Block Copolymer Self‐assembly: Exploitation of Hydrogen Bonding for Nanoparticle Morphology Control via Incorporation of Triazine Based Comonomers by RAFT Polymerization

Synthesis of polymeric nanoparticles of controlled non‐spherical morphology is of profound interest for a wide variety of potential applications. Self‐assembly of amphiphilic diblock copolymers is an attractive bottom‐up approach to prepare such nanoparticles. In the present work, RAFT polymerization is employed to synthesize a variety of poly(N,N‐dimethylacrylamide)‐b‐poly[butyl acrylate‐stat‐GCB] copolymers, where GCB represents vinyl monomer containing triazine based Janus guanine‐cytosine nucleobase motifs featuring multiple hydrogen bonding arrays. Hydrogen bonding between the hydrophobic blocks exert significant influence on the morphology of the resulting nanoparticles self‐assembled in water. The Janus feature of the GCB moieties makes it possible to use a single polymer type in self‐assembly, unlike previous work exploiting, e.g., thymine‐containing polymer and adenine‐containing polymer. Moreover, the strength of the hydrogen bonding interactions enables use of a low molar fraction of GCB units, thereby rendering it possible to use the present approach for copolymers based on common vinyl monomers for the development of advanced nanomaterials. The use of hydrogen bonding is explored for the purpose of directing self‐assembly of amphiphilic diblock copolymers. The supramolecular assembly is primarily dominated by highly directional hydrogen bonds generated by the triazine based Guanine Cytosine nucleobase and thereby, it expands the potential for this Janus motif to control the morphology of functional nanoparticles for prospective applications.