetraglyme, a water-soluble organic liquid. The subsequent analysis consists of dispersion of a sample aliquot in water followed by purge-and-trap and gas chromatographic separation. Physico-chemical data were investigated for 10 volatile organic compounds, providing information on the possibilities and limitations of the tetraglyme method. The target analytes included chlorinated alkanes and alkenes, and monocyclic aromatic hydrocarbons. Air/tetraglyme partition coefficients Kat were determined over an environmental relevant temperature range of 2-25 degrees C to evaluate sorption efficiencies and estimate breakthrough volumes at the sampling stage. At 2 degrees C breakthrough volumes (allowing 5% of breakthrough) ranged from 5.8 (1,1-dichloroethane) to 312 l (1,1,2-trichloroethane) for 20 ml of tetraglyme. With regard to the desorption stage, the effect of tetraglyme on the air/water partition of organic compounds was investigated through the measurement of air/tetraglyme-water partition coefficients Kat-w for 2-31% (v/v) tetraglyme in water. Finally a clean-up procedure for tetraglyme was evaluated. Analysis of a blank tetraglyme-water (17:83, v:v) mixture by gas chromatography-flame ionization detection/mass spectrometry showed minor background signals. None of the target compounds were detected.     

Coupling the extraction efficiency of imidazolium-based ionic liquid aggregates with solid-phase microextraction-gas chromatography-mass spectrometry. Application to polycyclic aromatic hydrocarbons in a certified reference sediment

Three ionic liquid (IL)-based aggregates, 1-hexadecyl-3-methylimidazolium bromide (HDMIm-Br), 1-hexadecyl-3-butylimidazolium bromide (HDBIm-Br), and 1,3-didodecylimidazolium bromide (DDDDIm-Br) have been applied to the development of a quantitative solid-phase microextraction (SPME)-gas chromatography (GC)-mass spectrometry (MS) method. A sensitivity factor (SF) is defined and introduced for the first time to quantitatively compare the efficiency of the IL-based aggregates by SPME-GC-MS and to evaluate the partitioning strength of several polycyclic aromatic hydrocarbons (PAHs) to the three IL-aggregates. The ILs HDBIm-Br and HDMIm-Br have been used successfully to extract seven PAHs from the certified reference sediment BCR-535 using focused microwave-assisted extraction followed by SPME-GC-MS. Average recoveries for six of the seven certified PAHs were 84.6% for HDMIm-Br and 101% for HDBIm-Br, with relative standard deviation values (RSDs) lower than 19%. The overall extraction method requires short extraction times (around 7 min for the microwave step) and avoids the use of organic solvents.     

Measuring gas-liquid partition coefficients of aroma compounds by solid phase microextraction, sampling either headspace or liquid

Hydrophobic compounds are important odorants and nutrients in foods and beverages, as well as environmental contaminants and pharmaceuticals. Factors influencing their partitioning within multi-component systems and/or from the bulk liquid phase to the air are critical for understanding aroma quality and nutrient bioavailability. The equilibrium partitioning of hydrophobic analytes between air and water was analyzed using solid phase microextraction (SPME) in the headspace (HS-SPME) and via direct immersion in the liquid (DI-SPME). The compounds studied serve as models for hydrophobic aroma compounds covering a range of air-water partition coefficients that extends over four orders of magnitude. By varying the total amount of analyte as well as the ratio of vapor to liquid in the closed, static system, the partition coefficient, K(vl), can be determined without the need for an external calibration, eliminating many potential systematic errors. K(vl) determination using DI-SPME in this manner has not been demonstrated before. There was good agreement between results determined by DI-SPME and by HS-SPME over the wide range of partitioning behavior studied. This shows that these two methods are capable of providing accurate, complementary measurements. Precision in K(vl) determination depends strongly on K(vl) magnitude and the ratio of the air and liquid phases.     

