G. Sartor et Gp. Johari, POLYMERIZATION OF A VEGETABLE PROTEIN, WHEAT GLUTEN, AND THE GLASS-SOFTENING TRANSITION OF ITS DRY AND REACTED STATE, Journal of physical chemistry, 100(50), 1996, pp. 19692-19701
The heat evolved as a result of irreversible chemical changes that occ
ur on heating 2, 5.6, 15, 25, and 50 wt % water containing wheat glute
n has been measured by differential scanning calorimetry. Further, the
effects of the removal of water vapors on evaporation of the gluten's
moisture on its polymerization have been investigated. The amount of
moisture removed during heating and the heat of the reaction were meas
ured and correlated with the extent of reaction. When the moisture and
gases produced on heating gluten were prevented from escaping partial
ly, the total heat evolved decreased, and the reaction exotherm shifte
d to a higher temperature. These observations have been interpreted in
terms of a chemical equilibrium that is attained within the short dur
ation allowed by the heating rate. By varying the amount of water and
the time allowed for its diffusion at both ambient temperature and 253
K, it is shown that the thermal effects observed are a consequence of
two processes: the vaporization of water, which is endothermic, and t
he condensation reaction, which is exothermic. The kinetics of this re
action depends upon the amount of water present, which plasticizes the
proteins. Increase in the molecular mobility due to the presence of w
ater thus allows further bond formation by chemical reactions, but aft
er the bond has formed, the mobility decreases and some of the water e
scapes by vaporization because of the exothermic nature of the reactio
ns, thus preventing further reaction. This negative feedback between t
he physical process of plasticization by water and the chemical proces
s of polymerization thus prevents the reaction from reaching completio
n. The ultimately formed dry wheat gluten undergoes a glass-softening
transition at 436 +/- 2 K. The shape of this endotherm, and so the imp
licit molecular dynamics, depend upon the thermal treatment conditions
of the gluten, but not its T-g onset. It has a broader distribution a
fter reacting in excess water kept at 373 K than when it was degraded
and charred by heating to 523 K. This distribution of relaxation times
and other characteristics of its heat capacity relaxation are similar
to those of synthetic polymers. Wheat gluten seems to be the only mat
erial for which a T-g endotherm becomes observable in an experiment do
ne to measure the reaction kinetics.