Controlling
the biotechnical properties
of synthetic hydrogels allows their application in a wide range of
biomedical fields. Cross-linker concentration and monomer mole ratio
of poly(2-hydroxyethylmethacrylate-co-N-(2-hydroxypropyl) methacrylamide) [poly(HEMA-co-HPMA)]-based hydrogels were used to control the degree of hydration
and water distribution within constructs. Cross-linker concentrations
corresponding to 0.1, 0.5, 1.0, and 3.0 mol % tetraethylene glycol
(TEGDA) with HEMA/HPMA mole ratios of 1:0 and 4:1, and poly(HEMA-co-HPMA) of cross-linker concentration corresponding to
1.0 mol % TEGDA with a HEMA/HPMA ratio of 1:1 were investigated for
their degree of hydration, water distribution, and corresponding physiochemical
and mechanical properties. Copolymerization of HEMA and HPMA was confirmed
by Fourier-transform infrared spectroscopy. Both cross-linker concentration
and chemical composition (HEMA/HPMA) systematically changed the water
content and free/bound water distribution in the polymer, which resulted
in different biochemical and transport properties. The addition of
20% HPMA (poly(HEMA-co-HPMA) (4:1)) increased total
hydration (25%) and glass-transition temperature (9%) and decreased
elastic modulus (31%) and nonfreezable bound water (33%) of the hydrogel.
Increasing cross-linker concentration resulted in a stiffer hydrogel
with less total water but larger nonfreezable water content. Evaluation
of poly(HEMA-co-HPMA) (1:1) revealed that further
increase of HPMA content increased the degree of hydration by 25%
and decreased nonfreezable water content and elastic modulus by 33
and 16%, respectively, compared to that of poly(HEMA-co-HPMA) (4:1). The hydrogel correspondingly had a higher void fraction
and rougher freeze-fractured surface. The diffusion-related processes
depended more on water distribution within the hydrogel. The poly(HEMA)
showed the fastest swelling kinetics with a concomitant burst release
profile of fluorescein isothiocyanate–dextran (a drug surrogate),
while the compositions containing HPMA showed a sustained release
pattern. The biotechnical properties are illustrative examples of
key properties that are influenced by the water distribution rather
than the absolute water content of hydrogels.