Optical tracking of the heterogeneous solvent diffusion dynamics and swelling kinetics of single polymer microspheres

The diffusion dynamics of small molecules into polymer entities is crucial for driving their morphology and function, which can be applied to research fields such as optical identification, medical implantation and intelligent sensing platforms. Herein, we demonstrate a nondestructive bright-field imaging strategy to monitor and control the morphology of polymer microspheres by varying the interfacial interaction and diffusion in a penetrant bath. The nanoscale interface movement of single polymer microspheres was tracked and converted into the diameter variation during the swelling event with sub-pixel accuracy, which is consistent with the calculation using Li-Tanaka's kinetic equations. More interestingly, the solvent diffusion dynamics along different directions of one particle are heterogeneous, indicating the non-uniform internal structure of a soft confined assembly. The swelling characteristics of single polymer microspheres can be quantified by this simple imaging strategy, and the transient intermediate swelling states are captured. To model the lifetime and stabilization times of microplastic entities, solvent selectivity and thermodynamic regulation were introduced to obtain the activation energy down to the single micro-entity level. This optical methodology shows capability for decoding the complex diffusion mechanism in polymer entities and provides guidance for the design of drug delivery systems, sensor platforms, and optical responsive materials.