Volatile Characterization of Recovery Minority Grape Varieties from Castilla-La Mancha Region (Spain).

Nowadays, the identification and characterization of grapevine cultivars resilient to climate and water stress while preserving quality traits is crucial for the wine industry. Therefore, the objective of this work was to characterize according to their aromatic potential nine white and six red minority cultivars recently recovered from Castilla-La Mancha region (Spain), subjected to two different water-deficit regimes: rainfed, with subsistence irrigation, and irrigated. For this, the varietal aromatic potential index (IPAv) and the detailed aromatic composition were analyzed via HS-SBSE-GC/MS in extracts of two different pHs. For IPAv values, red varieties did not show a clear trend with respect to irrigation. However, in white minority varieties, higher values were obtained under irrigation conditions. Thus, a clear differentiation of the minority varieties in comparison to the references was observed, primarily attributed to the content of esters and acids, in both white and red varieties. A notable contrast was observed at different pHs, indicating a greater extractability of certain compounds like linalool, under more acidic conditions. This suggests that some recovered minority cultivars could be promising for cultivation in semi-arid regions with limited water, contributing to the sustainability of the wine sector in the future.

Gastrointestinal digestion of olive leaf waste from olive mill production chain in a simulator of the gastrointestinal tract.

BACKGROUND: Currently, olive leaves are considered waste, although their high phenolic content makes them a source of antioxidants that could be used directly. The aim of this work was to study the behavior of phenolic compounds contained in olive leaf from the olive mill production chain during their gastrointestinal digestion. RESULTS: Phenolic compounds in the gastric digestion analyzed by high-performance liquid chromatography-diode array detection-mass spectrometry increased by 58% to 314.5% compared to the meal, while in the intestinal stage they ranged from 1.87 to 9.04 times higher. An increase of between 187% and 903% in bioaccessibility of phenolic compounds in the intestinal phase was observed, except for verbascoside. Furthermore, such compounds were fully bioavailable, except for apigenin-7-O-glucoside, which showed a bioavailability of 56%. CONCLUSION: The current study showed that the concentration of oleuropein, apigegin-7-O-glucoside, hydroxytyrosol hexoside and hydroxytyrosol contained in olive leaf continued to be extracted during the gastrointestinal digestion process. Furthermore, the results obtained with respect to their bioaccessibility and bioavailability suggest a good disposition to pass into the bloodstream where they could exert beneficial effects. Therefore, these results are promising for olive leaf becoming a consumable by-product that could be directly ingested through a simple infusion. © 2024 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Chemical and sensorial profile of Tempranillo wines elaborated with toasted vine-shoots of different varieties and micro-oxygenation.

The positive impact of use SEGs ("Shoot from vines - Enological - Granule") in winemaking for wines of the same variety has been extensively demonstrated, but their combination with different SEGs varieties and micro-oxygenation (MOX) remains unstudied. In this study, Tempranillo wines were in contact along 35 days with two doses of Tempranillo and Cabernet Sauvignon SEGs (12 and 24 g/L) and two fixed doses of MOX (LOTR, 6.24 mg/L·month, and HOTR, 11.91 mg/L·month). Chemical composition and sensory profiles were analyzed after SEGs-MOX treatments. Results indicated a greater impact of MOX on volatile composition when Cabernet Sauvignon SEGs were used, with similar results for CS12-HOTR and CS24-LOTR wines. Phenolic compounds showed a total concentration decrease in all treated wines, though trans-resveratrol increased in all cases, particularly with the highest MOX dose. In sensory evaluation, MOX accelerated the integration of characteristic SEGs aromas into the wine, reducing the required bottle time for round them.

Application of near-infrared spectroscopy for the estimation of volatile compounds in Tempranillo Blanco grape berries during ripening.

