Analysis of beer volatiles by polymeric imidazolium-solid phase microextraction coatings: Synthesis and characterization of polymeric imidazolium ionic liquids.

Two polymeric ionic liquids, 3-(but-3″-en-1″-yl)-1-[2'-hydroxycyclohexyl]-1H-imidazol-3-ium bis(trifluoromethanesulfonyl)imide (IL-1) and 1-(2'-hydroxycyclohexyl)-3-(4″-vinylbenzyl)-1H-imidazol-3-ium bis(trifluoromethylsulfonyl)imide (IL-2), have been synthesized by a free radical polymerization reaction and used as coatings for solid-phase microextraction (SPME). These new fibers exhibit good film stability, high thermal stability (270-290°C) and long lifetimes, and are used for the extraction of volatile compounds in lemon beer using gas chromatography separation and flame ionization detection. The scanning electron micrographs of the fiber surface revealed a polymeric ionic liquid (PIL) film, which is distributed homogeneously on the fiber. The developed PIL fiber showed good linearity between 50 and 2000µg/L with regression coefficients in the range of 0.996-0.999. The relative standard deviations (RSD) obtained in the peak area were found to vary between 1% and 12%, which assured that adequate repeatability was achieved. The spiked recoveries for three beer samples ranged from 78.4% to 123.6%. Experimental design has been employed in the optimization of extraction factors and robustness assessment. The polymeric IL-1 butenyl fiber showed a greater efficiency compared to the PDMS-DVB (65µm) and CAR-PDMS (75µm) for the extraction of all of the analytes studied.

Polymeric imidazolium ionic liquids as valuable stationary phases in gas chromatography: chemical synthesis and full characterization.

Seven new functionalized polymerizable ionic liquids were chemically prepared, and later applied for the preparation of polymeric stationary phases in gas chromatography. These coated GC columns, which exhibited good thermal stabilities (240-300°C) and very high efficiencies (3120-4200 plates/m), have been characterized using the Abraham solvation parameter model. The chromatographic behavior of these polymeric IL columns has been deeply studied observing excellent selectivities in the separation of many organic substances such as alkanes, ketones, alcohols, amines or esters in mixtures of polar and non polar solvents or fragrances. Remarkably, the challenging separation of xylene isomers has been possible using a bis(trifluoromethylsulfonyl)amide based imidazolium IL coated column as a gas chromatography stationary phase.

Characterization of hexacationic imidazolium ionic liquids as effective and highly stable gas chromatography stationary phases.

Polycationic ionic liquids (ILs) are an attractive class of ILs with great potential applicability as gas chromatography stationary phases. A family of hexacationic imidazolium ILs derived from the cycloalkanol family was chemically first prepared in a straightforward manner and then applied for analytical separation purposes. Four tuneable engineering vectors, namely cation ring size structure, anion nature, spatial disposition of cycloalkanol substituents and O-substitution, were considered as experimental parameters for the design of the desired ionic liquids. A total number of five new phases based on a common benzene core respectively exhibited column efficiencies around to 2500 plates/m, broad operating temperature ranges and also, even more importantly, good thermal stabilities (bleeding temperature between 260 and 365°C), finding variations in the selectivity and analytes elution orders depending on the IL structures. Their solvation characteristics were evaluated using the Abraham solvation parameter model, establishing clear correlations between their cation structure and retention capability with respect to certain analytes. The study of relationships between the ILs structure and solvation parameters gives us an idea of the IL stationary phase to be used for specific separations.

Evaluation of new ionic liquids as high stability selective stationary phases in gas chromatography.

Two ionic liquids (ILs), namely (S,S)-1-butyl-3-(2'-hydroxy-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate and (S,S)-1-butyl-3-(2'-acetyl-cyclohexyl)-3H-imidazol-1-ium tetrafluoroborate have been employed as stationary phases in capillary gas chromatography. These new phases exhibit a column efficiency of 1,600 and 2,100 plates m(-1) for IL 1 and IL 2, respectively, a wide operating temperature range and good thermal stability (bleeding temperature of 250 °C for IL 1 and 160 °C for IL 2). Inverse gas chromatography (GC) analyses were used to study the solvation properties of these ILs through a linear solvation energy model. The application of these ILs as new GC stationary phases was studied. These stationary phases exhibited unique selectivity for many organic substances, such as alkanes, ketones, esters, and aromatic compounds. The efficient separation of several mixtures containing compounds of different polarities and the good separation of fatty acid methyl esters (FAMEs) and cis/trans isomers indicate that these ILs may be applicable as a new type of GC stationary phases.

A novel method for the determination of total 1,3-octanediols in apple juice via 1,3-dioxanes by solid-phase microextraction and high-speed gas chromatography.

In this work, a novel, simple and fast method based on solid-phase microextraction (SPME) followed by high-speed gas chromatography (HSGC) was developed for the analysis of total 1,3-octanediols in apple juices by means of derivatization reaction to volatile 1,3-dioxanes. The derivatization reaction, SPME conditions, glycosidically bound fraction and 1,3-nonanediol as a surrogate standard were studied. The formation of 1,3-dioxanes from 1,3-diols was confirmed by GC-MS. The method was validated obtaining a regression coefficient (r(2)) of 0.9996, precisions between 0.3 and 9.8%, extraction recoveries in the range 94.7-112.2% and LOD of 2.9 microg l(-1). Experimental design has been employed in the optimization of extraction factors and robustness assessment. The method was applied to the analysis of 21 Asturian apple varieties finding a double reciprocal relationship between the concentrations of saturated and unsaturated 1,3-octanediol.

