Grapes are rich in primary and secondary metabolites. Among the secondary metabolites, polyphenolic compounds are the most abundant in grape berries. Besides their important impacts on grape and wine quality, this class of compounds has beneficial effects on human health. Due to their antioxidant activity, polyphenols and phenolic acids can act as anti-inflammatory and anticancerogenic agents, and can modulate the immune system. In grape berries, polyphenols and phenolic acids can be located in the pericarp and seeds, but distribution differs considerably among these tissues. Although some classes of polyphenols and phenolic acids are under strict genetic control, the final content is highly influenced by environmental factors, such as climate, soil, vineyard, and management. This review aims to present the main classes of polyphenolic compounds and phenolic acids in different berry tissues and grape varieties and special emphasis on their beneficial effect on human health.

(1) Background: Solid phase microextraction (SPME)-Arrow is a new extraction technology recently employed in the analysis of volatiles in food materials. Grape volatile organic compounds (VOC) have a crucial role in the winemaking industry due to their sensory characteristics of wine.; (2) Methods: Box–Behnken experimental design and response surface methodology were used to optimise SPME-Arrow conditions (extraction temperature, incubation time, exposure time, desorption time). Analyzed VOCs were free VOCs directly from grape skins and bound VOCs released from grape skins by acid hydrolysis.; (3) Results: The most significant factors were extraction temperature and exposure time for both free and bound VOCs. For both factors, an increase in their values positively affected the extraction efficiency for almost all classes of VOCs. For free VOCs, the optimum extraction conditions are: extraction temperature 60 °C, incubation time 20 min, exposure time 49 min, and desorption time 7 min, while for the bound VOCs are: extraction temperature 60 °C, incubation time 20 min, exposure time 60 min, desorption time 7 min.; (4) Conclusions: Application of the optimized method provides a powerful tool in the analysis of major classes of volatile organic compounds from grape skins, which can be applied to a large number of samples.

Phenolic compound profiles were investigated by high-performance liquid chromatography-diode array detector in three vintages to assess genotypic variation in berry skins of six resistant grapevine varieties: “Cabernet Cortis,” “Chancellor,” “Léon Millot,” “Maréchal Foch,” “Monarch,” and “Regent.” The research has revealed a significant difference among the varieties in the total phenolic content, anthocyanins, flavanols, and flavan-3-ols. A clear differentiation of all varieties by means of the polyphenol profile using discriminant analyses has been achieved. “Regent” reached the significantly highest total polyphenol content, as well as total anthocyanin and total flavonol content. The polyphenol profile of “Chancellor” was quite different from all of the other studied varieties. Although being closely related, “Maréchal Foch” and “Léon Millot” showed qualitatively and quantitatively quite different polyphenol contents. No clear connection between the genetic origin of the varieties and their polyphenol profiles has been found.

During the ripening process of grapes, the grapevine leaves are the most active green organs that are important for photosynthesis, which is closely linked to the development and metabolism of the plant. The detection of plant pigments and phenolic compounds in grapevine leaves can be a good indicator of the ageing process, vine vigor and the plant’s ability to respond to fungal attack. In a one-year study, the development of leaf chlorophylls, carotenoids and phenolic compounds during the ripening of six indigenous Croatian grape cultivars and the international cultivars Merlot and Chardonnay was investigated. The chlorophyll a/b ratio and total chlorophyll and total carotenoid concentrations were also investigated. PCA was used to highlight relevant information from the data with the aim of distinguishing individual compounds based on the cultivar and phenological stage. The leaf total hydroxycinnamic acid and flavan-3-ol concentrations decreased slowly during grape development, with the highest concentration immediately after flowering and the lowest during grape ripening. The concentrations of β-carotene, lutein and xanthophylls tended to decrease during bunch closure or veraison, while the concentration of chlorophylls a and b peaked during veraison and then decreased during grape ripening. This research will provide an opportunity to select cultivars with the physiological adaptation to synthesize secondary metabolites that are important for managing stress conditions.

The biochemical response and gene expression in different grapevine cultivars to water deficit are still not well understood. In this study, we investigated the performance of four traditional Croatian Vitis vinifera L. cultivars (‘Plavac mali crni’, ‘Istrian Malvasia’, ‘Graševina’, and ‘Tribidrag’), and one wild (Vitis vinifera subsp. sylvestris) genotype exposed to water deficit (WD) for nine days under semi-controlled conditions in the greenhouse. Sampling for biochemical and gene expression analyses was performed at days six and nine from the beginning of WD treatment. The WD affected the accumulation of metabolites with a significant increase in abscisic acid (ABA), salicylic acid (SA), and proline in the leaves of the stressed genotypes when the WD continued for nine days. Lipid peroxidation (MDA) was not significantly different from that of the control plants after six days of WD, whereas it was significantly lower (297.40 nmol/g dw) in the stressed plants after nine days. The cultivar ‘Istrian Malvasia’ responded rapidly to the WD and showed the highest and earliest increase in ABA levels (1.16 ng mg⁻¹ dw, i.e., 3.4-fold increase compared to control). ‘Graševina’ differed significantly from the other genotypes in SA content at both time points analyzed (six and nine days, 47.26 and 49.63 ng mg⁻¹ dw, respectively). Proline level increased significantly under WD (up to 5-fold at day nine), and proline variation was not genotype driven. The expression of aquaporin genes (TIP2;1 and PIP2;1) was down-regulated in all genotypes, coinciding with the accumulation of ABA. The gene NCED1 (9-cis-epoxycarotenoid dioxygenase) related to ABA was up-regulated in all genotypes under stress conditions and served as a reliable marker of drought stress. This work suggests that the stress response in metabolite synthesis and accumulation is complex, treatment- and genotype-dependent.

In the era of sustainable grapevine production, there is a growing demand to define differences between Vitis vinifera varieties in susceptibility to downy mildew. Croatia, as a country with a long tradition of grapevine cultivation, preserves a large number of native grapevine varieties. A leaf disc bioassay has been conducted on 25 of them to define their response to downy mildew, according to the International Organisation of Vine and Wine (OIV) descriptor 452-1, together with the stress response of the leaf discs using chlorophyll fluorescence and multispectral imaging with 11 parameters included. Time points of measurement were as follows: before treatment (T₀), one day post-inoculation (dpi) (T₁), two dpi (T₂), three dpi (T₃), four dpi (T₄), six dpi (T₅), and eight dpi (T₆). Visible changes in form of developed Plasmopara viticola (P. viticola) sporulation were evaluated on the seventh day upon inoculation. Results show that methods applied here distinguish varieties of different responses to downy mildew. Based on the results obtained, a phenotyping model in the absence of the pathogen is proposed, which is required to confirm by conducting more extensive research.