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The INFOGEST standardized method was applied to assess the potential bioaccessibility and bioaccessibility of the phenolic compounds from a Galician extra-virgin olive oil (EVOO). The in vitro digestion model involves three steps and generates two fractions after each one: an aqueous fraction (namely, water phase (Wp)) and an oily fraction (namely, oily phase (Op)). The results showed that secoiridoids were the most abundant family in the Galician EVOO polar fraction, representing 98% of the total phenolic compounds. After oral digestion, phenolic acids and simple phenols were mainly detected in Wp, while lignans and flavonoids were mostly found in Op. After gastric digestion, extensive hydrolysis of secoiridoids was observed to generate free tyrosol, hydroxytyrosol, and hydroxytyrosol acetate. The instability of secoiridoids after intestinal digestion was again responsible for the release of simple phenols, which were mainly recovered in Wp together with flavonoids. In contrast, lignans were stable to duodenal conditions and remained in Op. Financiado para publicación en acceso aberto: Universidade de Vigo/CISUG Agencia Estatal de Investigación | Ref. RTI2018-098633-B-I00

The Mediterranean diet includes virgin olive oil (VOO) as the main fat and olives as snacks. In addition to providing nutritional and organoleptic properties, VOO and the fruits (olives) contain an extensive number of bioactive compounds, mainly phenolic compounds, which are considered to be powerful antioxidants. Furthermore, olive byproducts, such as olive leaves, olive pomace, and olive mill wastewater, considered also as rich sources of phenolic compounds, are now valorized due to being mainly applied in the pharmaceutical and nutraceutical industries. The digestive system must physically and chemically break down these ingested olive-related products to release their phenolic compounds, which will be further metabolized to be used by the human organism. The first purpose of this review is to provide an overview of the current status of in-vitro static digestion models for olive-related products. In this sense, the in-vitro gastrointestinal digestion methods are widely used with the following aims: (i) to study how phenolic compounds are released from their matrices and to identify structural changes of phenolic compounds after the digestion of olive fruits and oils and (ii) to support the functional value of olive leaves and byproducts generated in the olive industry by assessing their health properties before and after the gastrointestinal process. The second purpose of this review is to survey and discuss all the results available to date. Ministerio de Ciencia, Innovación y Universidades | Ref. RTI2018-098633-B-I00 Ministerio de Ciencia, Innovación y Universidades | Ref. IJC2019-038895-I Xunta de Galicia | Ref. ED481D- 2019/001

The influence of mepanipyrim (Mep) and tetraconazole (Tetra) and their formulations (Mep-Form and Tetra-Form) on the chromatic characteristics of Mencia wines was evaluated. Fungicides were applied at concentrations corresponding to their Maximum Residue Levels (MRL) on grapes and at 2MRL. The decay rate of both fungicides during winemaking process confirmed the high dissipation percentage (>85%). To evaluate possible modifications in phenolic composition and colour, control wines were also analysed. No effects on anthocyanins for Mep, Mep-Form and Tetra (MRL) treatments were observed. Only a decrease of these pigments was registered when Tetra (2MRL: 43%) and Tetra-Form (MRL: 75% and 2MRL: 64%) were applied. Besides, the addition of Mep, Mep-Form and Tetra to the must did not decrease the content of flavonols, flavan-3-ols and non-flavonoids; meanwhile the addition of Tetra-Form reduced these phenolic compounds (around 35%, 52% and 17%, respectively).

