Ionic Liquid Column Research Articles

Determination of solvation parameter model compound descriptors by gas chromatography

The solvation parameter model uses five system independent descriptors to characterize compound properties defined as excess molar refraction, E, dipolarity/polarizability, S, hydrogen-bond acidity, A, hydrogen-bond basicity, B, and the gas-liquid partition constant at 25 °C on n-hexadecane, L, to model transfer properties in gas-condensed phase biphasic systems. The E descriptor for compounds liquid at 20 °C is available by calculation using a refractive index value while E for solid compounds at 20 °C and the S, A, B, and L descriptors are determined by experiment. As a single-technique approach, it is shown that with up to 20 retention factor measurements on four columns comprising a poly(siloxane) containing methyloctyl or dimethyldiphenylsiloxane monomers (SPB-Octyl or HP-5), a poly(siloxane) containing methyltrifluoropropylsiloxane monomers (Rtx-OPP or DB-210), a poly(siloxane) containing bis(cyanopropylsiloxane) monomers (HP-88 or SGE BPX-90), and a poly(ethylene glycol) stationary phase (DB-WAXetr or HP-INNOWAX) are suitable for assigning the S, A, and L descriptors. Using the descriptors in the updated WSU compound descriptor database as target values the average absolute error in the descriptor assignments for 52 varied compounds in the temperature range 60–140 °C was 0.072 for E, 0.016 for S, 0.008 for A, and 0.022 for L corresponding to 30 %, 3.5 %, and 0.6 % as a relative average absolute error for E, S, and L, respectively. For the higher temperature range of 160–240 °C and 34 varied compounds that are liquid at 20 °C the average absolute error for the S, A and L descriptors was 0.026, 0.020, and 0.031, respectively, with the largest relative average absolute error for S of 3.2 % (< 1 % for the L descriptor). For 35 varied compounds that are solid at 20 °C the relative absolute error for the E, S, A, and L descriptors in the higher temperature range was 0.068, 0.035, 0.020, and 0.020, respectively, with a relative average absolute error for E (6.5 %), S (3.5 %) and L (0.88 %). The S, A, and L descriptor can be accurately assigned on the four-column system over a wide temperature range. The E descriptor for solid compounds at 20 °C exhibits greater variability than desirable. The B descriptor cannot be assigned by the four-column system, which lack hydrogen-bond acid functional groups, and is only poorly assigned on the weak hydrogen-bond acid ionic liquid column SLB-IL100.

Leveraging the use of ionic liquid capillary columns and GC×GC-MS for fatty acid profiling in human colostrum samples.

Lipids in human colostrum provide the majority of energy intake and essential fatty acids for developing infants. The fatty acid composition of human colostrum is highly variable and influenced by multiple factors. Human colostrum is a complex sample bringing challenges to fatty acid profiling. This work aimed to optimize the use of ionic liquid (IL) columns and flow-modulated comprehensive two-dimensional gas chromatography coupled to mass spectrometry (FM-GC×GC-MS) for fatty acid profiling in human colostrum. Derivatization strategies were optimized and the elution behavior of fatty acid methyl esters (FAME) on various 1D column phases (Solgel-WAX, SLB-IL60i, SLB-IL76i, and SLB-IL111i). Derivatization with sodium methoxide yielded a satisfactory recovery rate (90%) at milder conditions and reduced time. The use of IL60 as the 1D column provided superior separation, good peak shape, and better utilization of elution space. As a proof of concept, the developed method was applied to access the effects of the mode of neonatal delivery (vaginal vs. C-section) on the fatty acid profile of human colostrum samples. The integrated multidimensional gas chromatography strategy improved FAME detection and separation and can be a useful tool for accessing the effects of different factors on the fatty acid profiling of complex samples.

Biomarkers for cheese authentication by detailed and fast gas chromatographic profiling of triacylglycerol fatty acids.

