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The detailed phenolic composition of different berry parts from two novel V. vinifera L. red grape genotypes (Moribel and Tinto Fragoso), together the well-known Tempranillo, was established using high performance liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS/MS) over two consecutive vintages (2016 and 2017). More than 50 phenolic compounds were identified and quantified: 25 anthocyanins, 17 flavonols, 7 hydroxycinnamic acid derivatives, 2 stilbenes, and several flavan-3-ols. As far as we know, some anthocyanin and flavonol dihexosides were reported for the first time in V. vinifera L. grapes. Application of Principal Component Analysis (PCA) to experimental data showed a good separation of the novel grape genotypes and Tempranillo according to the phenolic profile of skins and seeds, mainly based on the proportion of trisubstituted anthocyanin derivatives, flavonols and flavan-3-ols, being a useful tool to differentiate these grape varieties.

The berries from the native Chilean Gaultheria phillyreifolia and G. poeppigii are appreciated for their sweet taste and aroma. Fruits from both species were investigated for their secondary metabolite composition and antioxidant activity. The extracts were submitted to membrane chromatography to separate anthocyanins from copigments. Four anthocyanins were isolated by counter-current chromatography (CCC) and identified as cyanidin galactoside, cyanidin arabinoside, delphinidin galactoside and delphinidin arabinoside. From the copigments, CCC allowed the separation of quercetin(Q)-3-arabinoside, Q-3-rutinoside Q-3-rhamnoside and 3-caffeoylquinic acid. Additionally, the iridoids monotropein-10-trans-coumarate, monotropein-10-trans-cinnamate and 6α-hydroxy-dihydromonotropein-10-trans-cinnamate were isolated. The latter two iridoids are reported here for the first time. Some 34 other compounds were tentatively identified by HPLC-DAD-ESI-MSn. The antioxidant activity showed differences between anthocyanins and copigments from both species. Main compounds were quantified and submitted to a Partial-Least Square Discriminant Analysis (PLS-DA). This is the first report on the isolation of phytochemicals from the selected Chilean Gaultheria species.

The chemical oxidation of white wines through the Fenton reaction has been widely studied, wherein the primary species is the hydroxyl radical ( OH). This radical possesses high oxidising power and may oxidise the primary components in wines. The Fenton reaction in wines is complex and includes the participation of phenolic compounds, organic acids, and metals. However, there has been no systematic study to date that relates wine composition to OH production in real white wines. In this paper, a multivariate model was generated using the partial least squares (PLS) algorithm, and linear correlations were established between wine composition and OH production. Based on the results, the variables were classified as either pro-oxidants (malic acid, p-coumaric acid, and caffeic acid, % prodelphinidins, procyanidins B1, Mn, Cu, and Zn) or antioxidants (cis-piceid, ellagic acid, gallic acid, proanthocyanins, glucose, and proton concentration). Finally, the pathways by which wine compounds participate in OH production are discussed.

BACKGROUND 'Karaerik' is a novel table grape (Vitis vinifera L.) native to Turkey and widely cultivated in areas bordering the city of Erzincan. Because of the demonstrated beneficial effects on human health of the grape phenolic composition, the aim of this work was to conduct a detailed profiling of non-anthocyanin phenolic fractions from different grape tissues of the 'Karaerik' table grape. Both qualitative and quantitative characterization of phenolic compounds were achieved using high-performance liquid chromatography-diode array detection-electrospray ionization-tandem mass spectrometry. Total phenolic content and oxygen radical absorbance capacity were also determined to evaluate the antioxidant properties of this table grape. RESULTS A high number of non-anthocyanin phenolic compounds was identified in 'Karaerik' table grape skins and seeds, including 11 flavonols, six hydroxycinnamic acid derivatives, two stilbenes, several monomeric and dimeric flavan-3-ols and proanthocyanidins. Quercetin-type derivatives dominated the flavonol profile of grape skins, followed by myricetin type. Tartaric acid esters of three acids (caffeic, coumaric and ferulic acids) were the main hydroxycinnamic acid derivatives in this cultivar. Qualitative and quantitative differences were observed in flavan-3-ol composition among the grape tissues. Proanthocyanidins were the most abundant class of phenolic compounds in 'Karaerik' grapes, being mainly located in seeds. Higher antioxidant capacity values were determined in grape seeds, in correlation with the total phenolic content. CONCLUSION These results provide useful information for a better understanding of phenolic antioxidants from the 'Karaerik' table grape and will contribute to promoting the varietal identity and health-related properties of this fruit. © 2021 Society of Chemical Industry.