‘Brava’ and ‘Mansa de Figueiredo’ extra-virgin olive oils (EVOOs) are two varieties identified from north-western Spain. A systematic phenolic characterization of the studied oils was undertaken by LC-ESI-IT-MS. In addition, the role of dietary polyphenols from these EVOOs has been evaluated against the inhibition of key enzymes (α-glucosidase and α-amylase) in the management of diabetes mellitus (DM). Oleuropein and ligstroside derivatives comprised 83% and 67% of the total phenolic compounds in ‘Brava’ and ‘Mansa de Figueiredo’ EVOOs, respectively. The main secoiridoids from oleuropein were DOA (3,4-DHPEA-EDA, 59 and 22 mg kg−1, respectively) and the main isomer of OlAgl (3,4-DHPEA-EA, 74 and 23 mg kg−1). The main secoiridoids from ligstroside were D-LigAgl (p-HPEA-EDA or oleocanthal, 23 and 167 mg kg−1) and the main isomer of LigAgl (p-HPEA-EA, 214 and 114 mg kg−1). For α-glucosidase, both EVOO extracts displayed stronger inhibitory activity (IC50 values of 60 ± 8 and 118 ± 9 μg mL−1, respectively) than the commercial inhibitor acarbose (IC50 = 356 ± 21 μg mL−1). Nevertheless, for α-amylase, only ‘Brava’ extracts showed anti-α-amylase capacity. A daily VOO intake lower than the requirements of EFSA seem to be enough to reach both 50% for α-glucosidase and 25% for α-amylase inhibition. These findings support the potential health benefits derived from Galician EVOOs that might be probably linked to the outstanding high concentration levels of phenolic acids and flavonoids.

In this study, a new selective pressurised liquid extraction (SPLE) methodology was optimised for determining about 70 organic pollutants (OPs) including organochlorine (OCPs), organophosphate (OPPs) and pyrethroid (PYRs) pesticides, polychlorinated biphenyls (PCBs), polybromodiphenyl ethers (PBDEs), as well as, polycyclic aromatic hydrocarbons (PAHs) in wild boar liver samples considering the temperature, pressure and time of contact between the solvent and the matrix as influential variables. Clean-up of extracts was performed by solid-phase extraction (SPE) using EZ-POP cartridges. Detection of OPs was carried out by gas chromatography (GC) coupled to tandem mass spectrometry (QqQ-MS/MS). This new approach offers:•A new non-time consuming SPLE methodology for determining about 70 OPs in wild boar.•Recoveries achieved ranged between 74 to 119 % with RSD less than 20 %.•Detection and quantification limits in the low to mid pg/g range., Graphical abstract Image, graphical abstract

Organic pollutants (OPs) are widely distributed around the globe, their presence has become an issue of great concern in the last years due to their potential health effects. Wildlife biomonitoring of OPs has been nowadays a common approach to assess chemical exposure in wildlife and humans. In a sample of 60 wild boars (Sus scrofa) from NW Spain, we evaluated the suitability of using liver and hair samples for the assessment of exposure and bioaccumulation of polychlorinated biphenyls (PCBs) including dioxin and non-dioxin like PCBs (DLPCBs and NDLPCBs), organochlorine and organophosphate pesticides (OCPs and OPPs, respectively), polybromodiphenyl ethers (PBDEs), pyrethroids (PYRs) and polycyclic aromatic hydrocarbons (PAHs). Selective pressurized liquid extraction (SPLE) and liquid-liquid extraction (LLE) methodologies were used to determine the target OPs in liver and hair samples. Clean-up of extracts was performed by solid-phase extraction (SPE) using EZ-POP cartridges and detection by gas chromatography coupled to tandem mass spectrometry (GC-QqQ-MS/MS). We found a distribution pattern of ΣPAHs ΣOCPs ΣPYRs ΣNDLPCBs ΣOPPs ΣDLPCBs ΣPBDEs in liver and of ΣPAHs ΣOCPs ΣNDLPCBs ΣPYRs ΣOPPs ΣDLPCBs ΣPBDEs in hair. Significant correlations (p 0.050) between the socio-demographic characteristics (gender, age and place) and OP concentrations of OCPs, PBDEs, PYRs, OPPs and PAHs were detected. Moderate correlation was found between HCB, PCB28, PCB157 and chlorpyrifos contents in both hair and liver samples. On the basis of these results, our data shows the correlation and complementary information given by both biological samples.

