From Monomer to Nanostructure in One Step: Switchable Polymerization-Induced Electrostatic Self-assembly (PIESA) as Artificial Reaction-Assembly Network

• Applicant: Dr. Fabian Sobotta
• Subject Area: Polymer Materials
• Term: since 2023
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 525180722

The main goal of the project is to develop a novel, synthetic reaction-assembly network based on simultaneous polymerization and complex coacervation mimicking naturally occurring assembly mechanisms. The concept of spatiotemporal coupling the polymerization and self-assembly of charged macromolecules, through the usage of a complementary template, will be introduced with the aim to obtain superior control over the polymer and nanoparticle structure during the assembling process, enabling the next-generation of block copolymer nanomaterials with precisely defined shape and domain sizes, which would not be attainable with traditional techniques. Based on a systematic approach, a library of structures will be created under varying conditions, which will serve as a screening platform for in-depth polymer and particle characterization and the localization of state transitions. Therefore, fundamental relationships between the network conditions and the structural evolution of the assemblies will be revealed, providing insights into the underlying assembly pathways, which are required for a rational material design. In a further step, the unique potential of switchable assembly mechanism to alter the assembly pathway by fine-tuning the structural relaxation times will be exploited to tailor the size and shape of nanostructures assembled even from the same building blocks. The coupling of polymerization and self-assembly in switchable assembly opens up the opportunity to tune the topology of the growing polymer chains itself affecting their intrachain folding and interchain assembly. Combining the switching mechanism with the copolymerization of a second monomer will enable the modulation of the block sequence of the growing copolymer chains by adjusting the switching steps instead of consecutive polymerizations. This spatiotemporal control over both assembly kinetics and monomer sequence, similar to natural networks, constitutes a new paradigm in the design of the next-generation of polymeric nanomaterials and marks a step towards perfect monodispersity, the “Holy grail” in polymer science. Due to the widespread application of polymeric complex coacervate nanostructures, this work will stimulate new developments in the fields of precision drug delivery, biomaterials, or cellular mimics as well as contribute to our understanding of the underlying principles of the hierarchical assembly of biomacromolecules.

• DFG Programme: WBP Fellowship
• International Connection: Netherlands
• Host: Professorin Dr. Ilja Voets