Unsaturated fatty acid isomers and odd- and branched-chain fatty acids (OBCFAs) in milk triacylglycerols (TAGs) can be quantitated using gas chromatography (GC), providing access to biomarkers of animal species, breeds, diet, geographic origin, and environmental conditions. Such analysis requires expensive cyanopropyl siloxane or ionic liquid columns of at least 50m in length, which increases the elution time. Aiming to use GC for cheese authentication and characterization while keeping the experiment time short and maintaining a good separation between fatty acid (FA) isomers, we considered using a 30m polyethylene glycol-2-nitroterephthalate column. The FAs thus quantitated allowed the discovery of specific biomarkers for the origins of cheese varieties highly consumed in several countries. In addition, the simple and multivariate correlations we found between FAs in the cheese TAG matrix were alternative means for characterization and authentication purposes.

Numerical investigation on the wave transformation in the ionic liquid compressor for the application in hydrogen refuelling stations

The ionic liquid compressor exhibits excellent advantages in hydrogen refuelling stations due to the specific design based on the hydraulic system and the ionic liquid piston. The application of the ionic liquid column results in a complex two-phase flow issue inside the compression chamber. This two-phase flow behaviour is critical for the compressor design as it influences the wave dynamics during the compression, but it is absent in the open literature. In this paper, transit numerical simulations were carried out to investigate the wave transformation during a compression cycle by the volume of fluid (VOF) method under different heights of the ionic liquid piston. The effect of liquid height on the wave transformation, discharged quantity of ionic liquid and hydrogen gas, and the turbulence kinetic energy was analysed. The minimum crest value of the turbulent kinetic energy was observed as 0.54 kJ in the cases of 30 and 40 mm. The optimal height of the ionic liquid piston was recommended 40 mm under the presented design condition based on the simulation results.

Ionic liquids as stationary phases for the gas chromatographic separation of fentanyl analogues

The continuous emergence of novel fentanyl analogues has created a need for improved methods able to distinguish between fentanyl analogues and their isomers. In this study, the utility of commercially available ionic liquid columns is demonstrated for GC-FID and GC–MS separation and unambiguous identification of fentanyl, 22 fentanyl analogues and U-47700. The selectivity of the IL column towards these compounds was determined as well as the effectiveness of detection from complex illicitly synthesized drug samples. The results of this study were compared to a 5% diphenyl/95% dimethylpolysiloxane column to show increased selectivity and applicability towards seized illicit drug samples. 24 compounds were separated 36% faster with an elution window increase of 33% on the ionic liquid phase compared to the 5% diphenyl/95% dimethylpolysiloxane phase. The selectivity of 11 isomeric analogue sets (out of 12) increased by 2 to 25% over the 5% diphenyl/95% dimethylpolysiloxane phase showing an ionic liquid column is more favorable for separating fentanyl analogues. The ionic liquid column provides better signal to noise, and a faster and more selective option for forensic laboratories looking to identify confiscated illicit drug samples.

Total-transfer comprehensive three-dimensional gas chromatography with time-of-flight mass spectrometry

Although comprehensive two-dimensional (2D) gas chromatography (GC × GC) is a powerful technique for complex samples, component overlap remains likely. An intriguing route to address this challenge is to utilize the additional peak capacity and chemical selectivity provided by comprehensive three-dimensional (3D) gas chromatography (GC3), especially with time-of-flight mass spectrometry detection (GC3-TOFMS). However, the GC3-TOFMS instrumentation reported to date has employed one or both modulators with a duty cycle < 100%, making the potential gain in detection sensitivity over GC × GC modest, or perhaps even worse. Herein, we describe instrumentation for GC3-TOFMS in which both modulators provide total-transfer (100% duty cycle). Specifically, the instrument is based on the facile modification of a commercial thermally modulated comprehensive GC × GC-TOFMS platform for modulation from the 1D column to the 2D column, with recently described dynamic pressure gradient modulation (DPGM) as the second modulator from the 2D column to the 3D column, which is a total-transfer flow modulation technique. Area measurements of 1D peaks are compared to the sum of 3D peak areas to validate the assumption that total-transfer from 1D to 3D is accomplished. Additionally, peak heights were amplified by as high as a factor of 177 (x̅ = 130, s = 47) via comparison of 1D peak heights to the maximum 3D peak heights. Column selection is explored, with emphasis on the resulting peak width-at-base on each dimension and usage of 3D space as evaluation metrics. Using a nonpolar × polar × ionic liquid column combination, an effective peak capacity which considers modulation-induced broadening as high as 32,300 for select analytes was achieved (x̅ = 19,900, s = 10,700). The analytical benefits of employing three selective phases, mass spectrometry detection, and total-transfer modulation are explored with separations of a metabolomics-type sample, i.e., derivatized porcine serum, and a jet fuel spiked with various sulfur-containing compounds.

