Determination of volatile compounds in cider apple juices using a covalently bonded ionic liquid coating as the stationary phase in gas chromatography.

A chromatographic method for the separation of volatile compounds in Asturian cider apple juices has been developed. For this separation purpose, a monocationic imidazolium-based ionic liquid bearing a reactive terminal iodine atom was synthesized by a quaternization-anion exchange chemical sequence. Next, the gas chromatography (GC) stationary phase was prepared by covalently linking the imidazolium monolith to the reactive silanol groups of the inner capillary wall at 70 °C. This coated GC column exhibited good thermal stability (290 °C), as well as good efficiency (2000 plates/m) in the separation of volatile compounds from Asturian apple cider juices, and was characterized using the Abraham solvation parameter model. The intra-day and inter-day precision of the chromatographic method was evaluated, obtaining relative standard deviations from 3.7 to 12.9% and from 7.4 to 18.0%, respectively. Furthermore, recoveries from 82.5 to 122% were achieved. Graphical Abstract Covalent bonding of an ionic liquid to inner column wall led to a great improvement of the separation efficiencies of stationary phases in gas chromatography.

Characterization of Spanish ciders by means of chemical and olfactometric profiles and chemometrics.

A comparative study of the aroma (volatile composition and olfactometric profiles) of Asturian and Basque still ciders in two maturation stages was conducted. Among the major volatile compounds, amyl alcohols, ethyl lactate and ethyl acetate were quantitatively relevant in all of the ciders studied. The minor fraction mainly consisted of fatty acids, volatile phenols and alcohols. Three PLS-discriminant models with low prediction errors were constructed. When the volatile composition was used, ciders could be differentiated by their maturation stage, 4-ethylcatechol being strongly associated to matured ciders. The olfactometric profiles allowed the classification of ciders according to both their origin and maturation stage. Odorants such as p-cresol and a sweet-character unknown component were correlated to origin of ciders, whereas 1-octen-3-one and one unknown spicy-vegetal odorant were highly correlated to the maturation stage.

Impact of different techniques involving contact with lees on the volatile composition of cider.

The effect of different treatments involving contact with natural lees on the aromatic profile of cider has been evaluated. Comparing with the untreated ciders, the contact with lees brought about a significant increase of the concentrations of most of the volatile compounds analysed, in particular fatty acids, alcohols, ethyl esters and 3-ethoxy-1-propanol. The opposite was observed among fusel acetate esters and 4-vinylguaiacol. The addition of ß-glucanase enhanced the increase of ethyl octanoate, but produced a decrease in the contents of decanoic acid and all of the major volatiles excepting acetaldehyde, ethyl acetate and acetoine, whereas the application of oxygen influenced the rise of the level of 3-ethoxy-1-propanol only. The olfactometric profiles also revealed significant effects of the treatment with lees for ethyl propionate, diacetyl, cis-3-hexenol, acetic acid, benzyl alcohol, and m-cresol, while the addition of oxygen significantly influenced the perception of ethyl hexanoate, 1-octen-3-one, 3-methyl-2-butenol, t-3-hexenol and c-3-hexenol.

A chemometric approach to characterization of ionic liquids for gas chromatography.

A chemometric study was carried out to characterize three ionic liquid types (ILs) with hexacationic imidazolium, polymeric imidazolium, and phosphonium cationic cores, using a range of contra-anions such as halogens, thiocyanate, boron anions, triflate, and bistriflimide. The solvation parameter model developed by Abraham et al., unsupervised techniques as cluster analysis (CA), and supervised techniques as linear discriminant analysis (LDA), step-LDA, quadratic discriminant analysis (QDA), and multivariate regression techniques as discriminant partial least squares (D-PLS), or multiple linear regression (MLR) were used to characterize the functionalized ILs above. CA established two main groups of phases, those with an acidic H-bond and those with basic ones. Once detected, the two natural groups, a linear and quadratic delimiters with good classification (>96 %) and prediction (>92 %) capacities were computed. The use of step-LDA technique allowed us to establish that a, b, and s solvation parameters were the most discriminant variables. These variables were used for modeling purposes, and a D-PLS and MLR models were constructed using a binary response. The explained variance of categorical variable by the model validated by cross-validation was 65 %, and 94.5 % of ILs were correctly predicted. IL characterization carried out would allow the appropriate selection of phases for gas chromatography (GC).

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.

Screening of cider yeasts for sparkling cider production (Champenoise method).

A total of 350 colonies isolated from a cider cellar in Asturias (Spain) were identified by rDNA ITS-RFLP restriction analysis. Saccharomyces spp. strains were characterized by mitochondrial DNA (mtDNA) restriction analysis. Fifty-four different Saccharomyces spp. strains were identified and tested to ascertain their capacity to carry out secondary fermentation of sparkling ciders. The screening of yeasts to determine their principal enological characteristics (tolerance to ethanol, production of volatile acidity and hydrogen sulphide) was accomplished by means of rapid, non-expensive assays (plate agar). As a result, 13 (24%) of the 54 initial Saccharomyces spp. yeast strains were eliminated. The technological properties assessed were flocculation capacity, ethanol and sulphite tolerance, and production of major volatiles. Ten Saccharomyces cerevisiae strains were characterized as true flocculants; all of these strains were able to grow in ethanolic medium and in the presence of 200mg/l of sulphite. Applying cluster analysis to the production of amyl alcohols, isobutanol, propanol and 2-phenylethanol, the strains were classified in two natural groups. Two flocculent yeast strains referred to as 3' and 50', representative of the each statistical group, were selected together with two reference strains (Saccharomyces bayanus C6 and S. cerevisiae Levuline CHP) to elaborate four sparkling ciders by the Champenoise method. The analysis of variance (p<0.01) among ciders revealed that glycerol, acetaldehyde, ethyl acetate, methanol, propanol, i-butanol and 2-phenylethanol were significantly influenced by the secondary yeast strain. The results of sensory analysis indicated that all the sparkling ciders were scored as good. No significant differences among sparkling ciders were found for odour attributes and taste intensity.