Thermosetting supramolecular polymerization of compartmentalized DNA fibers with stereo sequence and length control

DNA nanostructures are highly addressable and compatible with biological systems but often require hundreds of unique strands for their assembly. On the other hand, nature can assemble complex structures from identical building blocks by compartmentalizing the process: assembling molecules into sub-components and bringing these together across multiple length scales. Inspired by this process, we report DNA-polymer conjugates that assemble through a unique heat-driven hierarchical mechanism to form fibers displaying blocks of different DNA sequences along their axis of polymerization. These one-dimensional “thermoset” DNA fibers retain the compartmentalization programmed in the pre-assembled segments. Length control over fiber segments is also achieved through gel purification of pre-assembled cylindrical micelles. Importantly, we show that the stereochemical sequence of the hydrophobic core can be amplified into distinctive morphological traits in the DNA fibers. Molecular dynamics simulations are used to model the structure and elucidate how stereochemical sequence manifests itself in different fiber-fiber interactions.