Hierarchical Assembly of Inhomogeneous Supramolecular Polymers from Hybrid Particle-Field Simulations

Through hierarchical assembly at multi-scales, inhomogeneous supramolecular polymers (ISP) serve as self-assembly foundries for fabricating materials that can perform multiple functions through combinations of structural and functional capabilities. Understanding the mechanisms governing hierarchical assembly of ISP plays a key role in unlocking such potential. Using a “bare-bones” case of ISP, this study applies hybrid particle-field simulations to elucidate interplay of chemical and thermodynamic equilibrium, reaction kinetics and polymer dynamics in the system. Extent of reaction, effective bonding kinetics, and segmental diffusions measured in ordered micro-phase, homogeneous phase, and in a reference system of “dead” polymers are compared to illustrate couplings of different mechanisms. It is found that compositional ordering reduces reaction conversion, increases effective associative bond life, and slows down polymer diffusion compared to the homogenous phase. Reversible associative reactions greatly enhanced mobility of the ordered micro-phase as compared to the “dead” system. Associative segments exhibit faster-than-Rouse diffusion behaviors, and a distinct diffusion mechanism in the ordered phase. Future studies on more complicated IPS systems will also be discussed.