The desulfation of galactans was shown to be acid catalysed, and most
likely to proceed through an intermediate complex in which SO3 is tran
sferred to an acceptor molecule. The reaction is inhibited by molecule
s such as methanol and water, frequently included as 'catalysts'. The
reaction for l-carrageenan appears to be stepwise, to be dependent on
the nature of the acid and the sulfate acceptor, and is essentially in
dependent of the initial counterion, unless these are the actual reage
nts. A useful preparative procedure is to dissolve the oven-dried sodi
um salt of the polysaccharide in anhydrous dimethyl sulfoxide and reac
t it at about 120 degrees C for approximately three hours in the prese
nce of a pyridinium salt of pyromellitic acid, excess pyridine, and an
amphoteric nonhydrogen-bonding sulfate acceptor, of which arsenous ox
ide and antimony trioxide are preferable for removing all forms of sul
fate ester in good yield. The procedure appears to work satisfactorily
for each of the types of sulfate ester present in algal galactans, wi
thout significant degradation occurring of the underlying polysacchari
de skeletons. (C) 1998 Elsevier Science Ltd. All rights reserved.