Molecular imprinting in network polymers under high pressure was studi
ed as a means of inducing selective binding sites for molecular recogn
ition. Network polymers of methacrylic acid and ethylene glycol dimeth
acrylate were prepared in the presence of a template, atrazine or amet
ryn, by free radical polymerization at either 1 or 1000 bar in three d
ifferent solvents. After washing, they were chromatographically evalua
ted for rebinding selectivity. In one case, a significantly stronger r
ebinding of the template to the polymer prepared at high pressure than
to the polymer prepared at normal pressure was observed. On an ametry
n-imprinted polymer prepared at 1 bar using 2-propanol as solvent, the
capacity factor for ametryn was 2.3, whereas on a polymer prepared at
1000 bar the capacity factor was 3.2. The capacity factors of atrazin
e on these materials were 1.2 and 1.4, respectively. With atrazine as
the template, no pressure effect was observed and the capacity factors
were, within the experimental error, the same on the high-pressure an
d the normal-pressure materials. The polymers were characterized by po
rosimetry, swelling measurements, IR, and SEM. These data showed that
the high-pressure polymers exhibited a more compact structure with low
er pore volume, higher density, and higher swelling compared to the po
lymers prepared at normal pressure. The origin of the pressure effect
on selectivity was discussed in terms of the monomer-template associat
ion tendency and in terms of polymer morphology.