The understanding of mechanisms involved in the controlled release of active molecules
from the polymer matrix requires the study of hydration phenomenon. Fluorescence and attenuated total
reflection Fourier transform infrared (ATR−FTIR) spectroscopies were used to analyze the earlier steps
of hydration in acrylic copolymers. The effect of hydration on the anisotropy of the PRODAN fluorescent
probe showed a change in the dynamics of the macromolecular chains. By using ATR−FTIR spectroscopy,
the structure of dissolved water in polymers was studied. The evolution of this structure was performed
as hydration proceeds by band decomposition of the νOH vibration on the basis of the four-state model
which allows discriminating bound from free molecules: in the “early” stages of hydration, the water
network appears drastically perturbed as compared to that of bulk pure water, this perturbation vanishing
in the “later” stages of hydration. Besides, this study reveals that the polymer carbonyl groups constitutes
the major water binding sites as it was deduced from their progressive engagement in H bonds in the
time course of hydration. The rate and extent of this process was observed to be correlated with the
hydrophobicity of polymers. The present findings, obtained on similar time scales from noninvasive
techniques, indicate that both dynamic and structural consequences of hydration are correlated in most
of the polymers here studied.