Dicationic imidazolium ionic liquid modified silica as a novel reversed‐phase/anion‐exchange mixed‐mode stationary phase for high‐performance liquid chromatography

A dicationic imidazolium ionic liquid modified silica stationary phase was prepared and evaluated by reversed‐phase/anion‐exchange mixed‐mode chromatography. Model compounds (polycyclic aromatic hydrocarbons and anilines) were separated well on the column by reversed‐phase chromatography; inorganic anions (bromate, bromide, nitrate, iodide, and thiocyanate), and organic anions (p‐aminobenzoic acid, p‐anilinesulfonic acid, sodium benzoate, pathalic acid, and salicylic acid) were also separated individually by anion‐exchange chromatography. Based on the multiple sites of the stationary phase, the column could separate 14 solutes containing the above series of analytes in one run. The dicationic imidazolium ionic liquid modified silica can interact with hydrophobic analytes by the hydrophobic C₆ chain; it can enhance selectivity to aromatic compounds by imidazolium groups; and it also provided anion‐exchange and electrostatic interactions with ionic solutes. Compared with a monocationic ionic liquid functionalized stationary phase, the new stationary phase represented enhanced selectivity owing to more interaction sites.     

Impurity partitioning in Nafion and ceramic separators used for purification of spent chromium plating solutions

Cationic partitioning (Cu(II), Ni(II), and Fe(III)) into Nafion and ceramic membranes equilibrated with different salt solutions was investigated in this study. Both single-ion and multicomponent partitioning in a Nafion-117 membrane in a 2.12 M chromic acid solution was well characterized with the Freundlich isotherm. The affinity for the Nafion membrane was Fe(III)>Ni(II)>Cu(II). The partition coefficients of the divalent cations in multicomponent partitioning experiments were similar to those in single-ion experiments whereas the partition coefficients of the trivalent cation decreased. Among the factors investigated, pH had the most significant influence on the partition coefficients, especially in the pH range of about 0.5–1.5. In contrast, temperature in the range of 25–55 °C had an insignificant effect. The ceramic diaphragm had partition coefficients equal to the porosity (0.4) of the ceramic for all of the species implying that cations were not adsorbed to its surface.     

Utilization of a benzyl functionalized polymeric ionic liquid for the sensitive determination of polycyclic aromatic hydrocarbons; parabens and alkylphenols in waters using solid-phase microextraction coupled to gas chromatography-flame ionization detection

The functionalized polymeric ionic liquid poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide (poly(VBHDIm(+)NTf(2)(-))) has been used as successful coating in solid-phase microextraction (SPME) to determine a group of fourteen endocrine disrupting chemicals (ECDs), including polycyclic aromatic hydrocarbons (PAHs), alkylphenols, and parabens, in several water samples. The performance of the PIL fiber in direct immersion mode SPME followed by gas chromatography (GC) with flame-ionization detection (FID) is characterized with average relative recoveries higher than 96.1% from deionized waters and higher than 76.7% from drinking bottled waters, with precision values (RSD) lower than 13% for deionized waters and lower than 14% for drinking bottled waters (spiked level of 1 ng mL(-1)), when using an extraction time of 60 min with 20 mL of aqueous sample. Detection limits varied between 9 ng L(-1) and 7 ng mL(-1). A group of real water samples, including drinking waters, well waters, and swimming pool waters, have been analyzed under the optimized conditions. A comparison has also been carried out with the commercial SPME coatings: polydimethylsyloxane (PDMS) 30 μm, and polyacrylate (PA) 85 μm. The functionalized PIL fiber (～12 μm) demonstrated to be superior to both commercial fibers for the overall group of analytes studied, in spite of its lower coating thickness. A normalized sensitivity parameter is proposed as a qualitative tool to compare among fiber materials, being higher for the poly(VBHDIm(+)NTf(2)(-)) coating. Furthermore, the partition coefficients of the studied analytes to the coating materials have been determined. A quantitative comparison among the partition coefficients also demonstrates the superior extraction capability of the functionalized PIL sorbent coating.     