Parallel Ionic Liquid Semi-Packed Microfabricated Columns for Complex Gas Analysis.

The paper presents a parallel micro gas chromatography approach using three ionic liquid semipacked columns. Switching from single column to multiple parallel columns with different selectivity enhances the power of compound identification without increasing the analysis time. The columns are fabricated using microelectromechanical systems (MEMS) technology containing an array of microfabricated pillars. The columns are 1 m-long and 240 μm-deep with four pillars per row. All columns were functionalized with ionic liquid stationary phases using a modified static coating technique and demonstrated the number of theoretical plates between 5000 and 8300 per meter. The chip performance was investigated with four different samples: (1) a mixture of C7-C30 saturated alkanes, (2) a multianalyte mixture consisting of 20 compounds ranging from 80 to 238 °C in boiling point, (3) a mixture of five organic chemicals with varying degrees of polarity, and (4) 46-compounds mixture containing all the chemicals in the first three samples. The individual columns separated 75%-100% of the first three samples but failed to distinguish all 46 compounds due to coeluting analytes; however, the parallel configuration provided more retention time information by which all the compounds in all samples were fully determined.

Microfabricated ionic liquid column for separations in dry air

Micro gas chromatography (µGC) is a technique developed for rapid, in situ analysis of volatile organic compounds (VOCs) for environmental protection, industrial monitoring, and toxicology. While reduced µGC size and power requirements allow for increased portability, the low moisture and oxygen resilience of current microcolumn technology result in increased peak broadening and tailing for humid samples, which necessitates the use of bulky helium or nitrogen carrier gas cartridges. Developing a microcolumn to address these deficiencies is desirable to improve µGC field performance and further reduce µGC system size. This paper reports the development and characterization of a microfabricated phosphonium ionic liquid (µIL) column and demonstrates separation of both polar and nonpolar compounds using this column via analyses of alcohols, chloroalkanes, aromatics, aldehydes, fatty acid methyl esters, and alkanes. The µIL column achieved operation at temperatures up to 345 °C for fatty acid methyl ester and alkane separation. Notably, all separations in this study used dry air as the carrier gas, showing that analysis of a diverse range of compounds was possible in the presence of oxygen. After exposure to dry air for 48 h at temperatures up to 220 °C, the µIL column's peak capacity was only degraded by 8.92%, which validated its long-term robustness against oxygen. The column's separation performance was not degraded by high moisture concentrations or long-term moisture exposure, also manifesting its robustness to moisture. The high temperature, moisture, and oxygen resilience of the µIL column enable more rapid separations in varying field environments without requiring additional µGC accessories (e.g., humidity filters and carrier gas cartridges). The µIL column is therefore expected to be useful for integration into future µGC devices.

Evaluation of different ionic liquid stationary phases for the analysis of carbohydrates by gas chromatography-mass spectrometry.

