INTRINSIC-VISCOSITY OF MODEL STARBURST DENDRIMERS

The hydrodynamic radii (R(eta)) calculated from intrinsic viscosities of poly(amido amide) (PAMAM) starburst dendrimers increase rapidly with increasing generation number. This would seem to support a structure with strongly stretched tiers, which is relatively hollow near the core, and with most end groups near the surface. However, a computer simulation due to Lescanec and Muthukumar supports a more folded structure with higher density near the core and with end groups dispersed throughout the molecule. Here we calculate the hydrodynamic radii of the Lescanec-Muthukumar model using intrinsic viscosity formulas developed by Zimm and Fixman. The Lescanec-Muthukumar starbursts with relatively stiff spacers have hydrodynamic radii in good agreement with the experimental PAMAM radii in spite of their folded structure. The hydrodynamic radius is sensitive both to the molecular size and to the density. As the number of generations increases, the molecules become more dense and the hydrodynamic radius increases more rapidly than the radius of gyration.