Wine by-products: phenolic characterization and antioxidant activity evaluation of grapes and grape pomaces from six different French grape varieties.

Grenache, Syrah, Carignan Noir, Mourvèdre, Counoise and Alicante Bouchet grape seeds and skins, harvested in 2009 and 2010 in the Rhône valley area of France, and their respective pomaces remaining after vinification, were analyzed for their phenolic composition and antioxidant activity. The polyphenol content was quantified by HPLC and the Folin-Ciocalteu assay. The antioxidant potential was measured with four different assays: ORAC, FRAP, ABTS and DPPH. Seeds contained higher amounts of total polyphenols, up to 44.5 mg of gallic acid equivalent [GAE]/g dry weight in Alicante pomace, than skin extracts. The maximum total phenolic in skins was 31.6 mg GAE/g dry weight detected in 2010 Alicante pomace. Seeds also had the highest antioxidant capacity. HPLC analysis revealed that, despite the vinification process, pomaces still contained an appreciable amount of proanthocyanidins as well as several anthocyanin glycosides. Alicante and Syrah proved to be the varieties of most interest in terms of their potential development for nutraceutical purposes.

Evolution of analysis of polyhenols from grapes, wines, and extracts.

Grape and wine phenolics are structurally diverse, from simple molecules to oligomers and polymers usually designated as tannins. They have an important impact on the organoleptic properties of wines, that's why their analysis and quantification are of primordial importance. The extraction of phenolics from grapes and from wines is the first step involved in the analysis. Then, several analytical methods have been developed for the determination of total content of phenolic, while chromatographic and spectrophotometric analyses are continuously improved in order to achieve adequate separation of phenolic molecules, their subsequent identification and quantification. This review provides a summary of evolution of analysis of polyphenols from grapes, wines and extracts.

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.

Tannin composition of cabernet-sauvignon and merlot grapes from the bordeaux area for different vintages (2006 to 2009) and comparison to tannin profile of five 2009 vintage mediterranean grapes varieties.

The proanthocyandin composition of skins and seeds of Bordeaux Merlot (M) and Cabernet Sauvignon (CS) grapes was evaluated by HPLC-UV-fluorescence for four consecutive vintages (2006 to 2009). The results indicated a strong vintage effect on the tannin profile of each variety. However, and in spite of the vintage effect, some tannin characteristics such as mDP, %G and %P allow discrimination of both Bordeaux varieties. The same analyses were carried out for the 2009 vintage of five Mediterranean grape varieties (Syrah, Grenache, Mourvedre, Carignan and Counoise). The results demonstrated differences among these five varieties. Syrah appeared to exhibit the highest concentrations of flavanol monomers and dimmers, especially in skins. The comparison study between Bordeaux and Mediterranean grape varieties for the same vintage (2009) revealed that mDP and %G for seed extracts were parameters specific to each vineyard area.

Selection of potential impact odorants and sensory validation of their importance in typical chardonnay wines.

The aim of the present study was to validate the joint sensory impact of target compounds on the typicality degree of wine. Target compounds were selected from previous gas chromatography-olfactometry analysis. The preliminary experiment consisted in selecting odorants thought to have a positive effect on typical Chardonnay wines. Two sets of target compounds were chosen with regard to expected relationships between their concentrations and typicality scores. Target compounds were quantified in 20 wines. The second experiment was dedicated to the sensory evaluation of aroma models obtained by supplementation in wines. Three Chardonnay wines with intermediate typicality scores were supplemented with 6- or 10-compound combinations. The typicality degree of 24 samples was assessed by expert orthonasal perception. Wines supplemented with the 6-compound combinations were judged to be intermediate, whereas wines including the 10-compound combinations were considered to be quite representative of the Chardonnay concept. Such results confirm the active contribution of the 10 combined target compounds to typical Chardonnay wines.

Influence of phenolic compounds on the sensorial perception and volatility of red wine esters in model solution: an insight at the molecular level.

Impact of (+)-catechin and gallic acid on sensory perception and volatility of isoamyl acetate, ethyl isobutyrate, ethyl butyrate and ethyl octanoate was investigated in model solutions, by means of triangle tests, detection threshold determination and HS-GC-MS analyses. Catechin significantly altered the sensory perception of most esters (ethyl isobutyrate, ethyl butyrate and ethyl octanoate) while gallic acid displayed no impact. Ethyl butyrate and ethyl octanoate odour thresholds doubled or tripled in the presence of catechin, underlining a retention impact of phenolic compounds in liquid matrix. The headspace analyses displayed a decrease only in ethyl octanoate volatility in presence of catechin, whereas no significant difference in other esters concentrations was observed. This study indicated that phenolic compounds have a variable impact on aroma compounds' volatility and their sensory perception. The polarity of phenolic and volatile compounds as well as their spatial conformation also appeared to influence the interaction strength.