Five commercial ionic liquid (IL) columns have been evaluated for the first time for the gas chromatography-mass spectrometry (GC-MS) analysis of low molecular weight carbohydrate (LMWC) standards (mono-, di-, and trisaccharides, inositols, and iminosugars). A previous derivatization step was necessary to convert the LMWCs into their volatile and stable derivatives. Compared with conventional GC stationary phases, such as HP-1 and Supelcowax® 10, IL columns have shown a different selectivity in the separation of target compounds. Among the IL columns, only SLB™-IL82 allowed the elution of all the LMWCs studied. Its performance in terms of peak width and asymmetry, evaluated under different oven temperature conditions, was shown to be dependent on the carbohydrate class considered. As an example of application, a SLB™-IL82 column was successfully used to separate the complex mixtures of LMWCs in hyacinth and mulberry extracts. This column is an interesting alternative to the conventional stationary phases used in the GC analysis of LMWCs in real-world samples. Graphical abstract.

Simulation of peak position and response profiles in comprehensive two-dimensional gas chromatography

Approaches to simulate peak time and intensity profiles of compounds in comprehensive two dimensional gas chromatography (GC × GC) were developed, and which are demonstrated for separation of a mixture of saturated and unsaturated fatty acid methyl esters (FAME) using a range of column sets. The simulation of first and second dimension time (1tR and 2tR) of FAME relies on use of a Gibbs energy additivity approach to correlate with the structures of FAME. First and second dimension peak standard deviations (1σ and 2σ) of the compounds were further calculated from the 1tR and 2tR data according to the plate height concept which provided good agreement between the predicted and experimental peak widths at half height in one dimension GC (1DGC) with an overall R2 of 0.9628. The effect of 1σ distortion caused by the modulation process was also taken into account in the peak width simulation where the simulated 1σ data were rounded up to multiples of the scale of modulation period (PM). Two dimension Gaussian equations were then used to generate GC × GC results (2D contour plots) from simulated 1tR, 2tR, 1σ and 2σ data for FAME separation on different column sets employing ionic liquid and conventional columns. Good overall correlations between experimental and simulated 1tR and 2tR were obtained with R2 of 0.9951 and 0.9802, respectively, and the simulated 2D contour plots were an acceptable match with the experimental results.

Retention Behaviour of Alkylated and Non-Alkylated Polycyclic Aromatic Hydrocarbons on Different Types of Stationary Phases in Gas Chromatography

The gas chromatographic retention behaviour of 16 polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs on a new ionic liquid stationary phase, 1,12-di(tripropylphosphonium) dodecane bis(trifluoromethanesulfonyl)imide (SLB®-ILPAH) intended for the separation of PAH mixtures, was compared with the elution pattern on more traditional stationary phases: a non-polar phenyl arylene (DB-5ms) and a semi-polar 50% phenyl dimethyl siloxane (SLB PAHms) column. All columns were tested by injections of working solutions containing 20 parental PAHs from molecular weight of 128 to 278 g/mol and 48 alkylated PAHs from molecular weight of 142 to 280 g/mol on a one dimensional gas chromatography-mass spectrometry (GC-MS) system. The SLB PAHms column allowed separation of most isomers. The SLB®-ILPAH column showed a rather different retention pattern compared to the other two columns and, therefore, provided a potential for use in comprehensive two-dimensional GC (GC×GC). The ionic liquid column and the 50% phenyl column showed good thermal stability with a low bleed profile, even lower than that of the phenyl arylene “low bleed” column.

Orthogonality and Quality of GC × GC Separations for Complex Samples with Ionic Liquid Stationary Phases in First Dimension

In this paper, the advantages of using a pyridinium and imidazolium ionic liquids in the first column for GC × GC separation of complex mixtures—coal pyrolysis product, bio-oil, and essential oil from Pituranthos scoparius—in comparison with polyethylenglycol phase has been demonstrated. The nearest neighbor distance (NND) approach to evaluate the separation quality and orthogonality has been used for the comparison of GC × GC separations for different ionic liquid columns in the first dimension. It was found that they give essentially different results for both the separation quality and orthogonality, evaluated using parameters derived from NND approach. For a mixture of coal pyrolysis products containing only two classes of compounds—phenols and aromatic compounds—the most polar ionic liquid bis4MPyC6 shows nearly the highest orthogonality and separation quality. In the case of separation bio-oil and essential oil, the best orthogonality was demonstrated for the least polar of the tested ionic liquids—bis3.5MPyC9. At the same time, the efficiency of columns exerts a significant effect on the separation quality parameter. As a result, this parameter has the highest value for all mixtures tested using the polyethylene glycol (ZB-WAX) reference phase, which is the less polar from all series, but the most efficient.

