Copigmentation between malvidin-3-glucoside and some wine constituents and its importance to colour expression in red wine

Thermodynamic parameters for intermolecular copigmentation interactions involving malvidin-3-glucoside were determined by UV/visible spectroscopy at wine pH (pH 3.6). These included association constants, enthalpy and entropy changes, which were measured for chlorogenic acid, caffeic acid, quercetin, quercetin-3-glucoside, (−)-epicatechin, (+)-catechin, procyanidin dimer and seed tannin. Quercetin produced the strongest copigment (K_CP = 2900 ± 1300), whilst the addition of glucose at position 3 (quercetin-3-glucoside) reduced its effect by almost 10-fold. Malvidin-3-glucoside self-association (K_D = 3300 ± 300 mol⁻¹ l) was thermodynamically favoured over intermolecular interaction with any of the copigments tested. No colour enhancement due to self-association was observed for malvidin-3-glucoside-derived pigments that cannot enter hydration reactions. In addition, malvidin-3-(6-O-p-coumaryl)glucoside did not show colour enhancement suggesting that the p-coumaryl group prevents self-association. The malvidin-3-glucoside circular dichroism (CD) spectrum was not affected by indicated changes in malvidin-3-glucoside concentration. These observations demonstrate that self-association of malvidin-3-glucoside is more important than copigmentation in young red wine.     

Phenolic composition of Merlot and Cabernet-Sauvignon grapes from Bordeaux vineyard for the 2009-vintage: Comparison to 2006, 2007 and 2008 vintages

Cabernet-Sauvignon and Merlot skin and seed extracts from Bordeaux grapes were investigated to determine both grape variety and vintage effect on phenolic composition. The total content of polyphenols and tannins in Merlot seeds was higher than that of Cabernet-Sauvignon allowing to discriminate the varieties. HPLC analyses underlined significant differences in the absolute concentration of proanthocyanidins amongst the two varieties and in their composition: mean degree of polymerisation (mDP) and percentage of galloylation of seed extracts were good indicators of grape variety. The vintage effect on the phenolic composition was confirmed for 2009 in comparison to previous vintages. Low values of mDP and concentrations of proanthocyanidins and anthocyanins were found in 2009 seeds and skins. The climatic conditions of 2009 (high rainfall before flowering followed by a strong hydric stress during berries development until ripening) let us hypothesise a lower activation of flavonoid pathway.     

Phenolic acids and flavonoids in leaf and floral stem of cultivated and wild Cynara cardunculus L. genotypes

Ten genotypes, cultivated and wild of Cynara cardunculus L. were evaluated for their content of phenolic acids, flavonoids and their antioxidant activity. The major compounds present in the leaf were luteolin derivatives in globe artichoke and apigenin derivatives in wild and cultivated cardoon. Apart from ‘Cimiciusa di Mazzarino’ (var. scolymus), caffeoylquinic acids represent the main phenolic compounds in the floral stem. In particular, ‘Sylvestris Creta’ (var. sylvestris) and ‘Violetto di Sicilia’ (var. scolymus) show the highest content of caffeoylquinic acid ∼95% of the total measured polyphenols. The antioxidant capacity, in both leaf and floral stem, was qualitatively and quantitatively dependent on the phenolic acid and flavonoid profile. The phenolic acids and flavonoids in normally uneaten parts of wild and cultivated artichoke could be exploited as sources of natural antioxidants.     

Phenolic compound characterisation and antiproliferative activity of “Annurca” apple,a southern Italian cultivar

In Annurca apples, a southern Italian variety, polyphenols were studied. The phenolic composition of Annurca apple peel was determined by HPLC coupled with electrospray negative ionisation multistage ion trap mass spectrometry (HPLC/ESI–ITMSⁿ). In addition, the antiproliferative and pro-apoptotic activities of peel extracts enriched in polyphenols and prepared from Annurca (APE), Red Delicious (RDPE) and Golden Delicious (GPE) varieties were evaluated on an HL-60 cell line. APE exhibited the highest total phenol content among the three apple cultivars tested, as determined by Folin–Ciocalteau’s procedure and HPLC–UV analysis. APE also showed higher amounts of chlorogenic acid, procyanidins, flavonols, dihydrochalcones and cyanidin-3-O-galactoside than GPE or RDPE. All three apple extracts were able to significantly decrease cell viability, from 50% to 80%, with APE appearing the most effective, while GPE was the least cytotoxic among the three samples. Similarly, APE and RDPE induced a significant increase of caspase-3 activity, whose activation represents a hallmark of apoptosis.     

Purification and structural characterisation of lipid transfer protein from red wine and grapes

Lipid transfer proteins (LTP) play a major role in plant defence and are of particular interest due to their known ability to cause allergic reactions. These proteins are expressed in grapes and also remain detectable after vinification, especially in red wine. However, it remains unknown whether the protein undergoes any changes during the vinification process. Here, we present a purification method for LTPs from Dornfelder grapes and wine. By liquid-chromatography–mass spectroscopy (LC–MS/MS) we identified LTPs from two different species (Vitis vinifera and Vitis aestivalis). Additionally, the purified LTPs were characterised using spectrometric methods, confirming their high purity and structural stability during vinification. We conclude that LTPs are resistant to the alcohol content (13.5 vol%), acidic milieu of wine and other ingredients present during the vinification process, indicating that the allergenic potential of grape LTP is not diminished by the vinification process.     

