Development of a Solid-Phase Microextraction-Gas Chromatography/Mass Spectrometry Method for Quantifying Nitrogen-Heterocyclic Volatile Aroma Compounds: Application to Spirit and Wood Matrices.

Over wood aging, matured spirits developed a complex aromatic bouquet where roasted-like notes were often perceived. Since many nitrogen heterocycles were related to these olfactory nuances, a headspace solid-phase microextraction (HS-SPME) coupled to gas chromatography-mass spectrometry was developed and validated to quantify them in both spirit and wood matrices. The various parameters affecting the extraction of the analytes from both spirit and wood samples were first investigated (i.e., fiber coating phase, dilution, pH and volume sample, adding salt, extraction time and temperature, and incubation time) to determine the best compromise for a single-run analysis of the whole set of studied compounds. Good linearity (R2 > 0.99), repeatability, reproducibility, accuracy and low detection, and quantification limits were obtained, making this analytical method a suitable tool for routine analysis of the selected nitrogen compounds. Fifteen pyrazines, three pyrroles, and three quinolines were quantified in a series of oak wood and commercial spirit samples where some of them were identified for the first time. The significant impact of some barrel features and the spirit in-wood maturation step on the N-heterocycle profile in both matrices were finally discussed.

Isolation and structural characterization of anthocyanin-furfuryl pigments.

Condensation reactions of malvidin-3-glucoside with two representative oak wood furanic aldehydes (furfural and methylfurfural) were conducted in wine-like model solutions. Methylfurfural led to the formation of malvidin-3-glucoside-methylfurfural (603 m/z), whereas furfural led to the formation of malvidin-3-glucoside-furfural (589 m/z). The latter was structurally characterized by 1D and 2D NMR, allowing an elucidation of the formation mechanism of these anthocyanin-furanic aldehyde adducts in the absence of flavanols.

Conformational interpretation of vescalagin and castalagin physicochemical properties.

Vescalagin and castalagin are two diastereoisomers. The variability of their principal physicochemical properties, compared with their small structural differences, suggests important conformational variations. This study shows, experimentally, that vescalagin has a greater effect on polarity, oxidizability in solution, and thermodegradability than castalagin. Conformational analysis by molecular mechanics demonstrated that vescalagin was more hydrophilic and was more reactive to electrophilic reagents than castalagin. Experimental results were thus explained and demonstrated the distinct behaviors of vescalagin and castalagin. These results were attributed to the C1 position of the two compounds because vescalin and castalin have comparable characteristics. Experimental data were confirmed and interpreted by molecular mechanics. This work represents one of the first attempts to correlate conformation and the properties of phenolic compounds. This step constitutes a predictive method for the pharmacology or chemistry of new compounds.