This study gives new insights to understand the type of interactions between Ginkgo biloba L. and Scutellaria baicalensis Georgi, two Chinese medicinal plants with well documented neuroprotective effects, on three targets in Alzheimer's disease (AD): acetylcholinesterase (AChE) and butyrylcholnesterase (BuChE) inhibition and hydrogen peroxide scavenging. Individual samples, binary mixtures with different proportions of both plant species, and also a commercial multicomponent combination containing both plants together with unroasted Coffea arabica L. and quercetin-3-O-rutinoside were used to perform this in vitro evaluation. Sample phenolic profiles were also determined by HPLC-DAD, showing the presence of several flavonoid glycosides, phenolic acids and a methylxanthine. In order to investigate the possible synergism/antagonism interaction, data obtained were analyzed by CompuSyn software. The results showed that G. biloba and S. baicalensis alone display better activities than in mixtures, most of the interactions exhibiting different degrees of antagonism. A slight synergism interaction was only observed for the commercial multicomponent mixture tested against H2O2. Further analysis was carried out to understand which compounds could be responsible for the antagonistic interaction. Seventeen single pure compounds present in all extracts were tested against AChE inhibition, most of them displaying weak or no activity. Only caffeine had a remarkable activity. Five different binary and quaternary mixture compositions were design to deepen the interaction between these compounds, revealing mainly phenolic acid-flavonoid, flavonoid-flavonoid and methylxanthine-flavonoid-phenolic acid antagonistic interactions. These results clearly show that, for the targets evaluated, there is no potentiation of the neuroprotective effect by combining S. baicalensis and G. biloba extracts.

In this work, phenol-rich extracts from ‘Cornicabra’ and ‘Picual’ virgin-olive oils (EVOOs) were examined, for the first time, to establish their capacity to inhibit key enzymes involved in Alzheimer's disease (AD) (acetylcholinesterase (AChE), butyrylcholinesterase (BuChE) and 5-lipoxygenase (LOX)), major depressive disorder (MDD) and Parkinson's disease (PD) (monoamine oxidases: hMAO-A and hMAO-B respectively), and diabetes mellitus (DM) (α-glucosidase and α-amylase). ‘Cornicabra’ displayed the best inhibitory activity against all enzymes, when compared to ‘Picual’: BuChE (IC50 = 156 ± 4 and 308 ± 33 mg mL−1), LOX (IC50 = 26 ± 0.5 and 37 ± 3 mg mL−1), hMAO-A (IC50 = 20 ± 2 and 37 ± 0.2 mg mL−1), hMAO-B (IC50 = 131 ± 7 and 215 ± 13 mg mL−1) and α-glucosidase (IC50 = 154 ± 17 and 251 ± 31 mg mL−1), respectively. The behaviour observed can be associated with the higher content of secoiridoids, lignans and phenolic acids in ‘Cornicabra’ EVOO.

This study focused the toxicity against human gastric adenocarcinoma cells (AGS) and the antioxidant activity of hydromethanol (HME), acetone (AcE) and alkaloid (AE) extracts prepared from the leaves of tomato plant cultivars (Caramba, Valentine, Negro, Abuela, and Anairis). AE, HME and AcE extracts of all cultivars reduced cell viability, IC50 values ranging from 9 ± 2 to 55 ± 11, from 103 ± 25 to 171 ± 29 and from 291 ± 26 to 459 ± 14 μg mL −1 , respectively. Moreover, both HME and AcE extracts scavenged • NO (IC 50 values ranged from 0.87 ± 0.12 to 1.54 ± 0.23 and from 0.90 ± 0.01 to 2.23 ± 0.14 mg mL −1 , respectively), but only HMEs was able to scavenge O 2 •- showing IC 50 values from 0.12 ± ≤0.01 to 0.43 ± 0.08 mg mL −1 . Our results demonstrate that tomato leaves, a by-product of tomato processing industry, are a valuable source of bioactive compounds, providing beneficial properties for human health.

The impact of mepanipyrim (Mep) and its corresponding commercial formulation (Mep Form) on Saccharomyces cerevisiae metabolites was assessed, separately, by using laboratory-scale wine fermentation assays on pasteurized red must. The presence of Mep did not alter the fermentation course. With regard to volatiles formed at the intracellular level by fermenting yeast cells, Mep residues affected mainly the acetate and ethyl ester biochemical pathways. In particular, the target acetates showed a notorious increment, >90%, in presence of commercial Mep Form at the higher dose assayed. The addition of Mep and Mep Form, at both tested levels, highly increased ethyl caprylate (between 42 and 63%) and ethyl caprate (between 36 and 60%) contents as the same as their respective fatty acid precursors. No important effects were observed on colour and non-volatile pyranoanthocyanins, probably due to the low anthocyanin content characteristic of pasteurized musts.

