Comparative Study on Grape Berry Anthocyanins of Various Teinturier Varieties.

The red-fleshed grape cultivars, called teinturier or dyer grapes, contain anthocyanins in both the skin and flesh. These phenolic compounds exhibit excellent coloring ability, and as antioxidants, they are important bioactive compounds in food crops. In this work, anthocyanin patterns of grape berries of fifteen teinturier varieties collected from the gene bank located at Pécs in the southwest of Hungary were compared. Anthocyanin profiles of numerous varieties originating from Hungary such as 'Bíborkadarka', 'Kármin', 'Kurucvér', and 'Turán' are reported for the first time. Anthocyanins extracted separately from the skin and juice were analyzed using high-performance liquid chromatography coupled with a photodiode array detector. For the identification of compounds, high-resolution orbitrap mass spectrometry was used. All in all, twenty-one anthocyanins were identified and quantified. We found that anthocyanin patterns differed significantly in the skin and juice for all investigated cultivars. For Vitis vinifera varieties, the predominant anthocyanin in the skin was malvidin-3-O-glucoside, while the main pigment in the juice was peonidin-3-O-glucoside. For the first time, a significant amount of diglucosides was detected in two Vitis Vinifera cultivars with a direct relationship. In general, the pigment composition of the skin was much more complex than that of the juice. The comparative study with presented patterns gives valuable and beneficial information from a chemotaxonomical point of view. Our results also help to choose the appropriate teinturier varieties with the desired anthocyanins for food coloring or winemaking purposes.

Tannin phenotyping of the Vitaceae reveals a phylogenetic linkage of epigallocatechin in berries and leaves.

BACKGROUND AND AIMS: Condensed tannins, responsible for berry and wine astringency, may have been selected during grapevine domestication. This work examines the phylogenetic distribution of condensed tannins throughout the Vitaceae phylogenetic tree. METHODS: Green berries and mature leaves of representative true-to-type members of the Vitaceae were collected before 'véraison', freeze-dried and pulverized, and condensed tannins were measured following depolymerization by nucleophilic addition of 2-mercaptoethanol to the C4 of the flavan-3-ol units in an organic acidic medium. Reaction products were separated and quantified by ultrahigh pressure liquid chromatography/diode array detection/mass spectrometry. KEY RESULTS AND CONCLUSIONS: The original ability to incorporate epigallocatechin (EGC) into grapevine condensed tannins was lost independently in both the American and Eurasian/Asian branches of the Vitaceae, with exceptional cases of reversion to the ancestral EGC phenotype. This is particularly true in the genus Vitis, where we now find two radically distinct groups differing with respect to EGC content. While Vitis species from Asia are void of EGC, 50 % of the New World Vitis harbour EGC. Interestingly, the presence of EGC is tightly coupled with the degree of leaf margin serration. Noticeably, the rare Asian EGC-forming species are phylogenetically close to Vitis vinifera, the only remnant representative of Vitis in Eurasia. Both the wild ancestral V. vinifera subsp. sylvestris as well as the domesticated V. vinifera subsp. sativa can accumulate EGC and activate galloylation biosynthesis that compete for photoassimilates and reductive power.

Age- and season-dependent pattern of flavonol glycosides in Cabernet Sauvignon grapevine leaves.

Flavonols play key roles in many plant defense mechanisms, consequently they are frequently investigated as stress sensitive factors in relation to several oxidative processes. It is well known that grapevine (Vitis vinifera L.) can synthesize various flavonol glycosides in the leaves, however, very little information is available regarding their distribution along the cane at different leaf levels. In this work, taking into consideration of leaf position, the main flavonol glycosides of a red grapevine cultivar (Cabernet Sauvignon) were profiled and quantified by HPLC-DAD analysis. It was found that amount of four flavonol glycosides, namely, quercetin-3-O-galactoside, quercetin-3-O-glucoside, kaempferol-3-O-glucoside and kaempferol-3-O-glucuronide decreased towards the shoot tip. Since leaf age also decreases towards the shoot tip, the obtained results suggest that these compounds continuously formed by leaf aging, resulting in their accumulation in the older leaves. In contrast, quercetin-3-O-glucuronide (predominant form) and quercetin-3-O-rutinoside were not accumulated significantly by aging. We also pointed out that grapevine boosted the flavonol biosynthesis in September, and flavonol profile differed significantly in the two seasons. Our results contribute to the better understanding of the role of flavonols in the antioxidant defense system of grapevine.

Changes in grapevine leaf phenolic profiles during the day are temperature rather than irradiance driven.

Photosynthesis parameters, adaxial flavonoid index, phenolic profiles and antioxidant capacities of south-facing sun exposed grapevine leaves (Vitis vinifera, Pinot Noir cultivar) were measured hourly between 7 a.m. and 7 p.m. on a clear summer day. Changes in these parameters were statistically compared to changes in environmental conditions, including solar irradiance (photosynthetically active and UV radiations), leaf and air temperature, and relative air humidity. Epidermal UV absorbance, characterised by the flavonoid index, and total extractable phenolic contents were correlated to distinct environmental parameters. The former was positively correlated to irradiance and leaf temperature, while the latter was positively correlated to air temperature. HPLC phenolic profiling identified a positive correlation between air temperature and amounts of the dominant flavonol component, quercetin-3-O-glucuronide. The only phenolic component statistically connected to the flavonoid index was quercetin-3-O-glucoside. This correlation was positive and both parameters decreased during the day, although changes in the amount of this flavonol component showed no correlation to environmental factors. Total antioxidant capacities of leaf extracts were positively correlated to solar UV, and leaf and air temperature, but not to photosynthetically active radiation. Positive correlations of quercetin-3-O-glucoside contents with the flavonoid index, with photosynthesis and with sub-stomatal CO2 concentration suggest a special protective role of this flavonol. A short-term negative effect of solar UV-A and UV-B on photosynthetic CO2 uptake was also identified, which was unrelated to changes in stomatal conductance. A hypothesis is presented assuming UV- and photorespiration-derived hydrogen peroxide as the driver of daily changes in leaf antioxidant capacities.

