Architecture-driven surface conformations of backbone dictate folded morphology in bottlebrush amphiphiles

Bottlebrush amphiphiles have greatly expanded access to diverse nanocarriers useful for applications like drug delivery. A challenge concerning them is how architectural parameters precisely translate to the resultant folded or self-assembled nanostructures. Here, we computationally study single-chain heterograft bottlebrush amphiphiles using molecular dynamics. We explore the impact of monomer size, geometry, chain lengths and pi-stacking interactions on the morphological space of the folded structures. Simulations reveal a compartmental tug-of-war: that of the excluded volume of the core and the connectivity-limited coronal side chains. This block asymmetry drives a surface-constrained wrapping of the backbone. We pair this focal insight with scaling theory of polymers in confinement and attempt to delineate observed morphological transitions. Our study highlights the role of backbone connectivity as a key modulator in nanoscale building block design from bottlebrushes.