HS-SPME-GC-MS and Chemometrics for the Quality Control and Clustering of Monovarietal Extra Virgin Olive Oil: A 3-Year Study on Terpenes and Pentene Dimers of Italian Cultivars.

Terpenes and pentene dimers are less studied volatile organic compounds (VOCs) but are associated with specific features of extra virgin olive oils (EVOOs). This study aimed to analyze mono- and sesquiterpenes and pentene dimers of Italian monovarietal EVOOs over 3 years (14 cultivars, 225 samples). A head space-solid-phase microextraction-gas chromatography-mass spectrometry (HS-SPME-GC-MS) method recently validated was used for terpene and pentene dimer quantitation. The quantitative data collected were used for both the characterization and clustering of the cultivars. Sesquiterpenes were the molecules that most characterized the different cultivars, ranging from 3.908 to 38.215 mg/kg; different groups of cultivars were characterized by different groups of sesquiterpenes. Pentene dimers (1.336 and 3.860 mg/kg) and monoterpenes (0.430 and 1.794 mg/kg) showed much lower contents and variability among cultivars. The application of Kruskal-Wallis test-PCA-LDA-HCA to the experimental data allowed defining 4 clusters of cultivars and building a predictive model to classify the samples (94.3% correct classification). The model was further tested on 33 EVOOs, correctly classifying 91% of them.

Markers of sensory dynamics in phenols-rich virgin olive oils under optimal storage conditions.

Early changes in sensory quality of phenols-rich virgin olive oil (VOO) and their relationship with the chemical changes are less studied in the literature. Therefore, the objective of this study was to propose a predictive model of dynamics of sensory changes based on specific chemical markers. The evolution of the sensory quality of phenol-rich VOOs from Tuscan cultivars stored under optimal storage conditions (i.e., absence of light, no O2 exposure, low temperature) was investigated using a multi-step methodological approach combining sensory (official sensory analysis (so-called Panel Test), Descriptive Analysis and Temporal Dominance of Sensation) and chemical measurements. The sensory map from descriptive data was related to the phenolic and volatile profiles, measured using HPLC-DAD and HS-SPME-GC-MS, respectively. A predictive model of the sensory changes over storage based on chemical compounds was developed. Results showed that very early changes involving phenolic and volatile compounds profiles occur in VOOs stored under optimal storage conditions, which turn in changes in sensory properties evaluated by the official panel test, the descriptive analysis and the temporal dominance of sensation. Furthermore, a chemical marker of sensory dynamics of oils during storage was identified as the ratio between two groups of secoiridoids. The proposed model, supported by the mentioned chemical marker, has the potential of improving the control of sensory changes in phenols-rich virgin olive oils during storage in optimal conditions.

Can a Fraction of Flour and Sugar Be Replaced with Fruit By-Product Extracts in a Gluten-Free and Vegan Cookie Recipe?

Certain food by-products, including not-good-for-sale apples and pomegranate peels, are rich in bioactive molecules that can be collected and reused in food formulations. Their extracts, rich in pectin and antioxidant compounds, were obtained using hydrodynamic cavitation (HC), a green, efficient, and scalable extraction technique. The extracts were chemically and physically characterized and used in gluten-free and vegan cookie formulations to replace part of the flour and sugar to study whether they can mimic the role of these ingredients. The amount of flour + sugar removed and replaced with extracts was 5% and 10% of the total. Physical (dimensions, color, hardness, moisture content, water activity), chemical (total phenolic content, DPPH radical-scavenging activity), and sensory characteristics of cookie samples were studied. Cookies supplemented with the apple extract were endowed with similar or better characteristics compared to control cookies: high spread ratio, similar color, and similar sensory characteristics. In contrast, the pomegranate peel extract enriched the cookies in antioxidant molecules but significantly changed their physical and sensory characteristics: high hardness value, different color, and a bitter and astringent taste. HC emerged as a feasible technique to enable the biofortification of consumer products at a real scale with extracts from agri-food by-products.

Analysis of Volatile Hydrocarbons (Pentene Dimers and Terpenes) in Extra Virgin Olive Oil: Optimization by Response Surface Methodology and Validation of HS-SPME-GC-MS Method.