Diffusion coefficient and capacity factor in capillary electrokinetic chromatography with replaceable charged polymeric pseudophase

Apparent diffusion coefficients, Dapp,i, were determined in solutions with a polycationic additive -- poly(diallyidimethylammonium) -- acting as a pseudostationary phase for electrokinetic chromatography. They were determined for six small neutral analytes at five concentrations of the polymeric additive (between 0 and 4% w/w) by a stopped migration method. The apparent diffusion coefficients decrease with increasing polymer concentration only within 40% maximum, an effect that cannot be associated with the macroscopic viscosity of the polymer solution (which increases by a factor of 10). The change of the apparent diffusion coefficients is related to the interaction of the neutral analyte molecules with the polyelectrolyte chain. Applying the model of analyte partitioning between "free" solution and polymer, capacity factors and partition constants were derived from the slope of the 1/Dapp,i vs. polymer concentration curves. Partition constants determined by this method (ranging between 40 and 170) agree with those obtained by electrokinetic chromatography.     

New cold-fiber headspace solid-phase microextraction device for quantitative extraction of polycyclic aromatic hydrocarbons in sediment

A new automated headspace solid-phase microextraction (HS-SPME) sampling device was developed, with the capability of heating the sample matrix and simultaneously cooling the fiber coating. The device was evaluated for the quantitative extraction of polycyclic aromatic hydrocarbons (PAHs) from solid matrices. The proposed device improves the efficiency of the release of analytes from the matrix, facilitates the mass transfer into the headspace and significantly increases the partition coefficients of the analytes, by creating a temperature gap between the cold-fiber (CF) coating and the hot headspace. The reliability and applicability of previously reported cold-fiber devices are significantly enhanced by this improvement. In addition, it can be easily adopted for full automation of extraction, enrichment and introduction of different samples using commercially available autosampling devices. Sand samples spiked with PAHs were used as solid matrices and the effect of different experimental parameters were studied, including the extraction temperature, extraction time, moisture content, and the effect of sonication and modifier under optimal experimental conditions, linear calibration curves were obtained in the range of 0.0009-1000 ng/g, with regression coefficients higher than 0.99 and detection limits that ranged from 0.3 to 3 pg/g. Reproducible, precise and high throughput extraction, monitoring and quantification of PAHs were achieved with the automated cold-fiber headspace solid-phase microextraction (CF-HS-SPME) device coupled to GC-flame ionization detection. Determination of PAHs in certified reference sediments using the proposed approach exhibited acceptable agreement with the standard values.     

Determination of partition behavior of organic surrogates between paperboard packaging materials and air

The suitability of recycled paperboard packaging materials for direct food contact applications is a major area of investigation. Chemical contaminants (surrogates) partitioning between recycled paper packaging and foods may affect the safety and health of the consumer. The partition behavior of all possible organic compounds between cardboards and individual foodstuffs is difficult and too time consuming for being fully investigated. Therefore it may be more efficient to determine these partition coefficients indirectly through experimental determination of the partitioning behavior between cardboard samples and air. In this work, the behavior of organic pollutants present in a set of two paper and board samples intended to be in contact with foods was studied. Adsorption isotherms have been plotted and partition coefficients between paper and air have been calculated as a basis for the estimation of their migration potential into food. Values of partition coefficients (Kpaper/air) from 47 to 1207 were obtained at different temperatures. For the less volatile surrogates such as dibutyl phthalate and methyl stearate higher Kpaper/air values were obtained. The adsorption curves showed that the more volatile substances are partitioning mainly in air phase and increasing the temperature from 70 to 100 degrees C their concentrations in air (Cair) have almost doubled. The analysis of surrogates was performed with a method based on solvent extraction and gas chromatographic-flame ionization detection (GC-FID) quantification.     

