Currently, there are no straightforward methods to 3D print materials with nanoscale control over morphological and functional properties. In this talk, a novel approach for the fabrication of materials with controlled nanoscale morphologies using a rapid and commercially available Digital Light Processing 3D printing technique will be presented. The approach uses a controlled/living radical polymerization technique, more specifically, reversible addition-fragmentation chain-transfer (RAFT) polymerization, to control the topologies of the polymers. In this talk, we report a rapid visible light mediated polymerization process and applied it to a 3D printing system. Following the optimization of the resin formulation, a variety of 3D printing conditions will be presented to prepare functional materials. The mechanical properties of these 3D printed materials were investigated under different conditions, showing that the control of the polymer structure can affect the performance of these materials. By controlling the polymer architecture, we were able to precisely control the nanostructure of these 3D printed materials via a polymerization induced microphase separation. The effect of nanostructure on 3D printed material properties will be discussed as well as their potential applications in drug delivery and energy storage, such as their use as solid polymer electrolytes for supercapacitor application. Finally, we will discuss a new approach for the recovery of resin after 3D printing enabling to recycle these 3D printed materials.

While the self-assembly of amphiphilic block copolymers in solution is triggered by polarity differences between blocks and selective solvent, the relative block volumes control the shape of the resulting micelles to spheres, cylinders, and polymersomes.[1] Recently, the range of morphologies was extended to self-assembled block copolymer microparticles termed polymer cubosomes that are open porous and feature highly regular channel systems with triply periodic minimal surfaces often adotping double cubic (lm3m) and double diamond (Pn3m) lattices.[2] This presentation summarizes recent efforts to understand the formation of polymer cubosomes,[3] with emphasis of diverse polymer functionalities,[4] and showcases the appliction of their functions in agrochemistry, energy conversion, and more generally templating.[5]

Self-assembly of photonic nanostructures involves chitin, proteins and lipids in insects with structural colour , however nobody has experimentally reproduced it in 3D with the same mechanisms that nature uses. These insect scales are chitinous and contain unsaturated lipids . We hypothesise that lipids assist in self-assembly of photonic crystals via lyotropic liquid crystal mesophases like gyroid . We aim to exclusively use biomolecules to lead the first attempts at a total biomimetic framework for photonic materials. Methods are established to assemble vesicles and affect a phase change with pH and biopolymers. The resulting dense gels are characterised by X-ray Scattering and Dynamic Light Scattering. Confocal Microscopy and Cryogenic Electron Microscopy demonstrate localisation of vesicles in the gel network. Future work aims to study the influence of biopolymers on dimensions and stability of vesicles for fabrication of soft matter that produces colour.

Combining synthetic and biological building blocks offers sheer unlimited potential to design macromolecular architectures with emerging functionalities.[1] To generate synthetic polymers, radical polymerization is arguably the most applied method across both fundamental research and industry. However, its inherent transformation of vinyl monomer feedstock into polymers with an all-carbon backbone prevents the incorporation of functional groups into the polymer main chain, thus restricting the design freedom of polyvinyl-based polymers.
This lecture discussed how radical ring-opening polymerization can be used to endow the backbone of polyvinyl polymers with function. We report a synthetic strategy that enables the incorporation of peptides spanning all 20 standard amino acids into the backbone of polymers.[2] This diversification enhances the structural and functional capabilities of synthetic polymers, enabling the engineering of polymers to mimic complex biological structures and functions, such as on-demand folding into β-sheet architectures.[3]
To exert control over the lifespan of polymer architectures, we have developed monomers that allow the incorporation of photochemical targets into the polymer backbone.[4] As a result, the traditionally unresponsive all-carbon backbone resulting from radical polymerization can be broken down in a flash of light. By tuning the photoscission wavelength of the embedded monomers and their distribution across the polymer chains, it becomes possible to cleave polymers selectively by choosing specific irradiation wavelengths.[5] Importantly, the self-assembly of these polymers into higher-order architectures also affects their photochemistry, enabling the switching between different photochemical outcomes depending on the self-assembly state.