A head space-solid phase microextraction-gas chromatography-mass spectrometery (HS-SPME-GC-MS) method for the simultaneous analysis of pentene dimers from lipoxygenase (LOX) pathway, monoterpenes, and sesquiterpenes in extra virgin olive oil (EVOO) was proposed. A Doehlert design was performed; the conditions of the HS-SPME preconcentration step (extraction temperature, extraction time, sample amount, and desorption time) were optimized by response surface methodology, allowing defining the method operable design region. A quantitative method was set up using the multiple internal standard normalization approach: four internal standards were used, and the most suitable one was selected for area normalization of each external standard. The quantitative method was successfully validated and applied to a series of monocultivar EVOOs. This is the first paper in which a quantitative method using commercial standards has been proposed for the analysis of an important class of molecules of EVOO such as pentene dimers. The optimized method is suitable for routine analysis aimed at characterizing high quality EVOOs.

Chemical Data and Relationships for a Scoring Algorithm of Extra Virgin Olive Oil's Nutritional Value.

Extra virgin olive oil (EVOO) is a valuable product and is highly appreciated by consumers for its great nutritional value. However, to date, there has been a lack of uniform systems capable of ranking the nutritional value of EVOO based on its chemical composition in terms of macro- and micronutrients (including phenolic compounds and tocopherols). The aim of this study was to propose a scoring algorithm to rank the nutritional value of EVOO samples, considering their chemical composition in macro- and micronutrients and their sensitivity to oxidation phenomena. Data from more than 1000 EVOO samples were used to assess the variability of the data, considering the selected negative parameters (free acidity, peroxide value, spectrophotometric indices) and positive components (composition in tocopherols via HPLC-DAD, phenolic compounds via HPLC-DAD, and fatty acids via GC-MS) so as to ensure the universal validity of the scoring algorithm. The dataset included samples from the main producing countries worldwide, in addition to Australia, across several production years; data were selected to represent different production realities. A mathematical model was set up for each chemical component, resulting in six variable values. By combining these values with a dimensionless constant value, the algorithm for computing the nutritional value score (NVS) was defined. It allows the nutritional value of an oil to be ranked on a scale of 0 to 100 based on its chemical composition. The algorithm was then successfully tested using chemical data from about 300 EVOO samples obtained from laboratories from different Italian regions. The proposed NVS is a simple and objective tool for scoring the nutritional value of an EVOO, easy to understand for both producers and consumers.

Characterization of 20 Oenological Tannins from Different Botanical Origins for Formulation of Blends with Redox Potential Tuning Ability in Model Wine Solution.

Twenty oenotannins from different botanical origins were studied in model wine solution (1 g/L, 12% ethanol, pH 3.5). An original device was created for measuring Oxidation-Reduction potential (ORp) of the solutions at 20 °C in strict anoxic condition by the electrochemical method of the platinum electrode zero-current potential. Reactivity against proteins and antioxidant properties were related to the chemical structure and, consequently, to the botanical origin of the oenotannins. The highest turbidity after BSA addition (ΔNTU > 1000) values were measured for the gallic hydrolysable tannins. The ORp versus standard hydrogen electrode ranged from 420 to 260 mV. The ellagitannins had the highest antioxidant power (AP%), followed by condensed tannins and gallotannins, highlighting a correlation with the phenolic profile. Based on these findings, two formulations were prepared as a blend of some of the tested oenotannins, with the ability to increase (MIX1) and decrease (MIX2) the ORp of the model wine.

Chemical Characterization, Sensory Definition and Prediction Model of the Cider Dryness from New York State Apples.

Cider is a fermented drink obtained from apple juice. As a function of the used apple cultivar, cider can be classified in four different categories (dry, semi-dry, semi-sweet, sweet), distinguished by the attribute of "dryness," which reflects the sweetness and softness perceived. The dryness level is defined by scales (IRF, NYCA scales) based on the residual sugar, titratable acidity and tannin contents. Despite some adjustments, these scales show limitations in the prediction of actual perceived dryness, as they cannot consider the complicated interrelation between combined chemical compounds and sensory perception. After defining the perceived sensory dryness and its sensory description by using the quantitative descriptive analysis (QDA) method, a multivariate approach (PLS) was applied to define a predictive model for the dryness and to identify the chemical compounds with which it was correlated. Three models were developed, based on three different sets of chemical parameters, to provide a method that is easily applicable in the ordinary production process of cider. The comparison between the predicted rating and the relative scales scores showed that the models were able to predict the dryness rating in a more effective way. The multivariate approach was found to be the most suitable to study the relation between chemical and sensory data.

