L. Natural Signature: Chiral Recognition of Selected Informative Components in the Volatilome of High-Quality Hazelnuts.

The volatile fraction of plant-based foods provides useful functional information concerning sample-related variables such as plant genotype and phenotype expression, pedoclimatic and harvest conditions, transformation/processing technologies, and can be informative about the sensory quality. In this respect, the enantiomeric recognition of the chiral compounds increases the level of information in profiling studies, being the biosynthesis of native compounds often stereo-guided. Chiral native volatiles mostly show an enantiomeric excess that enables origin authentication or support correlation studies between chemical patterns and sensory profiles. This study focuses, for the first time, on the enantiomeric composition of a large set of chiral compounds within the complex volatilome of L. belonging to different cultivars (, , ) and harvested in different geographical areas (Italian and Georgian). Besides native components profiled in raw kernels, volatiles formed after technological treatment (i.e., roasting) are also considered. Headspace solid-phase microextraction combined with enantioselective gas chromatography-mass spectrometry enables the accurate tracking and annotation of about 150 compounds across many samples. The results show that chiral compounds have diagnostic distribution patterns within hazelnut volatilome with cultivar and harvest region playing the major role. Moreover, being some of these chiral molecules also key-aromas, their distribution has a decisive impact on the sensory properties of the product. In particular, the enantiomeric composition of ()-5-methyl-2-hepten-4-one (filbertone) resulted to be discriminant for origin authentication. The enantiomeric distribution showed, according to literature, an excess of the ()-enantiomer in both raw and roasted samples volatilome with larger differences in raw samples. The amount of both () and ()-filbertone increases during roasting; the most marked increase for ()-enantiomer is observed in Italian samples, thus supporting evidence of better hedonic properties and more pleasant odor and aroma.