Comprehensive lipid profiling in the Mediterranean mussel (Mytilus galloprovincialis) using hyphenated and multidimensional chromatography techniques coupled to mass spectrometry detection.

The task of lipid analysis and profiling is taking centre stage in many research fields and as a consequence, there has been an intense effort to develop suitable methodologies to discover, identify, and quantify lipids in the systems investigated. Given the high complexity and diversity of the lipidome, researchers have been challenged to afford thorough knowledge of all the lipid species in a given sample, by gathering the data obtained by complementary analytical techniques. In this research, an "omic" approach was developed to quickly fingerprint lipids in the Mediterranean mussel (Mytilus galloprovincialis), by exploiting multidimensional and hyphenated techniques. In detail, two-dimensional comprehensive hydrophilic interaction liquid chromatography coupled to reversed-phase liquid chromatography afforded both class-type separation and lipid assignment within the total lipid species in the sample, by the coupling of a 2.1-mm I.D. partially porous stationary phase in the first dimension, to a short (50mm) monodisperse octadecylsilica secondary column; individual molecular species were afterwards identified by means of their ion trap-time of flight mass spectra obtained by electrospray ionization. More than 200 neutral and polar lipids were identified, and among the latter, phosphatydylcholine and phosphatydylethanolamine were the most represented classes, together with their mono-acylated forms, plasmanyl and plasmenyl derivatives. Subsequently, separation of the saturated and unsaturated isomers of the fatty acids (including the saturated C16:0 and the polyunsaturated C22:6) in the offline collected phospholipid fractions was accomplished by gas chromatography analysis of the corresponding methyl esters, on a 200m × 0.25mm, 0.2μm d f ionic liquid column.

Ionic liquids as water-compatible GC stationary phases for the analysis of fragrances and essential oils

Fragrances and products deriving from essential oils are often formulated or diluted in aqueous media, usually ethanol/water. Gas chromatography (GC) is the technique of choice to analyze volatiles. However, when using columns coated with conventional stationary phases, its application to aqueous samples often requires time-consuming and/or discriminative sample preparation techniques to extract the target analytes from the aqueous medium, so as to avoid its direct injection. In GC with conventional columns, water produces peak asymmetry, poor sensitivity and efficiency, strong adsorption, stationary phase degradation, and, last but not least, it is not easy to detect reliably when present in high amounts. In 2012, Armstrong's group introduced new fully water-compatible ionic-liquid (IL)-based GC capillary columns based on phosphonium and imidazolium derivative cations combined with trifluoromethanesulphonate. These columns were recently made available commercially by Supelco, under the trade name Watercol™. These derivatives maintain IL's unique selectivity and chromatographic properties, and enable water to be used as injection solvent, thus avoiding the sample preparation procedures required by conventional columns. This study reports and critically discusses the results of commercially available water-compatible IL columns for direct analysis of aqueous samples in the fragrance and essential oil fields by GC with thermal conductivity (TCD) and/or flame ionization detectors (FID). The results showed that water-compatible IL-based stationary phases can successfully be adopted for qualitative and quantitative analysis of fragrances and essential oils directly diluted in aqueous solvents. On the other hand, the study also shows that their inertness needs to be further increased and (possibly) the range of operative temperature extended when water is the main solvent of the sample.