Virgin Olive Oil By-Product Valorization: An Insight into the Phenolic Composition of Olive Seed Extracts from Three Cultivars as Sources of Bioactive Molecules.

Olives are very rich in phenolic compounds with important health-promoting properties. The profile and content of phenols in olive pulp and virgin olive oil are strongly influenced by the fruit ripening degree, but little is known concerning the evolution of phenolic compounds in the seed. In this work, the phenolic composition of seed from Tuscan cultivars (Frantoio, Moraiolo, Leccino) was studied over maturation. Starting from each seed sample, a phenolic extract was prepared and analyzed by HPLC-DAD-MS. Nüzhenide and nüzhenide 11-methyl oleoside were by far the most abundant phenolic compounds; their content reached up to 46 g/kg in dry seeds, although this diminished in the final stage of fruit maturation. At the same time, the phenolic composition of the pulp was also characterized over the course of maturation, showing that oleuropein was by far the most abundant compound, with concentrations comparable to those of nüzhenide and nüzhenide 11-methyl oleoside in the seeds. Overall, the total amount of phenols in seed dry extracts was significant, reaching approx. 100 g/kg. The chemically characterized dry phenolic extracts from seeds could be used for future biological assays aimed at evaluating the potential bioactivities of these phytocomplexes.

Co-milling of sound olives with fresh chili peppers improves the volatile compound, capsaicinoid and sensory profiles of flavoured olive oil with respect to the typical infusion.

In the context of the olive oil flavoured with chili peppers, the aim of this study was to compare co-milling of sound olives and fresh chili peppers at mill scale to infusion of dried chili peppers in oil, using the same batch of olives for all oils. Capsaicinoids by HPLC-DAD, volatile profile by HS-SPME-GC-MS and HS-GC-IMS and sensory profile were characterized. Capsaicinoids were statistically higher in oils prepared with green (52.0-68.0 mg/kg) than red (48.0-60.2 mg/kg) chili peppers. Oils flavoured by infusion showed higher contents of volatile compounds linked to defects such as acetic acid, with winey/vinegary sensory defect (median, 1.72-2.02) and no fresh pepper flavour. Oils prepared by co-milling resulted rich in the typical esters of chili pepper (6.175 and 4.156 mg/kg with green and red chili peppers, respectively), with pleasant hotness sensation and fresh pepper flavour. Overall, the co-milling approach allowed obtaining flavoured samples with improved sensory quality.

Exploitation of virgin olive oil by-products (Olea europaea L.): phenolic and volatile compounds transformations phenomena in fresh two-phase olive pomace ('alperujo') under different storage conditions.

BACKGROUND: Much effort has recently been spent for re-using virgin olive oil by-products as nutraceutical ingredients for human diet thanks to their richness in bioactive phenols, but their management is not easy for producers. We aimed to provide useful information for a better management of fresh olive pomace before drying, by studying the phenolic and volatile compounds transformations phenomena of fresh olive pomace stored under different conditions planned to simulate controlled and uncontrolled temperature conditions in olive oil mills. RESULTS: The evolution of the phenolic and volatile compounds was studied by high-performance liquid chromatography-diode array detector mass spectrometry (HPLC-DAD-MS) and headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS). The phenolic profile varied rapidly during storage: the verbascoside content decreased about 70% after 17 days even at 4 °C, while the content of simple phenols such as hydroxytyrosol and caffeic acid increased over time. The low temperature was able to slow down these phenomena. A total of 94 volatile organic compounds (VOCs) were detected in the fresh olive pomace, with a prevalence of lipoxygenase (LOX) VOCs (78%), mainly aldehydes (19 490.9 µg kg-1 ) despite the higher number of alcohols. A decrease in LOX volatiles and a quick development of the ones linked to off-flavors (carboxylic acids, alcohols, acetates) were observed, in particular after 4 days of storage at room temperature. Only storage at 4 °C allowed these phenomena to be slowed down. CONCLUSION: To preserve the natural phenolic phytocomplex of fresh olive pomace before drying and to avoid off-flavors development, storage in open containers must be avoided and a short storage in cold rooms (7-10 days) is to be preferred. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Whole wheat bread enriched with silver fir (Abies alba Mill.) needles extract: technological and antioxidant properties.