Dietary iron-initiated lipid oxidation and its inhibition by polyphenols in gastric conditions.

The gastric tract may be the first site where food is exposed to postprandial oxidative stress and antioxidant activity by plant micronutrients. After food intake, dietary iron, dioxygen, and emulsified lipids come into close contact and lipid oxidation may take place. This study investigated lipid oxidation and its inhibition by dietary polyphenols in gastric-like conditions. Lipid oxidation induced by heme and nonheme iron was studied in acidic sunflower oil-in-water emulsions. The emulsifier type (bovine serum albumin, phospholipids), pH, and iron form were found to be factors governing the oxidation rates. Quercetin, rutin, and chlorogenic acid highly inhibited the metmyoglobin-initiated lipid oxidation in both emulsified systems at pH 5.8. Additionally, quercetin inhibited nonheme iron-initiated processes, while it was inefficient with hematin as an initiator. The presence of human gastric juice did not influence lipid oxidation, although it diminished the antioxidant activity of phenolics. Model emulsions may thus be valuable tools to study the gastric stability of polyunsaturated lipids.

Influence of serum albumin and the flavonol quercetin on the peroxidase activity of metmyoglobin.

Metmyoglobin (MbFe(III)), a major form of dietary iron, is an efficient inducer of lipid and protein oxidation. Indeed, MbFe(III) is able to cleave hydrogen peroxide and lipid hydroperoxides with subsequent formation of ferrylmyoglobin (MbFe(IV)=O) and lipid oxyl and peroxyl radicals. In the first part of this work, the mechanism of the reaction between MbFe(III) and H(2)O(2) is revisited with an emphasis on the influence of bovine serum albumin (BSA). BSA does not affect the rate of MbFe(IV)=O formation but inhibits the formation of a redox-inactive green pigment (heme-protein cross-link species). Although tightly bound to BSA, the flavonol quercetin is still able to reduce MbFe(IV)=O as a likely result of long-range electron transfers within a protein-protein complex. In the second part, BSA is shown to strongly slow down the metmyoglobin-catalyzed consumption of linoleic acid hydroperoxides with formation of ketones as the main products. In the process, only low concentrations of ferrylmyoglobin are slowly accumulated. A catalytic mechanism is proposed that involves a one-electron-oxidized metmyoglobin species distinct from ferrylmyoglobin.

Chemical modeling of heme-induced lipid oxidation in gastric conditions and inhibition by dietary polyphenols.

The gastric tract may be the first site exposed to diet-related oxidative stress. After food intake, dietary iron such as (met)myoglobin, the pigment of meat, oxygen, and polyunsaturated lipids come into close contact. The main goal of this work is the in vitro investigation of lipid oxidation taking place in the gastric compartment and its inhibition by dietary polyphenols. Oil-in-water emulsions stabilized either by bovine serum albumin (BSA) or egg yolk phospholipids (PL) were designed to model the gastric content. The metmyoglobin-initiated lipid oxidation led to the accumulation of lipid-derived conjugated dienes and volatile aldehydes. These reactions were faster in the BSA model than in the PL model, highlighting the influence of the interfacial composition. Quercetin, rutin, (+)-catechin, caffeic acid, and chlorogenic acid proved to be better inhibitors than alpha-tocopherol and ascorbic acid. Emulsions as models of the gastric environment are valuable tools to study the stability of macro- and micronutrients.

4-methylcoumarins as antioxidants: scavenging of peroxyl radicals and inhibition of human low-density lipoprotein oxidation.

The antioxidant activity of eight synthetic 4-methylcoumarins was systematically studied. The antioxidant capacity was measured using: (i) a competition kinetic test, to measure the relative capacity to quench peroxyl radical; (ii) the in vitro oxidative modification of human low-density lipoprotein, initiated by AAPH or catalyzed by copper. In both models, the ortho-OH substitutes were found to be better antioxidant than the meta one. The most efficient antioxidant was the 7,8-dihydroxy-4-methylcoumarin and the corresponding diacetoxy-substituted was unexpectedly a good antioxidant. Finally, the presence of an ethoxycarbonylethyl substituent at the C-3 position increased the antioxidant capacity of both 7,8-dihydroxy-4-methylcoumarin and 7,8-diacetoxy-4-methylcoumarin.