Chemical profiling of Buddleja globosa was performed by high-performance liquid chromatography coupled to electrospray ionization (HPLC-DAD-ESI-IT/MS) and quadrupole time-of-flight high-resolution mass spectrometry (HPLC-ESI-QTOF/MS). The identification of 17 main phenolic compounds in B. globosa leaf extracts was achieved. Along with caffeoyl glucoside isomers, caffeoylshikimic acid and several verbascoside derivatives (β-hydroxyverbascoside and β-hydroxyisoverbascoside) were identified. Among flavonoid compounds, the presence of 6-hydroxyluteolin-7-O-glucoside, quercetin-3-O-glucoside, luteolin 7-O-glucoside, apigenin 7-O-glucoside was confirmed. Campneoside I, forsythoside B, lipedoside A and forsythoside A were identified along with verbascoside, isoverbascoside, eukovoside and martynoside. The isolation of two bioactive phenolic compounds verbascoside and forsythoside B from Buddleja globosa (Buddlejaceae) was successfully achieved by centrifugal partition chromatography (CPC). Both compounds were obtained in one-step using optimized CPC methodology with the two-phase solvent system comprising ethyl acetate-n-butanol-ethanol-water (0.25: 0.75: 0.1: 1, v/v). Additionally, eight Natural Deep Eutectic Solvents (NADESs) were tested for the extraction of polyphenols and compared with 80% methanol. The contents of verbascoside and luteolin 7-O-glucoside after extraction with 80% methanol were 26.165 and 3.206 mg/g, respectively. Among the NADESs tested in this study, proline- citric acid (1:1) and choline chloride-1, 2- propanediol (1:2) were the most promising solvents. With these NADES, extraction yields for verbascoside and luteolin 7-O-glucoside were 51.045 and 4.387 mg/g, respectively. Taken together, the results of this study confirm that CPC enabled the fast isolation of bioactive polyphenols from B. globosa. NADESs displayed higher extraction efficiency of phenolic and therefore could be used as an ecofriendly alternative to classic organic solvents.

Due to the current dominance of a few grape varieties in the wine market, the aim of this work was to study the detailed phenolic and volatile composition, chromatic characteristics, and sensorial properties of red wines elaborated with new Vitis vinifera grapes (Moribel and Tinto Fragoso) identified using the High Perfomance Liquid Chromatography-Diode Array Detector-Electrospray Ionization-Tandem Mass Spectrometry (HPLC-DAD-ESI-MS/MS), Gas Chromatography- Mass Spectrometry (GC-MS), CIELab color space, and Napping ? techniques. RESULTS Tinto Fragoso wine showed higher phenolic content than Moribel, with more anthocyanins, flavonols, and stilbenes. These wines also contained anthocyanin diglucosides not reported for Vitis vinifera wines. The odor activity values of free volatile compounds were calculated to indicate their influence on wine aroma, the fruity aromas of Moribel standing out particularly. The wines studied were positively evaluated by the tasters. Moribel's sensory profile was characterized by red fruit aromas and Tinto Fragoso showed more aromatic intensity and persistence in the mouth. CONCLUSION The results obtained from the first characterization of red wines made from novel Vitis vinifera grapes suggest that Moribel and Tinto Fragoso could be appropriate raw materials for the elaboration of quality young red wines. Tinto Fragoso provided wines with sensorial properties different from those of Tempranillo, and could be an alternative to the well known red wines on the market. ? 2018 Society of Chemical Industry

Flavonols are a class of polyphenol compounds whose importance for wine quality has increased as their structures and properties have become better understood. Here, the acetylated and p-coumaroylated derivatives of the flavonol 3-O-glucosides of isorhamnetin, laricitrin and syringetin have been identified for the first time in Vitis vinifera grape skins and wines. First, the MS2 fragmentation patterns of the new flavonol derivatives showed a main signal attributable to the expected flavonol aglycone. In the p-coumaroylated derivatives, the signal corresponding to the intermediate loss of the phenolic acid was also observed. The structures of the aglycones were confirmed by their respective MS3 experiments that matched with those obtained from authentic standards of the aglycones. In addition, the fragmentation signals corresponding to the aglycone radical ions generated through homolytic cleavage assisted identification, and could support future studies of flavonoid compounds by ESI-MS. Using an HPLC-ESI-Q-ToF system, the observed m/z values of the compounds being studied were successfully matched with the expected formula. Surprisingly, just the minority methoxylated flavonol glucosides presented acylation, suggesting a high substrate specificity of the acyltransferases implicated in their synthesis. These findings show higher diversity of grape and wine flavonols. Additional studies and isolation strategies need to be followed to further characterize these metabolites as to test their presence in other grape varieties and it wines.