The interactive effects of irrigation,nitrogen fertilisation rate,delayed harvest and storage on the polyphenol content in red grape (Vitis vinifera) berries: A factorial experimental design

Polyphenol concentrations, including anthocyanidins, flavonols, flavan-3-ols and stilbenes, were quantified by liquid chromatography/mass spectrometry in two cultivars of red grapes for daily consumption, which were subjected to different kinds of water supply and nitrogen fertilisation rates. Samples from the same vineyards were also analysed after a 6 week storage in a refrigerator and 6 week delayed harvesting. Berry skins and seeds were analysed separately.     

Tocols of selected spring wheat (Triticum aestivum L.), einkorn wheat (Triticum monococcum L.) and wild emmer (Triticum dicoccum Schuebl [Schrank]) varieties

Wheat contributes significantly worldwide to antioxidant income with beneficial healthy effects. Two varieties of einkorn wheat (Triticum monococcum L. – Escana and Schwedisches Einkorn), two varieties of wild emmer [Triticum dicoccum Schuebl (Schrank)] (Rudico and Kahler Emmer) and three varieties of spring wheat (Triticum aestivum L. – Granny, Kärtner Früher and SW Kadrilj) were evaluated for tocols – tocopherols and tocotrienols by high performance liquid chromatography – electrospray ionisation tandem mass spectrometry (HPLC–ESI/MS/MS). Investigated emmer and einkorn wheat varieties have shown minor lower total tocols content in comparison with spring varieties, however significant typical levels of tocopherols and tocotrienols were found in these groups. In einkorn wheat varieties the major abundance of total tocols is represented by tocotrienols (Schwedisches Einkorn 65.0%, Escana 54.9%), in emmer wheat varieties the abundance of tocotrienols and tocopherols were similar (Rudico 48.9% of tocotrienols, Kahler Emmer 47.6%), whereas in spring bread wheat higher tocopherols (SW Kadrilj 54.5%, Kärtner Früher 60.2%, Granny 55.0%) were recorded.     

Correlation between plasma antioxidant capacity and verbascoside levels in rats after oral administration of lemon verbena extract

Phenylpropanoids are the main class of compounds from lemon verbena which have shown a wide biological activity, verbascoside being the most abundant one. In this work, the composition of a lemon verbena extract was elucidated by HPLC-ESI-MS/MS and one flavone and one methoxylated phenylpropanoid were found in this source for the first time. The antioxidant activity of the lemon verbena extract was fully characterised by several methodologies. Unexpectedly, the extract was especially active in lipophilic environments and lipid peroxidation inhibition assay, as it was found for pure verbascoside. The lemon verbena extract, containing verbascoside as its major bioactive compound, was acutely administered to rats and verbascoside was the only metabolite detected in plasma samples as measured by HPLC mass spectrometry. The correlation between the highest verbascoside concentration in plasma and maximum plasma antioxidant capacity was observed at 20 min as measured by different techniques, i.e. minimum malondialdehyde (MDA) generation, highest ferric-reducing ability of plasma (FRAP value) and maximum superoxide dismutase activity (SOD). Therefore, the in vitro measurements of the antioxidant activity of lemon verbena extract may significantly support the antioxidant activity observed in vivo in this work. Moreover, neither evidence of acute oral toxicity nor adverse effects were observed in mice when the lemon verbena extract containing 25% verbascoside was used at a dosage of 2000 mg/kg.     

Metabolic profile and biological activities of Lavandula pedunculata subsp. lusitanica (Chaytor) Franco: Studies on the essential oil and polar extracts

We investigated the metabolic profile and biological activities of the essential oil and polar extracts of Lavandula pedunculata subsp. lusitanica (Chaytor) Franco collected in south Portugal. Gas chromatography–mass spectrometry (GC–MS) analysis revealed that oxygen-containing monoterpenes was the principal group of compounds identified in the essential oil. Camphor (40.6%) and fenchone (38.0%) were found as the major constituents. High-performance liquid chromatography with diode array detection (HPLC–DAD) analysis allowed the identification of hydroxycinnamic acids (3-O-caffeoylquinic, 4-O-caffeoylquinic, 5-O-caffeoylquinic and rosmarinic acids) and flavones (luteolin and apigenin) in the polar extracts, with rosmarinic acid being the main compound in most of them. The bioactive compounds from L. pedunculata polar extracts were the most efficient free-radical scavengers, Fe²⁺ chelators and inhibitors of malondialdehyde production, while the essential oil was the most active against acetylcholinesterase. Our results reveal that the subspecies of L. pedunculata studied is a potential source of active metabolites with a positive effect on human health.