Energy partitioning in single-electron transfer events between gaseous dications and their neutral counterparts

Electron-transfer reactions between hydrocarbon dications and neutral hydrocarbons lead to an unequal deposition of the excess energy from the reaction in the pair of monocations formed. The initial observation of this phenomenon was explained by the different states accessible upon single-electron capture by a dication compared to single-electron ejection from a neutral compound. Alternatively, however, isomeric structures of the dicationic species, pronounced Franck-Condon effects, as well as excess energy in the dicationic precursors could cause the asymmetric energy partitioning in such dication/neutral collisions. Here, the investigation of this phenomenon in an interdisciplinary cooperation is described, shedding light not only upon a possible solution of the problem at hand, but also providing an example for the synergistic benefits of international research networks applying complementary approaches.     

A family of single‐isomer,dicationic cyclodextrin chiral selectors for capillary electrophoresis: Mono‐6A‐ammonium‐6C‐butylimidazolium‐β‐cyclodextrin chlorides

The first member of the single‐isomer, dicationic cyclodextrin (CD) family, 6^A‐ammonium‐6^C‐butylimidazolium‐β‐cyclodextrin chlorides (AMBIMCD), has been synthesized, analytically characterized, and used to separate a variety of acidic enantiomers and amino acids by CE. Starting from mono‐6^A‐azido‐β‐cyclodextrin, the cationic imidazolium and ammonium moieties were subsequently introduced onto primary ring of β‐cyclodextrin via nucleophilic addition and Staudinger reaction. The analytically pure AC regio‐isomer CD was further obtained via column chromatography. This dicationic CD exhibited excellent enantioselectivities for selected analytes at concentration as low as 0.5 mM, which were even better than those of its mono‐imidazolium or ammonium‐substitued counterpart CDs at 10 equivalent concentrations. The effective mobilities of all studied analytes were found to decrease with the concentration of AMBIMCD. Inclusion complexation in combination with eletrostatic interactions seemed to account for the enhanced chiral discrimination process.     

Temperature dependence of hydrogen bonding: an investigation of the retention of primary and secondary alcohols in gas-liquid chromatography

Configurational-bias Monte Carlo simulations in the Gibbs Ensemble were carried out to investigate the analyte partitioning of n-pentane, n-hexane, n-heptane, 1-propanol, and 2-propanol into a dioctyl ether retentive (stationary) phase used in gas-liquid chromatography. The united-atom version of the TraPPE (transferable potentials for phase equilibria) force field was used to model all analytes and the solvent. The analyte partition coefficients, Gibbs free energies of transfer, and Kovats retention indexes were calculated at four different temperatures ranging from 303.15 to 348.15 K. Although hydrogen bonding is a major contributor to the retention of the alcohol analytes over the entire temperature range, its importance for the separation factor between the primary and secondary alcohol decreases substantially with increasing temperature. The enthalpies and entropies for hydrogen bond formation were also estimated from the temperature dependence of the corresponding equilibrium constants. In agreement with experimental measurements, it is observed that the hydrogen bond involving 1-propanol is enthalpically favored, but entropically disfavored compared to 2-propanol.     

Molecular weight effect on latex film formation induced by solvent vapor: an optical transmission study

Vesicular electrokinetic chromatography was used to investigate solute partitioning from the aqueous phase into dihexadecyl hydrogen phosphate (DHP) vesicles. Retention factors of neutral solutes are related to their partition coefficients between the aqueous phase and vesicles (K(vw)). The K(vw) of the aromatic test solutes were readily obtained from the slopes of the linear relationships between retention factors versus DHP concentrations. The technique offers the advantages of speed, automation, and small sample size for determination of partition coefficients. The K(vw) values of 43 uncharged solutes were measured at below as well as above the phase transition temperatures. The logarithms of partition coefficients (log K(vw)) of solutes at 71 degrees C (above T(c)) were slightly higher than those at 36 degrees C (below T(c)). The solvation characteristics of DHP were also studied using linear solvation energy relationships at the two temperatures.