Corylus avellana 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 Corylus avellana L. belonging to different cultivars (Tonda Gentile Romana, Tonda Gentile Trilobata, Anakliuri) 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 (E)-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 (S)-enantiomer in both raw and roasted samples volatilome with larger differences in raw samples. The amount of both (R) and (S)-filbertone increases during roasting; the most marked increase for (R)-enantiomer is observed in Italian samples, thus supporting evidence of better hedonic properties and more pleasant odor and aroma.

Corylus avellana L. Aroma Blueprint: Potent Odorants Signatures in the Volatilome of High Quality Hazelnuts.

The volatilome of hazelnuts (Corylus avellana L.) encrypts information about phenotype expression as a function of cultivar/origin, post-harvest practices, and their impact on primary metabolome, storage conditions and shelf-life, spoilage, and quality deterioration. Moreover, within the bulk of detectable volatiles, just a few of them play a key role in defining distinctive aroma (i.e., aroma blueprint) and conferring characteristic hedonic profile. In particular, in raw hazelnuts, key-odorants as defined by sensomics are: 2,3-diethyl-5-methylpyrazine (musty and nutty); 2-acetyl-1,4,5,6-tetrahydropyridine (caramel); 2-acetyl-1-pyrroline (popcorn-like); 2-acetyl-3,4,5,6-tetrahydropyridine (roasted, caramel); 3-(methylthio)-propanal (cooked potato); 3-(methylthio)propionaldehyde (musty, earthy); 3,7-dimethylocta-1,6-dien-3-ol/linalool (citrus, floral); 3-methyl-4-heptanone (fruity, nutty); and 5-methyl-(E)-2-hepten-4-one (nutty, fruity). Dry-roasting on hazelnut kernels triggers the formation of additional potent odorants, likely contributing to the pleasant aroma of roasted nuts. Whiting the newly formed aromas, 2,3-pentanedione (buttery); 2-propionyl-1-pyrroline (popcorn-like); 3-methylbutanal; (malty); 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel); dimethyl trisulfide (sulfurous, cabbage) are worthy to be mentioned. The review focuses on high-quality hazelnuts adopted as premium primary material by the confectionery industry. Information on primary and secondary/specialized metabolites distribution introduces more specialized sections focused on volatilome chemical dimensions and their correlation to cultivar/origin, post-harvest practices and storage, and spoilage phenomena. Sensory-driven studies, based on sensomic principles, provide insights on the aroma blueprint of raw and roasted hazelnuts while robust correlations between non-volatile precursors and key-aroma compounds pose solid foundations to the conceptualization of aroma potential.

Shelf-Life Evolution of the Fatty Acid Fingerprint in High-Quality Hazelnuts (Corylus avellana L.) Harvested in Different Geographical Regions.

Hazelnuts are characterized by a relatively high abundance of oleic acid and poly-unsaturated fatty acids, which give this fruit a high nutritional value. As a counterbalance, such a lipid profile is more susceptible to autoxidation and/or degradation reactions under enzymatic catalysis. Lipid oxidation occurs on fatty acids (FAs), both esterified on triacylglycerols and in free form (after lipolysis), but with favorable kinetics on the latter. In this study, the quali-quantitative changes in FA profiles (both free and esterified) were monitored during the shelf life (time 0, 6, and 12 months) as a function of different drying and storage conditions and different cultivars and geographical areas. A derivatization/extraction procedure was performed to quantify the profile of free and esterified fatty acids accurately. The overall profile of the free and esterified fatty acids concurred to create a biological signature characteristic of the cultivar and of the harvest region. The free and esterified forms' characterization enabled the efficient monitoring of the effects of both the hydrolytic activity (increment in overall free fatty acids) and the oxidative process (decrease in unsaturated free fatty acids versus esterified fatty acids) over the 12 months of storage.

Exploring extra dimensions to capture saliva metabolite fingerprints from metabolically healthy and unhealthy obese patients by comprehensive two-dimensional gas chromatography featuring Tandem Ionization mass spectrometry.

This study examines the information potential of comprehensive two-dimensional gas chromatography combined with time-of-flight mass spectrometry (GC×GC-TOF MS) and variable ionization energy (i.e., Tandem Ionization™) to study changes in saliva metabolic signatures from a small group of obese individuals. The study presents a proof of concept for an effective exploitation of the complementary nature of tandem ionization data. Samples are taken from two sub-populations of severely obese (BMI > 40 kg/m2) patients, named metabolically healthy obese (MHO) and metabolically unhealthy obese (MUO). Untargeted fingerprinting, based on pattern recognition by template matching, is applied on single data streams and on fused data, obtained by combining raw signals from the two ionization energies (12 and 70 eV). Results indicate that at lower energy (i.e., 12 eV), the total signal intensity is one order of magnitude lower compared to the reference signal at 70 eV, but the ranges of variations for 2D peak responses is larger, extending the dynamic range. Fused data combine benefits from 70 eV and 12 eV resulting in more comprehensive coverage by sample fingerprints. Multivariate statistics, principal component analysis (PCA), and partial least squares discriminant analysis (PLS-DA) show quite good patient clustering, with total explained variance by the first two principal components (PCs) that increases from 54% at 70 eV to 59% at 12 eV and up to 71% for fused data. With PLS-DA, discriminant components are highlighted and putatively identified by comparing retention data and 70 eV spectral signatures. Within the most informative analytes, lactose is present in higher relative amount in saliva from MHO patients, whereas N-acetyl-D-glucosamine, urea, glucuronic acid γ-lactone, 2-deoxyribose, N-acetylneuraminic acid methyl ester, and 5-aminovaleric acid are more abundant in MUO patients. Visual feature fingerprinting is combined with pattern recognition algorithms to highlight metabolite variations between composite per-class images obtained by combining raw data from individuals belonging to different classes, i.e., MUO vs. MHO.Graphical abstract.

Nutrimetabolomics: An Integrative Action for Metabolomic Analyses in Human Nutritional Studies.

The life sciences are currently being transformed by an unprecedented wave of developments in molecular analysis, which include important advances in instrumental analysis as well as biocomputing. In light of the central role played by metabolism in nutrition, metabolomics is rapidly being established as a key analytical tool in human nutritional studies. Consequently, an increasing number of nutritionists integrate metabolomics into their study designs. Within this dynamic landscape, the potential of nutritional metabolomics (nutrimetabolomics) to be translated into a science, which can impact on health policies, still needs to be realized. A key element to reach this goal is the ability of the research community to join, to collectively make the best use of the potential offered by nutritional metabolomics. This article, therefore, provides a methodological description of nutritional metabolomics that reflects on the state-of-the-art techniques used in the laboratories of the Food Biomarker Alliance (funded by the European Joint Programming Initiative "A Healthy Diet for a Healthy Life" (JPI HDHL)) as well as points of reflections to harmonize this field. It is not intended to be exhaustive but rather to present a pragmatic guidance on metabolomic methodologies, providing readers with useful "tips and tricks" along the analytical workflow.