Discrimination of French wine brandy origin by PTR-MS headspace analysis using ethanol ionization and sensory assessment.

The headspace volatile organic compound (VOC) fingerprints (volatilome) of French wine brandies were investigated by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Protonated ethanol chemical ionization was used with dedicated experimental conditions that were previously validated for model wines. These included a reference vial containing a hydro-alcoholic solution with the same ethanol content (20% v/v) as the diluted sample spirits, which was used to establish steady-state ionization conditions. A low electric field strength to number density ratio E/N (85 Td) was used in the drift tube in order to limit the fragmentation of the protonated analytes. The obtained headspace fingerprints were used to investigate the origin of French brandies produced within a limited geographic production area. Brandies of two different vintages (one freshly distilled and one aged for 14 years in French oak barrels) were successfully classified according to their growth areas using unsupervised (principal component analysis, PCA) and supervised (partial least squares regression discriminant analysis, PLS-DA) multivariate analyses. The models obtained by PLS-DA allowed the identification of discriminant volatile compounds that were mainly characterised as key aroma compounds of wine brandies. The discrimination was supported by sensory evaluation conducted with free sorting tasks. The results showed that this ethanol ionization method was suitable for direct headspace analysis of brandies. They also demonstrated its ability to distinguish French brandies according to their growth areas, and this effect on brandy VOC composition was confirmed at a perceptive level.

Impact of swallowing on the dynamics of aroma release and perception during the consumption of alcoholic beverages.

The consumption protocol used during alcoholic beverage tasting may affect aroma perception. We used an integrated approach combining sensory analysis and physicochemistry to investigate the impact of swallowing on aroma release and perception. A panel of 10 persons evaluated the dynamics of aroma perception during the consumption of a commercial flavored vodka, using the method of temporal dominance of sensations. Two protocols (spitting out or swallowing of the product) were tested. Nosespace analysis was simultaneously carried out by proton transfer reaction mass spectrometry to evaluate aroma release in the nasal cavity. Comparison of the results obtained with the 2 protocols highlighted significant differences in both the perception and the release of aroma: the swallowing of the product resulted in more complex perceptions but decreased the dominance rates of aromatic attributes. Ethanol perception also had an impact when the product was swallowed. Aroma release data partly accounted for the differences in perception, particularly as concerned ethanol release. The time at which dominance appears as well as the dominance duration of some attributes can be related to some temporal parameters of release data. But the lack of knowledge concerning the variety and complexity of mechanisms continues to limit our understanding of relationship between aroma release and perception.

Photochemistry in everyday life: the effect of spontaneous emulsification on the photochemistry of trans-anethole.

The photochemical behaviour of spontaneously formed microemulsions obtained upon dilution of ethanolic solutions of trans-anethole (E-1-(4-methoxyphenyl)propene, t-A) with water is compared to that of homogeneous ethanolic t-A solutions. Significant differences in reactivity reflect the confined nature of the aggregated t-A which leads to reduced yields of isomerization and dimerization products. In contrast to homogeneous solutions, where a photostationary state enriched in the Z-isomer (c-A) is rapidly reached, the proportion of c-A formed upon irradiation of t-A microemulsions remains below 15%. In the presence of oxygen the formation of trans-anethole oxide is observed which, when formed in non-homogeneous environments, undergoes polymerization.

Probing the initial events in the spontaneous emulsification of trans-anethole using dynamic NMR spectroscopy.

The spontaneous emulsification of alcoholic solutions of trans-anethole (t-A) in water is investigated using EXSY and DOSY NMR techniques. The system investigated (5-10 mM t-A in 5% EtOH/H2O solution) is exceptional in providing sharp, clearly resolved signals for both t-A that is dissolved in the aqueous phase (free t-A) and t-A that is incorporated in aggregates (3-6 nm diameter) thus allowing both fractions to be probed simultaneously. This feature is utilized to explore the initial events that occur during the spontaneous emulsification process. Upon mixing, the majority of the t-A (ca. 75%) undergoes nucleation to form small aggregates (ca. 10 nm diameter), while 15% (corresponding to [t-A] = 7.5 x 10(-4) M) is dissolved in the aqueous phase. The kinetic rates governing the exchange process between aggregated and free t-A are found to be time-dependent and slow on the NMR time scale (k = 0.8-2 s(-1)). DOSY experiments indicate that the initially formed small aggregates undergo rapid coalescence to form larger droplets. Ostwald ripening of these droplets at the expense of the remaining small aggregates is responsible for the subsequent, slower time-evolution of the system.