Lycopersicon esculentum Mill. is one of the world’s most important crops and its enormous by-products, such as leaves, are an excellent source of bioactive compounds with potential application in several industries. In this work, extracts from tomato plant leaves (cultivars: Caramba, Valentine, Negro, Abuela, Rio Alto, Anairis, Rosa and Yack) were examined, for the first time, to establish their phytochemical fingerprint and capacity to inhibit key enzymes involved in Alzheimeŕs disease (AD) (acetylcholinesterase (AChE), butyrylcholinesterase (BuChE) and 5-lipoxygenase (LOX)) and in diabetes mellitus (DM) (α-glucosidase and α-amylase). The hydromethanol extracts were shown to contain high amounts of phenolics (3774–9252 μg g −1 of dry extract), quercetin-3- O -rutinoside, quercetin-3- O -pentosyl-rutinoside, and chlorogenic and neochlorogenic acids being the major ones. The acetone extracts rich in pigments, namely chlorophylls (46.40 ± 3.81–136.4 ± 7.94 mg g −1 of dry extract), as well as alkaloids extracts rich in tomatine (224 ± 4.39–745 ± 4.96 mg g −1 of dry extract), were also analysed. Moreover, hydromethanol extracts exhibited inhibitory activity against AChE (IC 50 = 3806 ± 113–9911 ± 50.5 μg mL −1 ), BuChE (IC 50 = 133.1 ± 2.68–369.1 ± 17.2 μg mL −1 ), LOX (IC 25 = 35.2 ± 0.49–533 ± 8.9 μg mL −1 ), α-glucosidase (IC 50 = 1.14 ± 0.04–6.48 ± 0.13 mg mL −1 ) and α-amylase (IC 50 = 1.11 ± 0.02–1.78 ± 0.03 mg mL −1 ). On the contrary, the alkaloid extracts were only effective against BuChE (IC 50 = 82.4 ± 1.34–172 ± 10.2 μg mL −1 ). Chemical fingerprint and biological activities varied according to the analysed cultivar. Overall, our results suggest that L. esculentum leaves are promising by-products and valuable sources of bioactive compounds for AD and DM management.

The diet management is imperative to anticipate risk factors that favour the development of diseases; indeed, the intake of virgin olive oil could be an alternative natural source of α-glucosidase enzyme inhibitors, which delay the digestion rate of carbohydrates. Consequently, the impact of diabetes mellitus (DM) could be diminished. Extra Virgin Olive Oils (EVOO) were elaborated from Galician autochthonous variety ‘Brava Gallega’ with olives selected at three different degree of ripeness (ripening index, RI: 1.4, 3.0, 5.5) in order to assess the effect of maturation on overall chemical composition, sensory quality, and enzyme inhibition. The phenolic profile of the EVOOs determined by LC-ESI-IT-MS exhibited quantitative differences as ripening advanced; for example oleocanthal, tyrosol, luteolin and apigenin concentrations were higher in the overripe olive oil (RI 5.5). Anyway, the phenolic extracts (from every tested RI) were more active than acarbose. In particular, those obtained from the most mature olives displayed the most powerful inhibitory activity (IC50 value of 143 µg of dry extract/mL). In addition, the significant effect of these compounds (i.e. luteolin, apigenin, tyrosol and oleocanthal) on the inhibitory activity of the olive oil extracts was demonstrated. Our results suggest that, regardless of RI, the inhibitory activity of ‘Brava Gallega’ olive oils could represent a valuable strategy for reinforcing the health claim of olive oil for phenolic compounds.