BACKGROUND: The knowledge of volatile compounds concentration in grape berries is very valuable information for the winemaker, since these compounds are strongly involved in the final wine quality, and in consumer acceptance. In addition, it would allow to set the harvest date according to aromatic maturity, to classify grape berries according to their quality and to make wines with different characteristics, among other implications. However, so far, there are no tools that allow the volatile composition to be measured directly on intact berries, either in the vineyard or in the winery. RESULTS: In this work, the use of near-infrared (NIR) spectroscopy to estimate the aromatic composition and total soluble solids (TSS) of Tempranillo Blanco grape berries during ripening was evaluated. For this purpose, the spectra in the NIR range (1100-2100 nm) of 240 intact berry samples were acquired in the laboratory. From these same samples, the concentration of volatile compounds was analyzed by thin film-solid-phase microextraction-gas chromatography-mass spectrometry (TF-SPME-GC-MS), and the TSS were quantified by refractometry. These two methods were used as reference methods for model building. Calibration, cross-validation and prediction models were built from spectral data using partial least squares (PLS). Determination coefficients of cross-validation (R2 CV ) above 0.5 were obtained for all volatile compounds, their families, and TSS. CONCLUSIONS: These findings support that NIR spectroscopy can be successfully use to estimate the aromatic composition as well as the TSS of intact Tempranillo Blanco berries in a non-destructive, fast, and contactless form, allowing simultaneous determination of technological and aromatic maturities. © 2023 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Monitorization of Varietal Aroma Composition Dynamics during Ripening in Intact Vitis vinifera L. Tempranillo Blanco Berries by Hyperspectral Imaging.

The measurement of aromatic maturity during grape ripening provides very important information for determining the harvest date, particularly in white cultivars. However, there are currently no tools that allow this measurement to be carried out in a noninvasive and rapid way. For this reason, in the present work, we have studied the use of hyperspectral imaging (HSI)) to estimate the aromatic composition of Vitis vinifera L. Tempranillo Blanco berries during ripening. A total of 236 spectra in the VIS+short wave near-infrared (VIS+SW-NIR) range (400-1000 nm) of intact berries were acquired contactless under laboratory conditions. As gold standard values, a total of 20 volatile compounds were quantified by gas chromatography-mass spectrometry (GC-MS), and the concentration of total soluble solids (TSS) was measured by refractometry. Calibration, cross-validation, and prediction models were built using partial least squares (PLS). Values of RCV2 ≥ 0.70 were obtained for α-terpineol, p-cymene, ß-damascenone, ß-ionone, benzaldehyde, benzyl alcohol, hexanal, citral, linalool, 2-phenylethanol, octanoic acid, nonanoic acid, 2-hexenal, 2-hexen-1-ol, (Z)-3-hexen-1-ol, total C13 norisoprenoids, total C6 compounds, total positive compounds (i.e., the sum of all families except C6 compounds), total benzenoids, and total soluble solids (TSS). Therefore, it can be affirmed that HSI in the VIS + SW-NIR range could be a good tool to estimate the aromatic composition of Tempranillo Blanco grape berries in a contactless, fast, and nondestructive way.

Chemical exchange in the vine shoots-wine system when used as an innovative enological procedure.

BACKGROUND: Pruned vine shoots prepared as toasted fragments (SEGs) have recently been proposed as enological additives capable of producing differentiated quality wines. In this work, the composition of phenolic and volatile compounds of SEGs, before and after contact with wines, has been studied. RESULTS: SEGs from Tempranillo and Cabernet Sauvignon were used, which were kept in contact for 30 days with red wines made with the same varieties. Phenolic compounds were the ones with the highest sorption in SEGs, but a variety-dependent behavior was observed in anthocyanins and flavonols, with an increase in some malvidin derivatives only in Tempranillo wine and an increase in (-)-epicatechin in SEGs and Cabernet Sauvignon wine. trans-Resveratrol was transferred from SEGs to wine but also increased in SEGs regardless of the variety used. The volatile compounds that were most retained in SEGs were phenylethyl alcohol and ethyl lactate, but in lower proportions than the phenolic compounds and without important changes in wines. CONCLUSION: The high content of phenolic compounds in SEGs after their use as enological additives suggests that they could be considered as a source of anthocyanins and as raw materials for phenolic compounds with recognized antioxidant properties. © 2022 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Preliminary Studies on Endotherapy Based Application of Ozonated Water to Bobal Grapevines: Effect on Wine Quality.

The application of ozonated water in the vineyard is an increasingly popular tool for disease management, but the quality of grapes and resulting wines is likely to be affected. Endotherapy, or trunk injection, is a particularly useful method to apply phytosanitary products since many fungal pathogens colonize the grapevine woody tissues. Thus, the present study aimed to evaluate the effect on wine quality of the ozonated water applied to Bobal grapevines, one of the most cultivated red varieties in Spain, through endotherapy (E) or its combination with spraying (E + S). Endotherapy was carried out four times before harvest for both E and E + S treatments, and spraying was performed 2 days before and after each endotherapy application. Grapes were harvested, vinified, and the quality of the finished wines was evaluated through several enological parameters and the phenolic and volatile composition. Both treatments resulted in less alcoholic and more acidic wines. The E treatment, although it reduced the content of phenolic acids, stilbenes and flavanols, significantly increased anthocyanins, whereas E + S decreased the overall amount of phenolics, which had different implications for wine colour. In terms of aroma, both treatments, but E to a greater extent, reduced the content of glycosylated precursors and differentially affected free volatiles, both varietal and fermentative. Thus, the dose of ozonated water, frequency and/or method of application are determining factors in the effect of these treatments on wine quality and must be carefully considered by winegrowers to establish the optimum treatment conditions so as not to impair the quality of wines.

