Influence of network defects on the conformational structure of nanogel particles: From "closed compact" to "open fractal" nanogel particles.

We propose an approach to generate a wide range of randomly branched polymeric structures to gain general insights into how polymer topology encodes a configurational structure in solution. Nanogel particles can take forms ranging from relatively symmetric sponge-like compact structures to relatively anisotropic open fractal structures observed in some nanogel clusters and in some self-associating polymers in solutions, such as aggrecan solutions under physiologically relevant conditions. We hypothesize that this broad "spectrum" of branched polymer structures derives from the degree of regularity of bonding in the network defining these structures. Accordingly, we systematically introduce bonding defects in an initially perfect network having a lattice structure in three and two topological dimensions corresponding to "sponge" and "sheet" structures, respectively. The introduction of bonding defects causes these "closed" and relatively compact nanogel particles to transform near a well-defined bond percolation threshold into "open" fractal objects with the inherent anisotropy of randomly branched polymers. Moreover, with increasing network decimation, the network structure of these polymers acquires other configurational properties similar to those of randomly branched polymers. In particular, the mass scaling of the radius of gyration and its eigenvalues, as well as hydrodynamic radius, intrinsic viscosity, and form factor for scattering, all undergo abrupt changes that accompany these topological transitions. Our findings support the idea that randomly branched polymers can be considered to be equivalent to perforated sheets from a "universality class" standpoint. We utilize our model to gain insight into scattering measurements made on aggrecan solutions.