The accepted mechanism of alginate gelation at ambient temperature is
by formation of egg-box junctions between pairs of polyguluronate chai
n sequences and an included array of site-bound calcium ions. We now p
resent evidence (circular dichroism and low-amplitude mechanical spect
roscopy data) of similar regular interactions at high temperatures whe
re all the active ingredients (alginate, salt and sequestrant) are hyd
rated in a hot medium. During controlled cooling, a second transition
is obtained at low temperatures, which may be attributed to the latera
l interaction of dimeric chains and thus the development of an extende
d, three-dimensional network. A subsequent temperature increase melts
the second wave of structure formation, thus producing substantial the
rmal hysteresis, but preserves the 'weak gel' properties of the algina
te-calcium reaction observed at elevated temperatures. At levels of sa
lt higher than 40% calcium conversion aggregation can occur even at 90
degrees C, leading to precipitation rather than a homogenous network.
Prolonged refrigeration (72 h at 4-5 degrees C) sustains a gradual mo
lecular rearrangement to a self-supporting (visual evidence), firmer (
frequency sweeps) network. Surprisingly, the strongest high guluronate
alginate is not only more elastic than its low molecular weight count
erpart (strain sweeps in dynamic oscillation) but it also exhibits hig
her yield strain on compression testing than the high molecular weight
, high mannuronate sample. The distinct differences in the long-range
properties of high guluronate and high mannuronate alginate samples wi
th comparable molecular weights might serve as a guide for the develop
ment of reformed products with the desired characteristics.