Peumus boldus Mol., is a Chilean medicinal tree used for gastrointestinal and liver diseases. Such medicinal properties are associated with the presence of bioactive flavonoids and aporphine alkaloids. In this study, a new green and efficient extraction method used seven natural deep eutectic solvents (NADES) as extraction media. The extraction efficiency of these NADES was assessed, determining the contents of boldine and total phenolic compounds (TPC). Chemical profiling of P. boldus was done by high-performance liquid chromatography coupled to photo diode array detector and electrospray ion-trap mass spectrometry (HPLC-PDA-ESI-IT/MS) and electrospray ionization quadrupole time-of-flight high-resolution mass spectrometry (HPLC-ESI-QTOF-MS). Among the NADES tested, NADES4 (choline chloride-lactic acid) and NADES6 (proline-oxalic acid) enable better extraction of boldine with 0.427 &plusmn, 0.018 and 2.362 &plusmn, 0.055 mg of boldine g&minus, 1 of plant, respectively. Extraction of boldine with NADES4 and NADES6 was more efficient than extractions performed with methanol and water. On the other hand, the highest TPC were obtained using NADES6, 179.442 &plusmn, 3.79 mg of gallic acid equivalents (GAE g&minus, 1). Moreover, TPC in extracts obtained with methanol does not show significant differences with NADES6. The HPLC-PAD-MS/MS analysis enable the tentative identification of 9 alkaloids and 22 phenolic compounds. The results of this study demonstrate that NADES are a promising green extraction media to extract P. boldus bioactive compounds and could be a valuable alternative to classic organic solvents.

Grapes are considered to be a major source of phenolic compounds as compared with other fruits. To improve the quality of table grapes, some techniques like thinning can be used. In addition, grape cultivars with distinct characteristics are directly linked to its phenolic profile. This study aimed to identify and quantify the phenolic compound profile and yield of the hybrid ‘BRS Vitoria’ seedless table grape under different bunch densities, using a combination of solid-phase extraction (SPE) methodologies and analytical high-performance liquid chromatography-diode array detector with tandem mass spectrometry (HPLC–DAD–ESI-MS/MS). A trial was carried out in 2016, in a commercial vineyard at Marialva, state of Parana (South Brazil). Three weeks after anthesis, the following bunch densities were evaluated: 4.0, 4.5, 5.0, 5.5, and 6 bunches per m2 (corresponding to an estimation of 16, 18, 20, 22, and 24 tons ha−1). The randomized block design was used as a statistical model with each treatment was replicated four times, with one vine per plot. Different characteristics were evaluated at harvest, e.g., soluble solids content (SS), total acidity (TA), maturation index (MI = SS/TA), bunch and berry masses, yield, as well hydroxycinnamic acid derivative (HCAD), anthocyanin, flavonol, and flavan-3-ol contents by HPLC–DAD–ESI-MS/MS analysis. The evaluated bunch densities did not interfere with the physicochemical characteristics of the berries, such as SS and MI. Under the density of 6.0 bunches per m2, the highest yield of 25 tons ha−1 was reached. Under all bunch densities, the phenolic profile presented the same compounds, but at different concentrations. Under a density of 5.0 bunches per m2, the compounds belonging to the anthocyanin and flavonol families were present in high concentrations. In contrast, at the densities of 4.0 and 4.5 bunches per m2, there was a reduction in the flavan-3-ol content. With respect to stilbenes, only the trans-piceid and its cis- isomer were detected. However, their concentrations had no significant influence on the evaluated bunch densities.

ObjectivesTo analyse the association between aminosalicylate-treated inflammatory bowel disease (IBD) and Parkinson’s disease (PD) at population level.DesignCross-sectional study.SettingThe study was performed based on electronic drug prescription and dispensation records of the Andalusian Public Health System.ParticipantsAll individuals aged ≥50 years with at least one drug dispensation during December 2014 were identified from the records.Primary and secondary outcome measuresGroups were formed: ‘possible PD’ group, including all who received an anti-Parkinson agent; ‘possible IBD’ group, those treated with mesalazine and/or derivatives (5-aminosalicylic acid (5-ASA)); and ‘possible PD and IBD’, including those receiving both anti-Parkinson agent and 5-ASA. Prevalence of possible PD was determined among those with possible IBD and among those without this condition. The age-adjusted and sex-adjusted OR was calculated.ResultsWe recorded 2 020 868 individuals (68±11 years, 56% female), 19 966 were included in possible PD group (75±9 years, 53% female) and 7485 in possible IBD group (64±10 years, 47% female); only 56 were included in both groups (76±8 years, 32% female). The prevalence of possible PD was 0.7% among those with possible IBD and 1% among those without this condition (adjusted OR=0.94; 95% CI 0.72 to 1.23; p=0.657). OR was 0.28 in individuals aged ≤65 years (95% CI 0.10 to 0.74; p=0.01) and 1.17 in older individuals (95% CI 0.89 to 1.54; p=0.257).ConclusionsWithin the limitations of this study, the results suggest a protective role for IBD and/or 5-ASA against PD development, especially among under 65-year olds. Further studies are warranted to explore this association given its scientific and therapeutic implications.

