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The distribution of proanthocyanidin (PA) polymer lengths, proanthocyanidin concentration at each polymer length, and polymer composition were determined in the seed, skin, and wine of Shiraz and Cabernet Sauvignon grape berries grown in southeast Australia. PA was fractionated by semipreparative high performance liquid chromatography (HPLC) and analyzed by phloroglucinolysis and HPLC to report the degree of polymerization (DP), concentration, and composition at 11 DP values in seed and wine and 21 DP values in skin. In skin, the highest PA concentration was observed at a DP of 31 in Shiraz and 29 in Cabernet Sauvignon representing 15% of the total PA in both varieties. The distribution of seed PA had the highest concentration at a DP of 7 in Shiraz and 6 in Cabernet Sauvignon representing around 30% of the total PA. In the wine PA distribution, the highest concentration was observed at a DP of 11 in Shiraz and 9 in Cabernet Sauvignon representing around 26 and 32% of the distribution, respectively. A second peak in wine PA concentration was observed at the largest DP of 18 in Shiraz and 15 in Cabernet Sauvignon representing around 20% of the distribution. The composition in wine did not vary at different DP, but the proportion of epicatechin gallate varied in seed PA less than 4 DP. The proportion of epigallocatechin increased with increasing DP in skin PA. Wine PA had a DP range and composition similar to the distribution of skin PA between DP 4 and 18 suggesting that larger skin PAs are not extracted into wine. This study provides information that could be used to target the important PA fractions in grapes that need to be measured to understand (or predict) PA extraction into wine and eventual mouthfeel.

Discrepancies in condensed tannin concentrations in grape skin determined by different analytical methods prompted the closer examination of aspects of the methodologies. One of these was the choice of extraction solvent. Condensed tannins were extracted from Shiraz grape skins using a range of aqueous solvent mixtures ranging from zero to 100% acetone and ethanol to examine the relative effectiveness of each solvent mixture and to determine whether different solvent mixtures extracted similar condensed tannin components. Acetone extracted more condensed tannin than ethanol. Mixtures of 50 to 70% acetone were equally effective. The most effective ethanol concentration was 50%. Epicatechin-gallate terminal subunits were not detected by HPLC following acid-catalysed cleavage in any of the extraction solvents. Extension subunit composition was similar between solvents across most mixtures. Polymers were generally shorter in the ethanol extracts than in the acetone extracts. Despite differences in tannin concentration and polymer length, the subunit composition was similar in 50% ethanol and 70% acetone. More tannin and tannins with longer polymer lengths were extracted with 70% acetone than with 50% ethanol. This suggests that all grape skin tannins are similar in composition, varying only in length. Thus, 50% ethanol and 70% acetone would give a fair indication of the grape skin tannin composition extracted into wine. However, both 50% ethanol and 70% acetone may overestimate the amount of tannin that is extracted into wine, as wine typically has a much lower solvent concentration, ranging between 10 and 15% ethanol.

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