The interaction between wine polyphenolic classes and poly-L-proline is impacted by oxygen

Abstract

Oxygen plays a key role in the evolution of wine chemistry, within the non-volatile matrix. Polyphenol composition and structure, as well as the process of tannin polymerisation are directly impacted by oxidation, and this can occur during both fermentation and ageing. Polyphenols play an important role in red wine and exhibit a wide diversity in their structure and properties. They are responsible for wine colour, texture and taste (astringency, bitterness) and exhibit some health properties. The principal class of non-flavonoid polyphenolic compounds are the phenolic acids and stilbenes. Among the flavonoids, anthocyanins and tannins are the major structural classes. The aim of this study was to characterise the detailed response of wine polyphenolic structure and composition to an oxygen treatment applied during fermentation. A specific focus was to determine the interaction of discrete polyphenolic classes with poly-L-proline (PLP). A control Shiraz wine was prepared under reductive conditions during fermentation, in triplicate. To the same grape source, an aeration treatment was initiated on day 3 following a 1.8 °Bé decrease for 48 h at 5 L/min, also in triplicate.  After a 12-month ageing period, wines were fractionated where: F1 = Phenolic acids, F2 = flavan-3-ol monomers, F3 = flavan-3-ol oligomers, F4 = anthocyanins, pyranoanthocyanins; and F5 = polymeric proanthocyanidins, pigmented proanthocyanins and other derived complexes. The composition of fractions F1 to F4 was verified by LC-MS, and F5 was characterised by a combination of analytical techniques specific to proanthocyanidins. The interaction between the polyphenol fractions and PLP was measured by isothermal titration calorimetry (ITC). A strong binding interaction was observed between F1, the phenolic acids, and PLP by ITC, and was not affected by the oxygen treatment. In fact, a strong hydrophobic interaction and hydrogen bonding was implicated in the interaction. It was found that for fractions F2 and F3, no binding events with PLP were observed by ITC, irrespective of the oxygen level applied. Stronger binding events with PLP were observed for the F4 and F5 polyphenolic fractions, but interestingly, only in those prepared from wines which had oxygen treatment. Moreover, hydrophobic interaction and hydrogen bonding was detected just for the oxygen treatment for F4 and F5. Contrary to expectation, no binding with PLP could be detected for F4 and F5 from the control wine. Further investigation of the properties of the fractions was conducted to account for the differences observed, including their composition, hydrophobicity and aggregation. This presentation will provide new insights into the potential role of discrete polyphenolic classes in driving in-mouth sensory properties, like astringency, which might be elicited following binding with proline-rich salivary proteins.