Cranberry proanthocyanidins associate with low-density lipoprotein and inhibit in vitro Cu2+-induced oxidation

Antioxidant activity of six fractions of cranberry phenolic compounds was determined by inhibition of Cu2+‐induced low‐density lipoprotein (LDL) oxidation. The phenolic composition of each fraction was determined by high‐performance liquid chromatography. The phenolic fractions were mixed with aliquots of modified human serum prior to LDL isolation. The serum was modified to remove very‐low‐density lipoprotein and chylomicrons that may bind phenolic compounds. Only fractions 5 and 6 that contained proanthocyanidins (PAs) significantly increased the lag time of LDL oxidation, and the lag time for fraction 6 was significantly higher than for fraction 5. The mass distribution of PAs in these fractions was obtained by matrix‐assisted laser desorption/ionisation time‐of‐flight mass spectrometry, a technique that allows rapid characterisation of the molecular weight distribution in mixtures of oligomeric compounds. Fraction 5 contained trimers through heptamers, whereas fraction 6 contained pentamers through nonamers. In addition, fraction 6 contained PA oligomers with more doubly linked, A‐type interflavan bonds. Results indicate that PAs specifically associate with LDL in modified serum and increase the lag time of Cu2+‐induced oxidation. Differences between fractions 5 and 6 in PA structure and effects on LDL oxidation suggest that the degree of polymerisation and the nature of the interflavan bond influence antioxidant properties. © 2001 Society of Chemical Industry