N. Kato et al., Saccharide effect on the deswelling process of the thermosensitive poly(N-isopropylacrylamide) gel, B CHEM S J, 74(11), 2001, pp. 2025-2029
The kinetic parameters of deswelling and the change of a lower critical sol
ution temperature (LCST) for poly(N-isopropylacrylamide) get, poly(NIPAAm)
gel, were investigated in the presence of glucose and other sugars as hydro
philic probes. The enthalpy of activation (DeltaH(double dagger)) and the e
ntropy of activation (AS) for deswelling were influenced by the concentrati
on of additive sugars. Plots of DeltaH(double dagger) against T DeltaS(doub
le dagger) fell on a straight line, of which the slope was approximately 0.
91-0.94. This result shows a compensation effect of the free energy of acti
vation (AG) concerning the relationship between Al-P and AS' for deswelling
of poly(NIPAAm) gel. The molecular interaction between sugar and water clu
sters involved with the polymer is responsible for the compensation effect
between DeltaH(double dagger) and DeltaS(double dagger). The equatorial hyd
roxy groups of sugar molecules interact easily with water clusters around t
he hydrophobic isopropyl groups (the iceberg) to form hydrogen bonds, which
give rise to change the situation of polymer hydration. A decrease of the
LCST has close connections with the number of equatorial hydroxy groups of
sugars as additives. The LCST decrease in sugar solutions was regarded as t
he situation change of polymer hydration in the iceberg.