The relationships between variations in grapevine (Vitis vinifera L. cv. Merlot) fruit zone light exposure and water deficits and the resulting berry flavonoid composition were investigated in a hot climate. The experimental design involved application of mechanical leaf removal (control, pre-bloom, post-fruit set) and differing water deficits (sustained deficit irrigation and regulated deficit irrigation). Flavonol and anthocyanin concentrations were measured by C18 reversed-phased HPLC and increased with pre-bloom leaf removal in 2013, but with post-fruit set leaf removal in 2014. Proanthocyanidin isolates were characterized by acid catalysis in the presence of excess phloroglucinol followed by reversed-phase HPLC. Post-fruit set leaf removal increased total proanthocyanidin concentration in both years, whereas no effect was observed with applied water amounts. Mean degree of polymerization of skin proanthocyanidins increased with post-fruit set leaf removal compared to pre-bloom, whereas water deficit had no effect. Conversion yield was greater with post-fruit set leaf removal. Seed proanthocyanidin concentration was rarely affected by applied treatments. The application of post-fruit set leaf removal, regardless of water deficit. increased the proportion of proanthocyanidins derived from the skin, whereas no leaf removal or pre-bloom leaf removal regardless of water deficit increased the proportion of seed-derived proanthocyanidins. The study provides fundamental information to viticulturists and winemakers on how to manage red wine grape low molecular weight phenolics and polymeric proanthocyanidin composition in a hot climate.

The correlation between tannin structure and corresponding activity was investigated by measuring the thermodynamics of interaction between tannins isolated from commercial red wine fermentations and a polystyrene divinylbenzene HPLC column. Must and/or wine samples were collected throughout fermentation/maceration from five Napa Valley wineries. By varying winery, fruit source, maceration time, and cap management practice, it was considered that a reasonably large variation in commercially relevant tannin structure would result. Tannins were isolated from samples collected using low pressure chromatography and were then characterized by gel permeation chromatography and acid-catalyzed cleavage in the presence of excess phloroglucinol (phloroglucinolysis). Corresponding tannin activity was determined using HPLC by measuring the thermodynamics of interaction between isolated tannin and a polystyrene divinylbenzene HPLC column. This measurement approach was designed to determine the ability of tannins to hydrophobically interact with a hydrophobic surface. The results of this study indicate that tannin activity is primarily driven by molecular size. Compositionally, tannin activity was positively associated with seed tannins and negatively associated with skin and pigmented tannins. Although measured indirectly, the extent of tannin oxidation as determined by phloroglucinolysis conversion yield suggests that tannin oxidation at this stage of production reduces tannin activity. Based upon maceration time, this study indicates that observed increases in perceived astringency quality, if related to tannin chemistry, are driven by tannin molecular mass as opposed to pigmented tannin formation or oxidation. Overall, the results of this study give new insight into tannin structure-activity relationships which dominate during extraction.