Proteoglycans (PGs) from bovine cornea showed a protective effect on l
iposome peroxidation induced by Fe2+. Both chondroitin sulfate, dermat
an sulfate-containing PG (CS,DS-PG) and keratan sulfate-containing PG
(KS-PG) inhibited thiobarbituric acid-reactive substance formation whe
n incubated with liposomes and Fe2+, CS,DS-PG being more effective tha
n KS-PG. The native structure of PGs contributed markedly to antioxida
nt activity. Papain digestion of core protein reduced the protective e
ffect of CS,DS-PG, whereas it abolished completely that of KS-PG. Appa
rently, only hexuronate-containing glycosaminoglycan (GAG) chains may
exert a significant antioxidant activity and this was confirmed using
standard GAGs. Quasielastic laser light scattering was used to evaluat
e the structural consequence of peroxidative damage induced by Fenton
reagent on liposomes. After exposure to the free-radical-generating sy
stem, a bimodal distribution of liposomes was observed, probably depen
ding on the loss of native structure and fragmentation. Both CS,DS-PG
and KS-PG prevented liposome breakdown. Again, free KS chains were ine
ffective against liposome damage, whereas DS and CS maintained the nor
mal distribution of liposome size, These data support the hypothesis t
hat PGs may represent part of the antioxidant mechanisms of organisms
and suggest that modifications of PG content and/or composition might
affect tissue sensitivity to oxidative stress. (C) 1996 Academic Press
, Inc.