The self-diffusion coefficients have been determined for five generations of poly(propylene
imine) dendrimers in methanol at three different temperatures5, 25, and 45 °Cover the whole
concentration range. Pulsed field gradient spin echo NMR has been used. The Stokes−Einstein hard
sphere radii have been calculated in the zero concentration limit. They were equal, within error, to the
radii found from the viscosity. The high-generation dendrimers have three concentration regimes: a dilute,
a semidilute, and a concentrated regime. For the lower generations, only a dilute and a semidilute regime
can be found. In the dilute regime, the self-diffusion coefficient decreases as a function of the concentration.
In the semidilute regime, this decrease continues. In part of the semidilute and in the concentrated regime
diffusion was very slow, and we were not able to measure the long time self-diffusion coefficient. As the
transition from semidilute to concentrated solutions corresponds to a decrease of the radius of the
dendrimer, dendrimers in concentrated solutions can be considered as collapsed though still separate
molecules. The behavior in the semidilute and the concentrated regimes is very different from polymer
diffusion.