Self-Assembled Nanostructures from Amphiphilic Block Copolymers Prepared via Ring-Opening Metathesis Polymerization (ROMP)

The development of controlled/living polymerization methodologies has underpinned a rapid expanse in our understanding of amphiphilic block copolymer self-assembly. In solution, amphiphilic block copolymers spontaneously organize to form a diverse set of nano-objects, such as spherical and worm-like micelles or vesicles, that have proven to be exceptionally useful in the fields of nanomedicine, sensing, and catalysis, amongst others. The properties of such polymeric assemblies are strongly dependent on the chemical structure of their constituent block copolymer amphiphiles and, by extension, the methodology employed in their synthesis. In the past, research in this area has centered on the use of radical or anionic polymerization strategies to prepare amphiphilic block copolymers. However, continued efforts in the development of living ring-opening metathesis polymerization (ROMP) have facilitated access to new families of block copolymers, primarily based on the polynorbornene scaffold, that provide specific advantages over more traditional block copolymers comprised of (meth)acrylic or styrenic components. This review article provides a comprehensive summary of the synthesis of amphiphilic block copolymers by ROMP and the methods utilized for their self-assembly into ordered nanostructures in solution. In addition, biomedical and biotechnological applications of these ROMP-based block copolymer assemblies are addressed in view of their advantages over nanoparticulate formulations prepared by other methods. Ultimately, this review aims to encourage the utilization of ROMP as a versatile and direct approach to create advanced functional nanomaterials by providing a deep understanding of theoretical and practical aspects relating to its implementation.