Nanostructured TiO2-induced photocatalytic stress enhances the antioxidant capacity and phenolic content in the leaves of Vitis vinifera on a genotype-dependent manner.

Over the past decades, nanotechnology has received great attention and brought revolutionary solutions for a number of challenges in scientific fields. Industrial, agricultural and medical applications of engineered nanomaterials have increased intensively. The ability of titanium dioxide nanoparticles (TiO2 NPs) to produce reactive oxygen species (ROS), when excited by ultra-violet (UV) light, makes them useful for effectively inactivate various pathogens. It is known that ROS also have signalling role in living organisms, therefore, TiO2 NPs-induced ROS can influence both enzymatic and non-enzymatic defence systems, and could play a role in the resistance of plants to pathogens. Herein, we studied the photocatalytic stress responses of grapevine (Vitis vinifera L.) as model plant, when exposed to a well-known photocatalyst, Degussa P25 TiO2 NPs. The photocatalytically produced ROS such as superoxide anion, hydroxyl radical and singlet oxygen were confirmed by electron paramagnetic resonance spectroscopy. Foliar exposure of five red cultivars (Cabernet sauvignon, Cabernet franc, Merlot, Kékfrankos and Kadarka) was carried out in blooming phenophase under field condition where plants are exposed to natural sunlight with relatively high UV radiation (with a maximum of ~ 45 W m-2). After two weeks of exposure, the effects of photogenerated ROS on the total phenolic content, antioxidant capacity, flavonol profile and the main macro-, microelements of the leaves were studied in detail. We found that foliar application of TiO2 NPs boosted the total phenolic content and biosynthesis of the leaf flavonols depending on the grapevine variety. Photocatalytically active TiO2 NPs also increased K, Mg, Ca, B and Mn levels in the leaves as shown by ICP-AES measurements.

Environmental plasticity of Pinot noir grapevine leaves: A trans-European study of morphological and biochemical changes along a 1,500-km latitudinal climatic gradient.

A 2-year study explored metabolic and phenotypic plasticity of sun-acclimated Vitis vinifera cv. Pinot noir leaves collected from 12 locations across a 36.69-49.98°N latitudinal gradient. Leaf morphological and biochemical parameters were analysed in the context of meteorological parameters and the latitudinal gradient. We found that leaf fresh weight and area were negatively correlated with both global and ultraviolet (UV) radiation, cumulated global radiation being a stronger correlator. Cumulative UV radiation (sumUVR) was the strongest correlator with most leaf metabolites and pigments. Leaf UV-absorbing pigments, total antioxidant capacities, and phenolic compounds increased with increasing sumUVR, whereas total carotenoids and xanthophylls decreased. Despite of this reallocation of metabolic resources from carotenoids to phenolics, an increase in xanthophyll-cycle pigments (the sum of the amounts of three xanthophylls: violaxanthin, antheraxanthin, and zeaxanthin) with increasing sumUVR indicates active, dynamic protection for the photosynthetic apparatus. In addition, increased amounts of flavonoids (quercetin glycosides) and constitutive ß-carotene and α-tocopherol pools provide antioxidant protection against reactive oxygen species. However, rather than a continuum of plant acclimation responses, principal component analysis indicates clusters of metabolic states across the explored 1,500-km-long latitudinal gradient. This study emphasizes the physiological component of plant responses to latitudinal gradients and reveals the physiological plasticity that may act to complement genetic adaptations.

Environmental Factors Correlated with the Metabolite Profile of Vitis vinifera cv. Pinot Noir Berry Skins along a European Latitudinal Gradient.

Mature berries of Pinot Noir grapevines were sampled across a latitudinal gradient in Europe, from southern Spain to central Germany. Our aim was to study the influence of latitude-dependent environmental factors on the metabolite composition (mainly phenolic compounds) of berry skins. Solar radiation variables were positively correlated with flavonols and flavanonols and, to a lesser extent, with stilbenes and cinnamic acids. The daily means of global and erythematic UV solar radiation over long periods (bud break-veraison, bud break-harvest, and veraison-harvest), and the doses and daily means in shorter development periods (5-10 days before veraison and harvest) were the variables best correlated with the phenolic profile. The ratio between trihydroxylated and monohydroxylated flavonols, which was positively correlated with antioxidant capacity, was the berry skin variable best correlated with those radiation variables. Total flavanols and total anthocyanins did not show any correlation with radiation variables. Air temperature, degree days, rainfall, and aridity indices showed fewer correlations with metabolite contents than radiation. Moreover, the latter correlations were restricted to the period veraison-harvest, where radiation, temperature, and water availability variables were correlated, making it difficult to separate the possible individual effects of each type of variable. The data show that managing environmental factors, in particular global and UV radiation, through cultural practices during specific development periods, can be useful to promote the synthesis of valuable nutraceuticals and metabolites that influence wine quality.