Proanthocyanidins in grapes

Nakamura, Y., Tsuji, S., and Tonogai, Y, Analysis of proanthocyanidins in grape seed extracts, health foods and grape seed oils, J. Health Set, 49, 45, 2003. 

Hayasaka, Y. and Asenstorfer, R.E., Screening for potential pigments derived from anthocyanins in red wine using nanoelectrospray tandem mass spectrometry. J. Agric. Food Chem. 50, 756, 2002. Hayasaka, Y. et al., Characterization of proanthocyanidins in grape seeds using electrospray mass spectrometry. Rapid Commun. Mass Spectrom. 17, 9, 2003. 

Figure 3.6 ESI mass spectra of PAs with DP (a) 3 and (b) 9 obtained by signal accumulation of 20 consecutive scans, m/z values major singly charged ions of PAs. Doubly charged ions of PAs monogallates. Analytical conditions ESI needle, orifice and ring potentials —4500, —60 and —350 V, respectively curtain gas N2, nebulizer gas air. (Reprinted from Rapid Communications in Mass Spectrometry 17, Hayasaka et al., Characterization of proanthocyanidins in grape seeds using electrospray mass spectrometry, p. 11, Copyright 2003, with permission from John Wiley Sons Ltd)...

Controlled acid-catalyzed degradation of the proanthocyanidins in grape seeds with L-cysteine as the capture nucleophile, gave a series of mono-, di-, and tri-meric-L-cysteine complexes. The flavan-3-ol adducts included the L-cysteine derivatives (173), (174), and (175) of epicatechin (3), catechin (2), and epigallocatechin, respectively. The dimers comprise the derivatives of procyanidin B-2 (176) and its C-ring... 

Fig. 3.2 Extraction efficiencies of grape seed proanthocyanidins in different solvents. Vertical bars represent standard deviation (adapted with permission from [23])...

Vidal SFL, Francis L, Guyot S et al (2003) The mouth-feel properties of grape and apple proanthocyanidins in a wine-hke medium. 1 Sci Food Agric 83 564-573... 

As discussed above, the development of mild MS techniques has led to further progress in the determination of proanthocyanidin size distribution. In particular, ESI-MS studies have demonstrated that prodelphinidin and procyanidin units coexist within the polymers, where they seem distributed at random. A list of mass signals attributed to proanthocyanidins detected in grape or wine extracts is given in Table 5.2. 

Proanthocyanidin Signals Detected in Grape and Wine Extracts by ESI-MS in the Negative Ion Mode... 

Ward, N.C., Croft, K.D., Puddey, I.B., and Hodgson, J.M., Supplementation with grape seed polyphenols results in increased urinary excretion of 3-hydroxyphenylpropionic acid, an important metabolite of proanthocyanidins in humans, J. Agric. Food Chem., 52, 5545, 2004. 

Sano, A., Yamakoshi, J., Tokutake, S., Tobe, K., Kubota, Y., and Kikuchi, M., Procyanidin B1 is detected in human serum after intake of proanthocyanidin-rich grape seed extract, Biosci. Biotechnol. Biochem., 67, 1140, 2003. 

Vidal, S., Francis, L., Guyot, S., Marnet, N., Kwiatkowski, M., Gawel, R., Chejmier, V., and Waters, E. J. (2003). The mouth-feel properties of grape and apple proanthocyanidins in a wine-like medium. /. Sci. Food Agric. 83, 564-573. 

The antiatherosclerotic effect of proanthocyanidin-rich grape seed extracts was examined in cholesterol-fed rabbits. The proanthocyanidin-rich extracts [0.1% and 1% in diets (w/w)] did not change the serum lipid profile, but reduced the level of the cholesteryl ester hydroperoxides (ChE-OOH) induced by 2,2/-azo-bis(2-amidinopropane-dihydrochloride (AAPH), the aortic malonaldehyde (MDA) content and severe atherosclerosis. The immuno-histochemical analysis revealed a decrease in the number of the oxidized LDL-positive macrophage-derived foam cells on the atherosclerotic lesions of the aorta in the rabbits fed the proanthocyanidin-rich extract. When the proanthocyanidin-rich extract was administered orally to the rats, proantho-cyanidin was detected in the plasma. In an in vitro experiment using human plasma, the addition of the proanthocyanidin-rich extract to the plasma inhibited the oxidation of cholesteryl linoleate in the LDL, but not in the LDL isolated after the plasma and the extract were incubated in advance. From these results, proanthocyanidins of the major polyphenols in red wine might trap ROSs in the plasma and interstitial fluid of the arterial wall, and consequently display antiatherosclerotic activity by inhibiting the oxidation of the LDL [92]. 

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