The influence of antifungal tetraconazole residues (either as an active substance or as a commercial formulation product) on the fermentative activity of Saccharomyces cerevisiae yeast was evaluated in pasteurized Garnacha red must by using laboratory-scale fermentation assays. The presence of this fungicide promoted a slight decrease in glucose consumption. Volatile fermentative-derived compounds were evaluated in deep. Statistically significant changes were found in methionol (with a mean decrease of around 24%), fatty acids (with increments ranged from 23% to 66%), and ethyl esters (with increases ranged from 23% to 145%) contents when grape musts were enriched with the commercial formulation at both contamination levels assayed. Based on protein mass fingerprinting analysis, it was possible to relate these variations on volatiles content with changes in the activity of several enzymes (Met3p, Met14p, Adh2p, Hmg1p, Erg5p, Erg6p, Erg11p, and Erg20p) involved in the secondary metabolism of yeasts.

The effect of the residues of two fungicides (mepanipyrim and fenhexamid) on the color and phenolic profile of Tempranillo and Graciano red wines has been studied. To evaluate possible modifications in color and phenolic composition of wines, control wines (not treated) and wines elaborated with spiked musts were analyzed. Thereby, changes in the color parameters of CIELab space were observed in the wines treated with mepanipyrim and also in Tempranillo wines treated with fenhexamid. In general, the anti-fungal substances had different effects depending on the cultivar and on the phenolic compound analyzed; being monomeric anthocyanins and flavan-3-ol monomers the compounds more affected by the presence of these fungicides.

The increasing interest in theMediterranean diet is based on the protective effects against several diseases, including neurodegenerative disorders. Polyphenol-rich functional foods have been proposed to be unique supplementary and nutraceutical treatments for these disorders. Extra-virgin olive oils (EVOOs) obtained from 0Brava0 and 0Mansa0, varieties recently identified from Galicia (northwestern Spain), were selected for in vitro screening to evaluate their capacity to inhibit key enzymes involved in Alzheimer0s disease (AD) (acetylcholinesterase (AChE), butyrylcholinesterase (BuChE) and 5-lipoxygenase (5-LOX)), major depressive disorder (MDD) and Parkinson0s disease (PD) (monoamine oxidases: hMAO-A and hMAO-B respectively). 0Brava0 oil exhibited the best inhibitory activity against all enzymes, when they are compared to 0Mansa0 oil: BuChE (IC50 = 245 ± 5 and 591 ± 23 mg.mL-1), 5-LOX (IC50 = 45 ± 7 and 106±14 mg.mL-1), hMAO-A (IC50 = 30 ± 1 and 72 ± 10 mg.mL-1) and hMAO-B (IC50 = 191 ± 8 and 208 ±14 mg.mL-1), respectively. The inhibitory capacity of the phenolic extracts could be associated with the content of secoiridoids, lignans and phenolic acids., This work received financial support from Programa de Cooperación Interreg V-A España—Portugal (POCTEP) 2014–2020 (projects Ref.: 0181_NANOEATERS_01_E and Ref: 0377_IBERPHENOL_6_E).

The impact of fungicides mepanipyrim (Mep) and tetraconazole (Tetra) and their corresponding commercial formulations (Mep-Form and Tetra-Form) on the aroma composition of wines was assessed. Fungicide residues can affect the biotransformation of aroma precursors from grapes and/or the yeast metabolism. The results confirmed that both maximum residue levels (MRL and 2xMRL) of Mep promoted benzyl alcohol and 4-vinylguaiacol contents; while MRL and 2xMRL of Mep-Form promoted benzene derivatives (benzyl alcohol, benzaldehyde, and trans-isoeugenol), 2-phenylethanol and γ-nonalactone. The addition of Tetra (2xMRL) and Tetra-Form (MRL and 2xMRL) release higher contents of cis-3-hexen-1-ol and ethyl vanillate and affected yeast metabolism related to phenylacetaldehyde, 2-phenylethanol, methionol, capric acid, ethyl 2-methylbutyrate, ethyl isovalerate, ethyl monosuccionate, diethyl succinate and γ-butyrolactone production. Fungicide residues did not display higher variations in global odour activity values with respect to control wines, although some variations on the "floral", "fruity", "spicy" and "lactic" nuances could be sensed.

