High-resolution cryo-electron microscopy structure of block copolymer nanofibres with a crystalline core

Seeded growth of crystallizable block copolymers and π-stacking molecular amphiphiles in solution using living crystallization-driven self-assembly is an emerging route to fabricate uniform one-dimensional and two-dimensional core–shell micellar nanoparticles of controlled size with a range of potential applications. Although experimental evidence indicates that the crystalline core of these nanomaterials is highly ordered, a direct observation of their crystal lattice has not been successful. Here we report the high-resolution cryo-transmission electron microscopy studies of vitrified solutions of nanofibres made from a crystalline core of poly(ferrocenyldimethylsilane) (PFS) and a corona of polysiloxane grafted with 4-vinylpyridine groups. These studies show that poly(ferrocenyldimethylsilane) chains pack in an 8-nm-diameter core lattice with two-dimensional pseudo-hexagonal symmetry that is coated by a 27 nm 4-vinylpyridine corona with a 3.5 nm distance between each 4-vinylpyridine strand. We combine this structural information with a molecular modelling analysis to propose a detailed molecular model for solvated poly(ferrocenyldimethylsilane)-b-4-vinylpyridine nanofibres. Detailed structures of both solvated corona chains and sub-nanometre crystalline core lattice of polymer-based nanofibres in solution are obtained using high-resolution cryo-electron microscopy.