BACKGROUND: The interest of consumers and market and scientific research for added-value foods obtained with environmentally sustainable productive chains is increasing. Silver fir (Abies alba Mill.) needles (SFNs), often by-products of forest management and logging, represent an unexploited source of bioactive compounds. RESULTS: For the first time, SFN aqueous extract obtained through controlled hydrodynamic cavitation was used to enrich whole wheat flour bread. The first trial found that 35% SFNs extract addition was the absolute threshold of taste perception. The second trial investigated dough rheological properties and bread technological and antioxidant properties in samples enriched with 35% and 100% SFNs extract compared with the control (0% SFNs extract). SFNs extract significantly increased bread antioxidant capacity in both 35% and 100% SFN fresh breads by ~42.5% and ~87% respectively and in 100% SFNs bread samples after 72 h of storage by ~76%. Enrichment of 35% showed higher alveograph dough extensibility (~11%) and different bread texture in terms of hardness, springiness, and chewiness. Enrichment with 100% SFNs extract significantly improved dough and bread technological quality: it increased alveograph dough extensibility L (~18%), swelling index G (~8%), and flour strength W (~14%) and showed the highest increase in bread specific volume (~0.200 L kg-1 ). CONCLUSIONS: SFNs aqueous extract produced with controlled hydrodynamic cavitation appeared a valuable technical material for the manufacturing of added-value and functional breads. © 2021 Society of Chemical Industry.

A Methodological Approach to Assess the Effect of Organic, Biodynamic, and Conventional Production Processes on the Intrinsic and Perceived Quality of a Typical Wine: The Case Study of Chianti DOCG.

The aim of this study was to propose a methodological approach to evaluate the impact of the organic, biodynamic, and conventional production processes on the intrinsic and perceived quality of a typical wine. For this purpose, fourteen commercial Chianti DOCG wines from the 2016 harvest were selected based on the type of production management. A survey was set up to get winemaking information from the estate's producer of the wines to estimate the carbon dioxide production under the three types of management. The eligibility, identity, and style properties (the intrinsic quality) of the wines were defined. A group of 45 experts evaluated the differences between wines by the Napping test and rated their typicality (perceived quality). The organic and biodynamic management showed a lower level of estimated values of carbon dioxide production. The overall statistical elaboration of the chemical and sensory data highlighted that the registered differences of the intrinsic, perceived quality, and typicality level of the respective wines, did not depend on the type of management. The comparison of the three kinds of wine by SIMCA modeling, put in evidence that the conventional ones showed a greater homogeneity regarding chemical composition, sensory characteristics, and typicality.

Characterisation of Extracts Obtained from Unripe Grapes and Evaluation of Their Potential Protective Effects against Oxidation of Wine Colour in Comparison with Different Oenological Products.

Unripe grapes (UGs) are a waste product of vine cultivation rich in natural antioxidants. These antioxidants could be used in winemaking as alternatives to SO2. Three extracts were obtained by maceration from Viognier, Merlot and Sangiovese UGs. The composition and antioxidant activity of the UG extracts were studied in model solutions at different pH levels. The capacity of the UG extracts to protect wine colour was evaluated in accelerated oxidation tests and small-scale trials on both red and white wines during ageing in comparison with sulphur dioxide, ascorbic acid and commercial tannins. The Viognier and Merlot extracts were rich in phenolic acids while the Sangiovese extract was rich in flavonoids. The antioxidant activity of the extracts and commercial tannins was influenced by the pH. In the oxidation tests, the extracts and commercial products showed different wine colour protection capacities in function of the type of wine. During ageing, the white wine with the added Viognier UG extract showed the lowest level of colour oxidation. The colour of the red wine with the UG extract evolved similarly to wine with SO2 and commercial tannins. The obtained results indicated that natural and healthy UG extracts could be an interesting substitute for SO2 during wine ageing.