The off-vine drying is one of the most important steps in the production of a high quality naturally sweet wine. However, only few studies have analyzed the changes in colour and phenolic compounds of the grapes throughout the process. In this work, UV/Vis spectrophotometry and HPLC/DAD-ESI/MS were applied to determine, respectively, the evolution of colour and phenolic compounds in the red grapes of Garnacha Tintorera during the raisining process. The total water loss in 83 days was about 62% and the sugar concentration rose from 225 to 464 g L −1 . Browning and low-medium molecular weight compounds increase during the dehydration process. In CIELab coordinates, raisining decreases a ∗ (red/green) and lightness and increases b ∗ (yellow/blue), colour saturation and hue angle. In general, most of the phenolic compounds determined (anthocyanins, flavonols, esters of hydroxycinnamic acids, flavan-3-ol monomers and proanthocyanidins) increase but to a lesser extent than expected because of the water loss of the grapes during drying. The lower increase was observed for esters of hydroxicinnamic acids suggesting these compounds could undergo strong enzymatic degradation. Despite this, both the terminal and the extension subunit compositions show little changes, while the mean degree of polymerization of proanthocyanidins decreases as raisining progresses.

Natural sweet wines are mainly characterised by their high sugar concentration which can be achieved by over-ripening of grapes and/or a previous process of grape dehydration. Although the quality of these sweet wines is determined essentially by aroma compounds, few reports on phenolic compounds and colour of sweet wines have been published. Phenolic composition and colour of natural sweet wines are described now in this review from two points of view: influence of drying or dehydration process on colour and phenolic composition of grapes for producing natural sweet wines; and also, influence of grape sugar process on colour and phenolic composition of their respective sweet wines. Grapes and wines are simultaneously grouped according to the dehydration -on or -off-vine. The grape drying process should be studied in greater depth to know mechanisms involving phenolic compounds that directly affect the colour, stability and ageing of natural sweet wines.

Galicia (N.W. Iberian Peninsula) is a Spanish region with several old-traditional winegrowing areas. Vitis vinifera L. cv. Mencía is one of the most often used to produce quality red wines in the five Galicia Denomination of Origin. However, there are traditional cultivars such as Brancellao, which were not exploited for their potential to produce quality red wines. Dynamics of anthocyanin and flavonol accumulation were studied separately in two different positions within the cluster (tips and shoulders), during 30 days before harvest. The objective of separating berries is to assess the existence of different polyphenol quality in both positions; as a consequence, the selection and harvest of those berries with a higher content of anthocyanins and flavonols could produce red wines with different qualities. Derivatives of five anthocyanins (malvidin, peonidin, petunidin, delphinidin and cyanidin) were detected in skins at both positions within the cluster. Anthocyanin contents stabilized in the 30 days prior to harvest in the berries from the shoulders whereas they continue to increase in those from the tips. Derivatives of six flavonols (quercetin, myricetin, kaempherol, laricitrin, isorhamnetin and syringetin) were detected in skin and flesh at both positions within the cluster. Dynamics of anthocyanins (from 400 to 515 mg/kg in tips; and from 598 to 574 mg/kg in shoulders) and flavonols (from 19 to 29.3 mg/kg in tips; and from 22.7 to 29.4 mg/kg in shoulders) over ripening confirmed that these polyphenols presented upward trends. Therefore, it is not necessary to harvest Brancellao berries separately and a high quality red wine will be obtained with berries from entire clusters regarding these compounds. © 2012 Elsevier Ltd. All rights reserved., EU FEDER; MCYT- INIA (Spain) (RF 2008-00002-C02); INCITE09 383 322 PR (Xunta de Galicia)

“Pedra hume caa” is the common name of five species of Myrcia genus used as traditional medicine for the treatment of diabetes mellitus. In this study, different extracts from Myrcia salicifolia, Myrcia sphaerocarpa, and Myrcia speciosa were investigated for the first time, to identify their phenolic compounds (being 3-O-rhamnoside derivatives of myricetin and quercetin the major ones) and in vitro inhibitory potential against α-glucosidase and α-amylase. These extracts inhibited 90–500 times more α-glucosidase (IC50 = 0.7 to 4.1 μg ml−1) than acarbose and displayed a mild inhibition against α-amylase (IC50 = 6.1 to 29 μg mL−1).

