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Diffusive transport of small molecules within the internal structures ofbiological and synthetic material systems is complex because the crowdedenvironment presents chemical and physical barriers to mobility. We exploredthis mobility using a synthetic experimental system of small dye moleculesdiffusing within a polymer network at short time scales. We find that thediffusion of inert molecules is inhibited by the presence of the polymers.Counter-intuitively, small, hydrophobic molecules display smaller reduction inmobility and also able to diffuse faster through the system by leveragingcrowding specific parameters. We explained this phenomenon by developing a denovo model and using these results, we hypothesized that non-specifichydrophobic interactions between the molecules and polymer chains couldlocalize the molecules into compartments of overlapped and entangled chainswhere they experience microviscosity, rather than macroviscosity. We introduceda characteristic interaction time parameter to quantitatively explainexperimental results in the light of frictional effects and molecularinteractions. Our model is in good agreement with the experimental results andallowed us to classify molecules into two different mobility categories solelybased on interaction. By changing the surface group, polymer molecular weight,and by adding salt to the medium, we could further modulate the mobility andmean square displacements of interacting molecules. Our work has implicationsin understanding intracellular diffusive transport in microtubule networks andother systems with macromolecular crowding and could lead to transportenhancement in synthetic polymer systems.

Entanglement and weak interaction driven mobility of small molecules in polymer networks