Volatile Profile of Two-Phase Olive Pomace (Alperujo) by HS-SPME-GC-MS as a Key to Defining Volatile Markers of Sensory Defects Caused by Biological Phenomena in Virgin Olive Oil.

An olive pomace from the two-phase decanter stored in different conditions was used as a model to simulate the detrimental biological phenomena occurring during olive oil processing and storage. A group of EVOO and defective oils were also analyzed. The volatile fraction was studied with HS-SPME-GC-MS; 127 volatiles were identified (55 of which tentatively identified) and evaluated over time. Seven volatiles were tentatively identified for the first time in olive oil; the role of C6 alcohols in detrimental biological phenomena was highlighted. Suitable volatile markers for defects of microbiological origin were defined, particularly the fusty/muddy sediment. They were then applied to olive oils with different quality categories; one of the markers was able to discriminate among EVOOs and all the defective samples, including the borderline ones. The marker was constituted by the sum of concentrations of 10 esters, 4 alcohols, 1 ketone, and 1 α-hydroxy-ketone but no carboxylic acids.

Use of the 1H NMR technique to describe the kneading step of wholewheat dough: The effect of kneading time and total water content.

The kneading step of wholewheat flour (WWF) dough was monitored using low-resolution 1H nuclear magnetic resonance (NMR). The tested variables were kneading time and total water content. Two 1H Free induction decay (FID) (A and B) and four 1H T2 Car-Purcell-Meiboom-Gill (CPMG) (C, D, E and F) proton populations were observed and the attribution to the different proton domains was made based on the literature and data acquisition. Kneading time significantly increased the mobility and the relative abundance of popA, the relative abundance and strength of protons of popC, D and E, while significantly reducing the relative amount of popF and increasing its mobility. This evolution of the proton populations during kneading was interpreted as chemical/physical transformations of the flour constituents. The use of WWF may reveal the changes in molecular dynamics underlying the higher water requirements of unrefined doughs, often associated with improved bread quality.

Protection of Wine from Protein Haze Using Schizosaccharomyces japonicus Polysaccharides.

Nowadays commercial preparations of yeast polysaccharides (PSs), in particular mannoproteins, are widely used for wine colloidal and tartrate salt stabilization. In this context, the industry has developed different processes for the isolation and purification of PSs from the cell wall of Saccharomyces cerevisiae. This yeast releases limited amounts of mannoproteins in the growth medium, thus making their direct isolation from the culture broth not economically feasible. On the contrary, Schizosaccharomyces japonicus, a non-Saccharomyces yeast isolated from wine, releases significant amounts of PSs during the alcoholic fermentation. In the present work, PSs released by Sch. japonicus were recovered from the growth medium by ultrafiltration and their impact on the wine colloidal stability was evaluated. Interestingly, these PSs contribute positively to the wine protein stability. The visible haziness of the heat-treated wine decreases as the concentration of added PSs increases. SDS-PAGE Gel electrophoresis results of the haze and of the supernatant after the heat stability test are consistent with the turbidity measurements. Moreover, particle size distributions of the heat-treated wines, as obtained by Dynamic Light Scattering (DLS), show a reduction in the average dimension of the protein aggregates as the concentration of added PSs increases.

A New Extract from Pomegranate (Punica granatum L.) By-Products as a Potential Oenological Tannin: Preliminary Characterization and Comparison with Existing Commercial Products.

Oenotannins are nowadays widely used as co-adjuvant in the winemaking process. The increasing cultivation and consumption of pomegranate (Punica granatum L.) leads to high amounts of by-products, mainly peels. Aim of this study was to propose a dried tannin-rich extract from pomegranate by-products as a new oenotannin. A decoction was prepared from mesocarp of the Wonderful pomegranate variety only using hot water as extracting solvent. The dried decoction was physical-chemically characterized and compared to 7 existing commercial oenotannins from different botanical origin (grape seed, oak, gallnut), according to UV-Vis Spectroscopy, Colorimetric analysis (CIELab), gelatin index, reactivity to proteins, HPLC-DAD, DPPH, and Total Polyphenols content by both Folin-Ciocalteu and the International Organization of Vine and Wine (OIV) methods. Data showed the lowest antiradical (AR) and total polyphenolic content (TPC) for the pomegranate tannin but also the highest AR/TPC ratio suggesting a good radical scavenging potential of this new tannin. Pomegranate tannin showed high reactivity with proteins, a unique chromatographic profile, and a low color impact. The new pomegranate tannin showed an interesting potential for oenological applications in particular for reducing the use of sulfites during vinification and for the white wine stabilization.