Cider proteins and foam characteristics: a contribution to their characterization.

A capillary sieving electrophoretic method for protein analysis and molecular weight determination was used to characterize ciders from Asturias, northern Spain. The total protein content (Bradford method) and the foam parameters (Bikerman method) were also analyzed to complete this characterization. The polypeptide profile, based on the molecular weight, together with exploratory and classification techniques, that is, principal component analysis (PCA) or linear discriminant analysis (LDA), allowed ciders to be differentiated on the basis of their foam assessment and the apple juice extraction technology used in the cidermaking process. In addition, the application of correlation analysis, that is, canonical correlations (CCA) or partial least-squares (PLS), revealed that the proteins with higher molecular weight were more relevant with respect to cider foamability. PLS analysis also provided a mathematical equation that is able to predict the stabilization time of foam from the polypeptide profile of the cider, because this is the foam parameter most influenced by these compounds.

Detection of apple juice concentrate in the manufacture of natural and sparkling cider by means of HPLC chemometric sugar analyses.

An HPLC method for sugar analyses in cider was used in order to detect the presence of apple juice concentrate. Sugars, previously derivatized with p-aminobenzoic ethyl ester, were analyzed by reversed-phase liquid chromatography using a C(8) column and a mobile phase of citrate buffer pH 5.5/tetrahydrofuran/acetonitrile, operated in gradient mode. The use of this analytical procedure together with chemometric techniques, such as principal component analysis and Bayesean analysis, allowed the authors to establish the minimum concentration of apple juice concentrate obtained by liquefaction or press technology that can be detected in natural cider.

Influence of distillation system, oak wood type, and aging time on composition of cider brandy in phenolic and furanic compounds.

A control of phenolic and furanic compounds in cider brandy was carried out during maturation in oak casks, studying three technological factors: distillation (rectification column vs double distillation), oak wood type (French vs American), and aging time (32 months). Gallic acid and benzoic and cinnamic aldehydes significantly increased during maturation of cider brandies, the highest level of these phenolics being obtained when aging was conducted in French oak casks. Benzoic acids increased during aging, though furanic compounds were not influenced by the time factor. Distillation and wood factors significantly influenced furanic concentration; 5-hydroxymethylfurfural not was detected in fresh spirits and was extracted in the highest proportion in French oak. Volatile furanics, such as 5-methylfurfural, furfural, and 2-furylmethyl ketone, were influenced by the distillation factor, with the use of the double distillation system producing a higher level of these compounds. Scopoletin was the majority coumarin detected in cider brandies, the highest yield of which was obtained with the use of American oak.

Influence of Fatty acids on foaming properties of cider.

Seventy-seven ciders from four consecutive harvests, which were produced at industrial scale by cider-makers from the region of Asturias (northern Spain), were analyzed to evaluate their foam capacity. The Bikerman method for the evaluation of foaming characteristics was adapted to ciders. In foaming, there are two parameters, foam formation and foam stability, which are found to be related to each other. To determine the relationship between fatty acid content and foaming properties of cider, the multivariate analysis technique of canonical correlation analysis was applied. Foam stability is positively related to the content of caprylic acid. Foam height is positively related to linolenic, pentadecanoic, and palmitic acid and negatively related to stearic and linoleic acid.

Evolution of sugars in cider brandy aged in oak barrels: a contribution to its characterization.

A chemometric study was carried out to typify cider brandies according to the type of wood employed in the maturation process and their aging time. Monosaccharides, previously derivatized with p-aminobenzoic ethyl ester, were analyzed using a reversed-phase high-performance liquid chromatographic method. Univariate data treatment was not sufficient to enable differentiation of the classes of cider brandies on the basis of wood type and maturation time. Two linear combinations of original variables, ascertained by principal components analysis, provided an adequate data structurization. A mathematical decision rule was established to classify cider brandies with prediction capacities of 92 and 97% using an LDA method and Bayesian analysis, respectively. The use of the PLS algorithm allowed the authors to differentiate cider brandies according to the age and type of oak used in the aging process.

Characterization of cider apples on the basis of their fatty acid profiles.

In the current study, the fatty acids composition of 30 monovarietal apple juices from six cider apple varieties belonging to two categories was analyzed. The different apple juices were obtained from three consecutive harvests (1997, 1998, and 1999). The fatty acids concentration in apple juice together with chemometric techniques such as principal components analysis (PCA), soft independent modeling of class analogy (SIMCA), and linear discriminant analysis (LDA), allowed us to differentiate apple juices on the basis of the sweet or sharp category to which the cider apple variety belongs. Fatty acids such as the unsaturated oleic and linoleic acids, and saturated caprylic, capric, stearic, and palmitic acids were related to the sweet cider apple category, while pentadecanoic acid is related to the sharp class.