Curdlan, a bacterial polysaccharide, can form different types of thermogels, having the very same chemical composition, but whose structures depend on the incubation temperature. Structural characterization of 10% (w/v) low-set and high-set curdlan gels was carried out by Fourier transformed infrared (FT-IR) imaging and environmental scanning electron microscopy (eSEM) in the hydrated state. Considerable differences were observed between the two gels, the high-set one being overall more homogeneous. The self-diffusion coefficients of a series of analytes of different sizes (water, phosphate, glucose-6-phosphate, polyphosphate, polyethylene glycol, and dextran labelled with rhodamine B) were measured in aqueous solution (D-s(s/n)) and in both types of curdlan gels (D-s(gel)) using H-1 and P-31 pulsed field gradient nuclear magnetic resonance (PFG NMR) spectroscopy. The mutual-diffusion coefficients (D-m(gel)) of dextran in the curdlan gels were determined from release experiments based on fluorescence spectroscopy. The dependence of the relative diffusion coefficient (D-s(gel) / D-s(s/n)) on the size of the analyte, expressed by its hydrodynamic radius (R-h), could be expressed by D-s(gel) / D-s(s/n) proportional to exp(-R-h(0.46)), valid for both types of gels. The self-diffusion measurements for the largest investigated analytes were not compatible with a single diffusion coefficient and, therefore, were analysed using an approach based on a normal distribution of self-diffusion coefficients. In the hydrogels, broadening of the self-diffusion coefficient distribution increased as a function of the analyte size. This phenomenon was associated with the limited distance travelled by the analytes during the measurements, and it is inferred that the distribution of diffusion coefficients is representative of the distribution of local environments of the individual analyte. It was found that the structural differences observed between both types of curdlan gels are not correlated with the gel transport properties, highlighting the complexity of the relationship between structural details and transport properties in gels. (C) 2011 Elsevier Inc. All rights reserved.