Background Grape berries exhibit various beneficial health effects due to the potent antioxidant roles of their phenolic compounds. A new Vitis vinifera grape cultivar (Karaerik) grown in Turkey has attracted growing interest due to its antioxidant phenolic compounds, which have still not been investigated. The phenolic/anthocyanin profile needs to be investigated to ascertain its potential health benefits and market value in the region. The present study therefore involves a detailed characterization of the anthocyanin composition of 'Karaerik' grape berries in conjunction with a determination of the antioxidant capacity value of the phenolics present in the skin and the whole berry. Results Total phenolic compounds (average 8.56 and 2.88 g gallic acid equivalent kg-1 fresh weight) and anthocyanin (7.48 and 1.66 g mv-3-glc equivalent kg-1 fresh weight) contents varied significantly in the skin and whole berry. Malvidin-based anthocyanins made the highest contribution to the pigment content of the berry. Accordingly, the major anthocyanin in the skin (average 42.08 mol%) and whole berry (39.98 mol%) was malvidin-3-glucoside (mv-3-glc). In addition, we found strong evidence of the occurrence of sometimes reported malvidin-3-pentoside and particularly of the not previously reported feruloyl derivative of malvidin-3-(6″-feruloyl)-glucoside (mv-3-ferglc) for V. vinifera grapes. Conclusion The current study is the first report to profile the anthocyanins of the grape with a detailed description of the rare and novel anthocyanin in V. vinifera grapes. The berry is also a potential source of phenolics/anthocyanins with a high antioxidant capacity value and is worthy of comparison with other V. vinifera grapes. © 2019 Society of Chemical Industry.

Determining the harvest date of table grapes is very important to achieve high-quality bunches with adequate soluble solids content, low titratable acidity, and high concentrations of polyphenols. Table grape consumption has increased worldwide due to its phenolic compound content and its beneficial effects on human health. Thus, this study aimed to characterize the phenolic ripening of ‘BRS Vitoria’ seedless table grapes at different ripening stages using HPLC–DAD–ESI-MS/MS. For this purpose, a trial was carried out during 2016 in a commercial vineyard of ‘BRS Vitoria’ seedless grape located in Marialva, state of Parana (Southern Brazil). Berry samples were assessed weekly, starting at veraison until full ripeness. At each ripening stage, the berries were analyzed to determine their physicochemical characteristics and polyphenolic profile. It was observed that ‘BRS Vitoria’ grapes can be harvested approximately 28 days after veraison, when the berries reach soluble solids content higher than 15°Brix and low titratable acidity. The grapes presented a typical anthocyanin profile of hybrid grapes, composed of 3-glucoside and 3,5-diglucoside derivatives. In addition, pelargonidin traces were also observed, and this aglycone is rarely detected in grapes. The total anthocyanin concentration, as malvidin-3,5-diglucoside equivalents, is close to 596.9 mg kg−1. Concerning flavonols, myricetin and quercetin are detected in greater proportions, and this cultivar can also be considered an important source of proanthocyanidins.

Lipids are important constituents of plant and animal cells, being essential due to their biological functions. Despite the significant role of these compounds in grape berries, knowledge of grape lipid composition is still limited. This study addresses the free fatty acid composition and other lipids in skins and seeds of several Vitis vinifera grape cultivars using LC-MS/MS. A different profile of free fatty acids was determined in the grape tissues, showing a higher proportion of unsaturated fatty acids in seeds (ca. 60%). Lignoceric acid was one of the main free saturated fatty acids found in grape skins, together with palmitic and stearic acids. Berry skins showed similar ranges of C18-unsaturated fatty acids, whereas linoleic acid was predominant in the seed fatty acid composition. Higher content of glycerophospholipids was determined in grape seeds. Uvaol and oleanolic acid were only quantified in skins (1.5–3.9 and 38.6–57.6 mg/kg fresh weight, respectively). These preliminary results suggest a certain diversity in grape lipids according to their location in the berry tissues and cultivar, providing useful information for the fermentation process due to their role in wine sensory profile and yeast growth.