Study on the Mixed-Mode HPLC Separation of Shuang-Huang-Lian and Xue‑Bi‑Jing Injections Based on an Ionic Liquid Column

Both Shuang-Huang-Lian and Xue-Bi-Jing injections are clinically proven efficient and low cost medicines. However, the studies of their chromatographic separation are limited. In this study, a column based on ionic liquid stationary phase was applied for the first time for the analysis of these two injections. For Shuang-Huang-Lian injection, U-shaped plots of retention factors vs. mobile phase constitutions were obtained. This unique kind of separation behavior allowed a flexible adjustment of retention by tuning the mobile phase constituents. Then acids group was analyzed with hydrophilic chromatography mode, while glycosides group was analyzed with reversed phase chromatography mode. Similarly, constituents in Xue-Bi-Jing injection were analyzed with mixed mode high performance liquid chromatography (HPLC). Higher, medium and lower polarity groups were analyzed with hydrophilic interaction, reversed phase and normal phase liquid chromatography modes, respectively. Results from this work provided valuable information for the separation of complicated systems such as traditional Chinese medicine injections.

Branched-chain dicationic ionic liquids for fatty acid methyl ester assessment by gas chromatography.

Twelve bis- or dicationic ionic liquids (ILs) including eight based on imidazolium, a single one based on phosphonium, and three based on pyrrolidinium cationic units were prepared with the bis(trifluoromethyl sulfonyl) imide anion. The two identical cationic moieties were attached by different alkyl spacers having three or five carbons and differing alkyl substituents attached to the spacer. The SLB-IL111 column, as the most polar commercial stationary phase known, was included in the study for comparison. Isothermal separations of a rapeseed oil fatty acid methyl ester (FAME) sample were used to study and compare the 12 IL-based column performances and selectivities. The retention times of the most retained methyl esters of lignoceric (C24:0) and erucic (C22:1) acids were used to estimate the IL polarity. The phosphonium dicationic IL column was, by far, the least polar. Imidazolium-based dicationic IL columns were the most polar. Polarity and selectivity for the FAME separation were somewhat related. The separation of a 37-FAME standard mixture allowed the investigation of selectivity variations observed on the 12 IL-based columns under temperature gradients up to 230°C. The remarkable selectivity of the IL-based columns is demonstrated by the detailed analysis of the cis/trans C18:1 isomers of a partially hydrogenated vegetable oil sample on 30-m columns, separations competing with that done following an "official method" performed on a 100-m column. Graphical abstract Separation of fatty acid methyl esters on a 30-m 3m2C5(mpy)2. 2NTf2 branched-chain dicationic IL-based column. Branched chain dicationic ILs show great selectivity for separation of cis/trans, ω-3/ω-6, and detailed analysis of cis/trans fats.

Ionic liquid capillary columns for analysis of multi-component volatiles by gas chromatography-mass spectrometry: performance, selectivity, activity and retention indices.

This study investigates applications and performance evaluation of SLB-IL60, SLB-IL76 and SLB-IL111 columns, in relation to a DB-Wax column, for the analysis of coffee volatile compounds. Both standards and an authentic coffee sample were analysed, with solid-phase microextraction (SPME) sampling of the latter. A cryofocusing method was applied to improve resolution of the earliest eluting peaks using splitless injection SPME sample analysis. The Grob test was used to verify the inertness and efficiency of the columns, helping to understand the interactions between analytes and stationary phases, particularly toward more polar coffee analytes. A DB-5 column was used only in analysis of n-alkanes and Grob test mixtures as an apolar reference. The evaluated ionic liquid columns showed a moderate acid-base character and low inertness for compounds with hydrogen bond capabilities, especially for the hydroxylated analytes, 2,3-butanediol in the Grob test, and furanones and acids in the coffee standards. The columns exhibiting the best resolution and efficiency were DB-Wax and SLB-IL60, both for samples and standards. Although the DB-Wax column is preferred for analysis of coffee volatiles, due to better inertness, the evaluated ionic liquid columns allowed identification of compounds that were not observed in separations with the Wax-phase column in this work. Among these compounds is 3,4-dimethyl-2,5-furandione, seldom reported in the literature of coffee. Proposed improvement by the manufacturer in the inertness of the columns evaluated in this study may lead to better results; so future versions of IL phases may be better applied in the separation of target analytes, especially those with basic character. Graphical abstract Illustrative representation of the sample (coffee) and the chemical structures of the stationary phases of the ionic liquid capillary columns used as object of study in the present work.