Classification of vine-shoots for use as enological additives.

BACKGROUND: Toasted vine shoots have recently been proposed as enological additives with the aim of improving the sensorial profile of wines. However, so far, there is no simple method for classifying vine shoots for this innovative enological practice. In this study, therefore, an enological aptitude classification for toasted vine shoots has been proposed for the first time. Moreover, given the need for quick techniques to be used in wineries to determine the main phenolic compounds of vine shoots, near-infrared (NIR) spectroscopy has been calibrated and validated. RESULTS: By means of a detailed statistical analysis, an enological classification of toasted vine shoots has been proposed based on their total polyphenol index and (+)-catechin, (-)-epicatechin, ellagic acid, and trans-resveratrol. Moreover, the NIR methodology that was developed showed good validation statistics and acceptable accuracy. CONCLUSIONS: This work proposes the first enological toasted vine-shoot classification and it provides a tool for rapid screening, mainly of phenolic compounds, in toasted vine shoots. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Oleuropein Degradation Kinetics in Olive Leaf and Its Aqueous Extracts.

Although olives leaves are currently considered a waste material from oil mills, they have great potential to be transformed into by-products due to their high oleuropein content. Oleuropein is a glycoside precursor of hydroxytyrosol, which is the phenolic compound with the highest antioxidant capacity in nature and which is associated with multiple health benefits. For this reason, the demand for oleuropein is growing in the pharmaceutical, cosmetic and food sectors. The objective of this study is to determine the stability of oleuropein in olive leaves from oil mills in solid and aqueous forms under different conditions of temperature, relative humidity and lighting. The results indicate that the degradation of oleuropein conforms well to first-order kinetics. The rate constants at the temperatures tested in the aqueous extracts indicate activation energies from RTl to 80 °C and from 7 °C to 14 °C, as the degradation reactions were different in these ranges. Furthermore, olive leaf powder stored at any temperature with an RH ≥ 57% showed greater stability after six months, which is an encouraging result for the storage and transformation of this waste in oil mills.

Vine-Shoots as Enological Additives. A Study of Acute Toxicity and Cytotoxicity.

Toasted vine-shoots have been recently proposed as enological additives that can be used to improve the sensorial profile of wines. However, the possible toxicity of this new winery practice has not been studied so far. The aim of this study was to evaluate the toxicity of Tempranillo, Cencibel, and Cabernet Sauvignon toasted vine-shoots when used in winemaking. First, vine-shoots were characterized in terms of minerals and phenolic and furan compounds, and then their acute toxicity and cytotoxicity were studied using Microtox® and the metabolic reduction of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assays. High EC50 values were obtained when the Microtox® assay was applied to vine-shoot aqueous extracts, similar to the case of herbal infusions. When the MTT assay was used, a cell viability above 70% was observed in all the wines made with those vine-shoots, and an even greater viability was observed in the case of Cabernet Sauvignon. Therefore, it was concluded that those vine-shoots have no cytotoxic potential.

Analysis of Intact Glycosidic Aroma Precursors in Grapes by High-Performance Liquid Chromatography with a Diode Array Detector.

Nowadays, the techniques for the analysis of glycosidic precursors in grapes involve changes in the glycoside structure or it is necessary the use of very expensive analytical techniques. In this study, we describe for the first time an approach to analyse intact glycosidic aroma precursors in grapes by high-performance liquid chromatography with a diode array detector (HPLC-DAD), a simple and cheap analytical technique that could be used in wineries. Briefly, the skin of Muscat of Alexandria grapes was extracted using a microwave and purified using solid-phase extraction combining Oasis MCX and LiChrolut EN cartridges. In total, 20 compounds were selected by HPLC-DAD at 195 nm and taking as a reference the spectrum of phenyl ß-D-glucopyranoside, whose DAD spectrum showed a first shoulder from 190 to 230 nm and a second around 200-360 nm. After that, these glycosidic compounds were identified by High-performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC-qTOF-MS). Disaccharides hexose pentose were the most abundant group observed with respect to the sugars and monoterpendiols the main aglycones found.

