Hydrogels were created by electron beam irradiation of aqueous solutio
ns of poly(ethylene oxide) (PEO) having a nominal molecular weight of
35000. The molecular weight between cross-links M(c) varied from 3000
to 15000, and the equilibrium volume fractions of polymer v2,s from 0.
01 to 0.08. These hydrogels were exposed to aqueous solutions of solut
es: tricyclic antidepressants, cyanocobalamin, four globular proteins
and three linear species of PEO. Partition coefficients and diffusion
coefficients were determined. For each solute the ratio diffusion coef
ficient in hydrogel/diffusion coefficient in free solution was determi
ned, and related to the hydrogel parameters M(c) and v2,s and to the s
olute effective radius r(E) (Einstein radius). The diffusion coefficie
nt ratio is greater for the flexible random coiling PEO than for the '
rigid' solutes at a given set of M(c), v2s and r(E), and the disparity
increases rapidly as r(E) increases. Among the globular proteins the
diffusion coefficient ratio decreases by orders of magnitude with smal
l changes in r(E) (20.6-27.6 angstrom) and was found to be nearly zero
for albumin (r(E) = 36.1 angstrom). The tricyclic antidepressants had
partition coefficients of around 2, whereas the other solutes had par
tition coefficients of about unity. By reason of the partition coeffic
ient of around 2, the diffusion coefficient ratio of a tricyclic antid
epressant having a value of r(E) = 5.5 angstrom is half that of the la
rger cyanocobalamin, for which r(E) = 8.5 angstrom.