Reversible Reactions, Mesh Size, and Segmental Dynamics Control Penetrant Diffusion in Ethylene Vitrimers.

The diffusion of two aromatic dyes with nearly identical sizes was measured in ethylene vitrimers with precise linker lengths and borate ester cross-links using fluorescence recovery after photobleaching (FRAP). One dye possessed a reactive hydroxyl group, while the second was inert. The reaction of the hydroxyl group with the network is slow relative to the hopping times of the dye, resulting in a large slowdown by a factor of 50 for a reactive probe molecule.

How Segmental Dynamics and Mesh Confinement Determine the Selective Diffusivity of Molecules in Cross-Linked Dense Polymer Networks.

The diffusion of molecules ("penetrants") of variable size, shape, and chemistry through dense cross-linked polymer networks is a fundamental scientific problem broadly relevant in materials, polymer, physical, and biological chemistry. Relevant applications include separation membranes, barrier materials, drug delivery, and nanofiltration. A major open question is the relationship between transport, thermodynamic state, and penetrant and polymer chemical structure.

Elucidation of the physical factors that control activated transport of penetrants in chemically complex glass-forming liquids.

Understanding the activated transport of penetrant or tracer atoms and molecules in condensed phases is a challenging problem in chemistry, materials science, physics, and biophysics. Many angstrom- and nanometer-scale features enter due to the highly variable shape, size, interaction, and conformational flexibility of the penetrant and matrix species, leading to a dramatic diversity of penetrant dynamics. Based on a minimalist model of a spherical penetrant in equilibrated dense matrices of hard spheres, a recent microscopic theory that relates hopping transport to local structure has predicted a novel correlation between penetrant diffusivity and the matrix thermodynamic dimensionless compressibility, () (which also quantifies the amplitude of long wavelength density fluctuations), as a consequence of a fundamental statistical mechanical relationship between structure and thermodynamics.