Virgin olive oil, the main fat of the Mediterranean diet, is per se considered as a functional food—as stated by the European Food Safety Authority (EFSA)—due to its content in healthy compounds. The daily intake of endogenous bioactive phenolics from virgin olive oil is variable due to the influence of multiple agronomic and technological factors. Thus, a good strategy to ensure an optimal intake of polyphenols through habitual diet would be to produce enriched virgin olive oil with well-known bioactive polyphenols. Different sources of natural biological active substances can be potentially used to enrich virgin olive oil (e.g., raw materials derived from the same olive tree, mainly olive leaves and pomaces, and/or other compounds from plants and vegetables, mainly herbs and spices). The development of these functional olive oils may help in prevention of chronic diseases (such as cardiovascular diseases, immune frailty, ageing disorders and degenerative diseases) and improving the quality of life for many consumers reducing health care costs. In the present review, the most relevant scientific information related to the development of enriched virgin olive oil and their positive human health effects has been collected and discussed.

Galicia (N.W. Spain) is a Spanish region with several old-traditional winegrowing areas. There are autochthonous grapevine varieties, such as Vitis vinifera L. cv. Mouratón, considered a biodiversity resource in viticulture and an opportunity for Galician sustainable wine production. Therefore, it is necessary to assess the potential of traditional cultivars to produce quality red wines. In this work, anthocyanin and flavonol evolution was followed in red berries from V. vinifera L. cv. Mouratón. The novelty of this study is that grapes were separately collected from two different positions (tips and shoulders) within the cluster, over ripening to examine the effects of berry position within the fruit cluster on the flavonoid compounds. Derivatives of five anthocyanins (malvidin, peonidin, petunidin, delphinidin and cyanidin) and derivatives of six flavonols (quercetin, myricetin, kaempherol, laricitrin isorhamnetin and syringetin) were detected in both positions within the cluster. Dynamic of anthocyanins (from 819 mg/kg to 1206 mg/kg in tips; and from 786 mg/kg to 1077 mg/kg in shoulders) and dynamic of flavonols (from 25 mg/kg to 41 mg/kg in tips; and from 18 mg/kg to 21 mg/kg in shoulders) confirmed their upward trends over ripening. Grapes located inside the shoulder bunch receive less sunlight radiation than those located inside the tip bunch and this fact could explain the different accumulation observed for both positions. These results can be useful for winemakers in order to obtain different final red wine quality., This work was granted by EU FEDER funds and by the INCITE09 383 322 PR (Autonomous Community Government in N.W. Spain) contracts. M. Figueiredo-González acknowledges Xunta de Galicia for her contract sponsorship through the above Spanish contract., EU-FEDER, Xunta de Galicia

Sweet wines are traditionally elaborated in Galicia (the N.W. corner of Spain). The denomination of origin (DO) Valdeorras, one of the five DOs in Galicia, wants to promote the production and marketing of new sweets wines. The first one is made with dried red grapes Vitis vinifera L. Garnacha Tintorera (GNSW); this cultivar is a teinturier cultivar which has excellent potential to produce wines from raisined grapes. The second one, a fortified sweet wine aged in oak barrels (GFSW). Additionally a dry young wine (GBW) was produced from the same variety. Their aroma profiles and chromatic characteristics (determined by simple spectrophotometric methods) have been previously established. Now, proanthocyanidins, flava-3-ol monomers, anthocyanins, phenolic acids, flavonols and resveratrol were determined by HPLC, for the same three wines. The highest concentration of total proanthocyanidins (PAs) was evaluated in the GBW (525mgL(-1)), which was about 2-fold the concentration in the GNSW (236mgL(-1)) and about more 10-fold the concentration in the GFSW (44mgL(-1)). No apparent difference in the aDP (mean degree of polymerisation) was observed for the GBW (1.9) and the GNSW (2.1), whereas a slightly lower value was obtained for the GFSW (1.5). Total anthocyanin concentration was described as follow as GBW: 390mgL(-1)≫GNSW: 57mgL(-1)>GFSW: 25mgL(-1), which indicates that sweet wines were polymerised in great extent. Only vitisin A and B were found the main concentration in GFSW when compared to GBW by the ageing process. In sweet wines, phenolic acids (hydroxybenzoic and hydroxycinnamic acids) and flavonols were lowest when compared to GBW and resveratrol not was found in sweet wines.