Evaluation of the Intrinsic and Perceived Quality of Sangiovese Wines from California and Italy.

Sangiovese is the most cultivated red grape variety in Italy where it is certified for the production of several Protected Designation of Origin (PDO) wines, and it is one of the most cultivated Italian red grape varieties in California. Despite the global distribution of this variety, there is a lack of international studies on Sangiovese grapes and wines. For this reason, the present study aimed to compare 20 commercial Sangiovese wines from 2017 harvest, 9 produced in Italy (Tuscany) and 11 in California, in order to evaluate the intrinsic and perceived quality. The eligibility, identity, and style properties (the intrinsic quality) of the wines were evaluated. A group of 11 Italian experts evaluated the perceived quality by rating the typicality of the wines. The experimental data showed that the intrinsic quality of Sangiovese wine samples was affected by the growing area; in particular, the wine resulted very different for the color indices and polyphenol composition. The above differences in intrinsic quality levels did not lead to a different evaluation of the perceived quality (typicality) by the wine experts. The results evidenced that Sangiovese variety is recognizable also if grown outside its original terroir, and fresh and fruity wines were considered more typical. This study expands our current knowledge of Sangiovese wines and the contribution of regional characteristics to the composition of wine.

Filtration Scheduling: Quality Changes in Freshly Produced Virgin Olive Oil.

Filtration is the most widespread stabilisation operation for extra virgin olive oil, preventing microbial and enzymatic changes. However, during the harvest, the workload of olive mills is at its peak. This results in two approaches to filtration: (i) delays it until after harvesting, increasing the risk of degraded oil quality, and (ii) filters it immediately, increasing the workload. The aim of our experiment is to assess the risk of delaying filtration and establish a safe delay time. Changes in the sensory profile and volatile compound contents were evaluated during 30 days in filtered and unfiltered samples. Significant differences were related to filtration: both turbidity grade and microbial contamination; no differences for the legal parameters were found. Two, contrasting, results were obtained with respect to oil quality: (i) the fusty defect, appearing in less than five days in unfiltered oils, leading to the downgrade of the oil's commercial category, and (ii) filtration removing some lipoxygenase volatile compounds. Consequently, a fruity attribute was more pronounced in unfiltered samples until day five of storage; it seems that, from this point, the fusty defect masked a fruity attribute. Hence, filtering within a few days strongly reduced the risk of degraded oil quality compared to a delayed filtration.

Winemaking Byproducts as Source of Antioxidant Components: Consumers' Acceptance and Expectations of Phenol-Enriched Plant-Based Food.

One of the food industry's priorities is to recover byproducts and move towards more sustainable systems. Among wine-chain byproducts, unripe grapes represent a promising source of antioxidants. However, the development of new foods enriched using phenol-rich ingredients is challenging due to their sensory attributes. The aims of the present study were to (1) use phenol-rich extract from unripe grapes to enrich a model plant-based food (beetroot puree-BP); (2) evaluate consumers' acceptance and expectations for the beetroot purée samples. The effect of information about the sustainability and pro-health activity of value-added ingredients on consumers' responses was also investigated. Four beetroot purees with increasing concentrations of phenol extract (0-1.93 g/kg) added were evaluated by 101 participants in three tasting conditions (blind: only samples; expected: only information without tasting; real: both samples and information).Liking slightly decreased with increasing concentrations of phenol extract, even if all the samples were considered acceptable. The health and sustainability information increased the hedonic expectations, although it was not assimilated by all consumers involved. The development of new phenol-enriched foods using functional ingredients from unripe grapes is challenging. However, it is also promising, since all the samples were generally accepted by the consumers and they presented phenol levels that were stable over time and that could have positive health effects when consumed.