Single-Particle Tracking in Poly(Ethylene Glycol) Diacrylate: Probe Size Effect on the Diffusion Behaviors of Nanoparticles in Unentangled Polymer Solutions.

A thorough understanding of the relevant factors governing the transport of nanoparticles in poly(ethylene glycol) diacrylate (PEGDA) is crucial for many applications utilizing this polymer. Here, single-particle tracking (SPT) was used to systematically investigate the role of the probe size (3-200 nm) on the diffusion behaviors of individual fluorescent nanoparticles in semidilute and unentangled PEGDA solutions. The quantitative assessment of the SPT data via the recorded single-particle trajectories and diffusion coefficients () not only showed that the observed probe dynamics in PEGDA were temporally and spatially heterogeneous, but more importantly that the measured were observed to be significantly reduced (vs in solvent) and strongly size-dependent. We explained these results based on a modified multiscale model for particle diffusion, built upon well-established hydrodynamics and obstruction theories. We furthermore showed that the presence of steric interactions and probe confinement effects in highly crowded, unentangled PEGDA microstructures can lead to deviations in the single-particle displacements from the expected Gaussian behavior, as revealed by the van Hove displacement distributions and the associated non-Gaussian parameters. This study has demonstrated the power of SPT methods in offering an advanced characterization of the transport characteristics in complex polymer structures, overcoming challenges posed by traditional characterization techniques.