Valdeorras (the N.W. corner of Spain) wants to promote the production and marketing of new sweet wines. The present work represents the first study on sweet wines manufactured with red grapes Vitis vinifera L. Garnacha Tintorera, a teinturier cultivar. Two different red sweet wines were elaborated: the first one was made with dried grapes; Vitis vinifera L. Garnacha Tintorera has excellent potential to produce wines from raisined grapes; the second one, a fortified sweet wine aged in oak barrels. Different red Garnacha Tintorera-based wines (a dry base wine, GBW; a naturally sweet wine, GNSW; and a fortified sweet wine, GFSW) were characterized. Chromatic characteristics and phenolic compounds were established by spectrophotometric methods in order to assess the technology of Garnacha Tintorera-based sweet wines. High molecular weight brown polymers, produced during the grape drying process and isolated from sweet wines by the dialysis process, were responsible for the brown colour of sweet wines. As a consequence, yellowness of sweet wines was also higher which was confirmed by colorimetric indexes. With respect to phenolic content, GFSW presented the lowest content because the maceration-alcoholic fermentation was stopped through the addition of alcohol before the diffusion of red pigments from skins to must was complete. GNSW presented the highest phenolic content due to the concentration effect resulting from evaporation of water from the grapes. Anthocyanins of sweet wines were polymerised in great extent. The percentage of polymerised tannins was sufficient to guarantee the aging process of sweet wines.

Galicia (the north-western corner of Spain) is a Spanish region with several old-traditional winegrowing areas. Vitis vinifera L. cv. Mencía is one of the most often used to produce quality red wines but the tendency of the world wine-making market is to reward the production of wines that have particular and differentiated characteristics. In Galicia, there are other red cultivars such as Gran Negro which were not exploited for their potential to produce quality red wines. Dynamics of anthocyanin and flavonol accumulation in Gran Negro berries were studied separately in two different positions within the cluster (tips and shoulders) during 30 days before harvest to assess the existence of different polyphenol quality in both positions and as a consequence, red wines with different qualities. Dynamics of anthocyanins over ripening confirmed that anthocyanins presented upward trends (from 1510 to 1727 mg/kg in tips; and from 1532 to 1728 mg/kg in shoulders) but dynamics of flavonols confirmed that maximum values were reached and stabilised thirty days before harvest (from 45 to 39 mg/kg in tips; and from 49 to 45 mg/kg in shoulders). No differences were observed in anthocyanin and flavonol contents collected from tips and shoulders which indicates that is not necessary to harvest them separately. The results from Gran Negro were compared with those of Brancellao and Mouratón. © 2012 Elsevier Ltd. All rights reserved., This work was granted by EU FEDER funds and Ministerio de Ciencia y Tecnología- INIA (Spain) RF 2008-00002-C02 and by the INCITE09 383 322 PR (Autonomous Community Government in N.W. Spain) contracts.

The presence of anthocyanins and flavonols in three selected red grape varieties was investigated, in order to use their polyphenolic characterisation as a fingerprint. Berry skins of Gran Negro grapes were characterised by the presence of high content of malvidin- and peonidin-3-O-glucoside; Mouratón grapes, by the presence of high content of petunidin- and delphinidin-3-O-glucoside; and Brancellao grapes, by the presence of high content of cyanidin-3-O-glucoside. The main flavonols found included the 3-O-glucosides of quercetin, myricetin, kaempferol, laricitrin, isorhamnetin and syringetin. Using cluster analysis and principal components analysis, Gran Negro could be characterised by their content of isorhamnetin-3-O-glucoside and syringetin-3-O-glucoside and, along with Mouratón, by their myricetin conjugates. Flavonol profile could not provide a fingerprint of Brancellao variety. Stepwise discriminant analysis was performed in order to find the polyphenolic compounds, which characterised the selected grape varieties. Finally, anthocyanin and flavonol profiles in red grapes were compared and results confirmed that biosynthesis of flavonols is closely related to that of anthocyanins. © 2011 Elsevier Ltd. All rights reserved., This work was granted by EU FEDER funds, but also by the INCITE09383322PR contract from the Autonomous Community Government in N.W. Spain.