Development and validation of an HPLC-DAD method for determination of oleuropein and other bioactive compounds in olive leaf by-products.

BACKGROUND: Oil mills could benefit by preparing their own aqueous extracts from olive leaves. Accordingly, the present study aimed to measure the bioactive compounds richness of such extracts, especially oleuropein. A water-based microwave extraction procedure was developed and a selective and precise high-performance liquid chromatography with diode array detection (HPLC-DAD) method was validated for the determination of oleuropein and others bioactive compounds from olive leaves. RESULTS: The water solubility of oleuropein was determined to be 9.5 g L-1 . The extraction procedure was optimized in terms of power, olive leaf weight/water volume ratio and time of extraction, and the results revealed that 2 mg mL-1 and a microwave irradiation at 800 W for 30 s resulted in the greatest efficiency. Oleuropein was determined by the new validation method, which showed good linearity (r2 = 0.996), precision (% relative standard deviation < 10%), recovery (118.6%), and limits of detection (17.48 mg L-1 ) and quantification (21.54 mg L-1 ). Good correlation (r2 = 0.979) was obtained between oleuropein of the olive leaf extracts determined by HPLC-DAD and by UV-visible spectrophotometry. CONCLUSION: A simple extraction method was developed and validated to obtain aqueous extract from olive leaves by microwave extraction, determining for the first time oleuropein water solubility. Validation of the method showed that oleuropein in olive leaves could be quantified when it is at least 1% of dry weight by means of HPLC-DAD. UV-visible spectrophotometry can be useful in oil mills because it enables the content of oleuropein and other bioactive compounds content to be determined in situ in such leaf aqueous extracts. © 2020 Society of Chemical Industry.

Winemaking with vine-shoots. Modulating the composition of wines by using their own resources.

Vine-shoots from two important Vitis vinifera, Airén and Cencibel, have been prepared in two different formats (chip and granule) and added (12 g/L) in their own wines in different winemaking steps. Results have shown significant differences depending in all conditions tested, and wine chemical composition was modulated while in contact with vine-shoots. Compounds such as trans-resveratrol, increased its concentration up to 4 mg/L in Airén white wines. In Cencibel red wines, vanillin was found in a concentration four times above its odor threshold and independently of the vine-shoot variety, format and moment of addition, compounds such as (-)-epicatechin and (+)-catechin increased the concentration with respect to the control wine. When vine-shoots were added after fermentation, ß-ionol appeared for first time in all wines. In case of guaiacol, the higher increment was observed for Airén wines. Therefore, it is possible to elaborate distinctive wines using their own resources.

Toasted vine-shoot chips as enological additive.

Different ways of vine-shoots revalorization have been proposed, but not in wine yet, as for example in the same way as oak chips are being used. In this work, vine-shoot samples were submitted to a thermogravimetric analysis to establish the temperature range for its lignin structure decomposition, resulting between 160 and 180 °C. Then, vine-shoot chips from Airén and Cencibel cultivars, with a particle size around 2.5-3.5 cm, were submitted to six toasting conditions: 160 °C and 180 °C for 45, 60 and 75 min. Their volatile composition was very similar to oak chips, being vanillin the most important compound. Moreover, such vine-shoots have an interesting content of prodelphinidins that together with the stilbenes may contribute to wine antioxidant activity. The toasting conditions at 180 °C/45 min were the most suitable one for releasing the mentioned valuable compounds in order to propose vine-shoots as new enological additive similar to oak chips.

Vine-Shoot Tannins: Effect of Post-pruning Storage and Toasting Treatment.

For the first time vine-shoot tannin composition was carried out by means of HPLC-DAD-ESI-MS/MS. Two vine-shoot cultivars (Airén and Cencibel) with different post-pruning storage times were submitted to a toasting process and assayed. There were no traces of gallotannins nor ellagitannins, but a high proanthocyanidin content and a mean degree of polymerization (mDP) close to 3 were characterized. The higher concentration of proanthocyanidins corresponded to Airén after 6 months post-pruning storage and at 3 months for Cencibel. Procyanidins were the most abundant fraction (70-95%), which decreased with storage, and especially significant was the contribution of B1, B2, and B4 dimers. Prodelphinidins were also found (8-24%), increasing their % with storage time. Toasting produced a considerable reduction of proanthocyanidin content and a loss of a monomer mDP unit, suggesting that if used as oenological tannins, then they may be more bitter and less astringent when compared with the nontoasted vine-shoot samples.