Analysis of essential oils and fragrances with a new generation of highly inert gas chromatographic columns coated with ionic liquids

In the fields of essential oils and fragrances, samples often consist of mixtures of compounds with similar structural and physical characteristics (e.g. mono- and sesquiterpenoids), whose correct identification closely depends on the synergic combination of chromatographic and mass spectral data. This sample complexity means that new GC stationary phases with different selectivities are continually being investigated. Ionic liquids (ILs) are of great interest as GC stationary phases in this field because of their selectivity (significantly different than that of currently phases) and their high temperature stability.A first generation of IL GC columns was found to be competitive when applied to these field, in terms of selectivity and efficiency, compared to conventional columns (polydimethylsiloxane, (e.g. OV-1), methyl-polysiloxane 5%-phenyl (e.g. SE-52), 7%-cyanopropyl, 7%-phenyl polysiloxane (e.g. OV-1701), and polyethylen glycol (e.g. PEG–20M). However, these columns showed significant activity towards polar or active analytes, which primarily affected their quantitative performance. A new generation of highly-inactive columns coated with three of the most widely-used ionic liquid GC stationary phases has recently been introduced; these phases are SLB-IL60i (1,12-di(tripropylphosphonium) dodecane bis(trifluoromethylsulfonyl) imide [NTf2], SLB-IL76i (tri-(tripropylphosphonium-hexanamido)-triethylamine [NTf2]), and SLB-IL111i (1,5-di (2,3-dimethyllimidazolium) pentane [NTf2]). This study carefully tested the new inert IL columns, in view of their routine application in the fragrance and essential oil fields. They were found to have unusually high selectivity, comparable to that of first-generation IL columns, while their inertness and efficiency were competitive with those of currently-used conventional columns. The IL column performance of first and second generations was compared, through the quali-quantitative analysis of components in a group of different complexity samples; these included the Grob test, a standard mixture of “suspected” skin allergens, and the essential oils of chamomile and sandalwood.

Ionic liquids as stationary phases for fatty acid analysis by gas chromatography.

The present paper provides an overview of the application of ionic liquid (IL) columns for GC analysis of fatty acid methyl esters (FAMEs). Although their separation can be carried out utilizing GC columns containing polar stationary phases, some ILs have been employed as stationary phases, either commercial or laboratory made, in GC analysis. Monodimensional and bidimensional GC methods have been optimized in order to achieve the best separation especially considering the geometric and positional isomers of unsaturated fatty acids. Several methods for the analysis of trans-fatty acids have also been reported. The use of GC-GC, using either the same IL columns or different columns in the first and second dimensions, allowed the separation of a large number of FAMEs. The application of the IL columns for GC analysis of FAMEs in different types of real samples is described, e.g., oil of different nature (fish, flaxseed, and olive), margarine and butter, biodiesel, milk, bacteria etc.

Separation of phenol-containing pyrolysis products using comprehensive two-dimensional chromatography with columns based on pyridinium ionic liquids.

We describe the application of columns with highly polar stationary liquid phases based on pyridinium ionic liquids for the two-dimensional chromatography separation of bio-oil and product of coal pyrolysis. By using inverse combination columns-a first ionic liquid column and a second nonpolar column-good separation results have been obtained. In the analysis of coal pyrolysis products, the suggested approach provides a much better resolution between components in comparison with a less polar first-dimension column (based on polyethylene glycol). A good selectivity for the peaks of phenols is observed, and the group of phenols is well detached and separated from the group of diaromatics. A good separation picture was obtained also for bio-oil, the groups of phenols and guaiacol derivatives are distinguished with good resolution of substances within each group.