Final Report Summary - SUPOCOSYS (From Supramolecular Polymers to Compartmentalized Systems)
“How far can we push chemical self-assembly?” was one of the 25 “What we don’t know questions” posed by Science Magazine at its 125 years birthday. It is this challenge that guided our research to bring supramolecular chemistry to the next level of complexity. Our group is active in three different subjects of functional supramolecular architectures, to wit supramolecular electronics with chiral π-conjugated assemblies; supramolecular chemical biology with dendritic structures; and supramolecular polymers. With these subjects we aim to bridge the gap between life sciences and materials science. Within this general challenge of our group, our ERC proposal focused on the many options provided by combining organic and polymer chemistry with supramolecular chemistry. Firstly, two projects are defined in the new field of supramolecular polymers and how these dynamic counterparts of traditional macromolecules can provide new functions and applications provided all insights into these systems become known. In a next step the ordered supramolecular stacks are used as folding elements in macromolecules, similar to DNA/RNA. Secondly, two projects are defined on how supramolecular interactions can be used to make single chain compartmentalized systems of nanometer sizes. For that we return to advanced polymer synthesis and aim at more sequence control.
Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. In the reporting period, we have successfully used these concepts to arrive at functionalities not observed before. We studied multi-component self-assembled architectures intended to mimic the natural extracellular matrix (ECM) to provide an engineered scaffold for tissue engineering. We have shown that by the use of the correct supramolecular synthesis strategies, guest-host incorporation is facilitated, and a biomimetic cell culturing environment for intestinal organoid expansion is created.
Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. We find that we can force aggregation completely down the previously not favoured pathway so that, upon removal of the auxiliary, we obtain only metastable assemblies. These insights are of profound importance for the understanding the morphology of polymers and organics in electronic devices.
The synthesis and characterization of ABA triblock copolymers that contain two complementary self-assembling motifs are synthesized and folded into single-chain polymeric nanoparticles (SCPNs) via orthogonal self-assembly. The sequential aggregation of both self-assembling motifs results in single-chain folding of the polymer, and nanometer-sized particles with a compartmentalized interior are obtained. Atomic force microscopy (AFM) gives perfect visualization of the folding process and elucidates the drastic chain collapses. The stepwise folding process using orthogonal self-assembling supramolecular interactions results in a compartmentalized single-chain polymeric nanoparticle (SCPN) comprising different segregated do-mains, mimicking two secondary structuring elements in proteins. Using SCPN’s with catalytically active groups in the interior, we were able to perform enzyme-like catalysis in solvents normally unsuitable for these catalysts, but due to the compartmentalization, this enzyme-like behavior was achieved. Further research is aimed for introducing these novel technologies into industrially relevant processes.
In conclusion, the ERC Advanced grant has enabled the group and its group members to perform at the frontiers of science with ample possibility for technological breakthroughs.
Supramolecular polymers can be random and entangled coils with the mechanical properties of plastics and elastomers, but with great capacity for processability, recycling, and self-healing due to their reversible monomer-to-polymer transitions. At the other extreme, supramolecular polymers can be formed by self-assembly among designed subunits to yield shape-persistent and highly ordered filaments. The use of strong and directional interactions among molecular subunits can achieve not only rich dynamic behavior but also high degrees of internal order that are not known in ordinary polymers. They can resemble, for example, the ordered and dynamic one-dimensional supramolecular assemblies of the cell cytoskeleton, and possess useful biological and electronic functions. In the reporting period, we have successfully used these concepts to arrive at functionalities not observed before. We studied multi-component self-assembled architectures intended to mimic the natural extracellular matrix (ECM) to provide an engineered scaffold for tissue engineering. We have shown that by the use of the correct supramolecular synthesis strategies, guest-host incorporation is facilitated, and a biomimetic cell culturing environment for intestinal organoid expansion is created.
Self-assembly provides an attractive route to functional organic materials, with properties and hence performance depending sensitively on the organization of the molecular building blocks. Molecular organization is a direct consequence of the pathways involved in the supramolecular assembly process, which is more amenable to detailed study when using one-dimensional systems. We find that we can force aggregation completely down the previously not favoured pathway so that, upon removal of the auxiliary, we obtain only metastable assemblies. These insights are of profound importance for the understanding the morphology of polymers and organics in electronic devices.
The synthesis and characterization of ABA triblock copolymers that contain two complementary self-assembling motifs are synthesized and folded into single-chain polymeric nanoparticles (SCPNs) via orthogonal self-assembly. The sequential aggregation of both self-assembling motifs results in single-chain folding of the polymer, and nanometer-sized particles with a compartmentalized interior are obtained. Atomic force microscopy (AFM) gives perfect visualization of the folding process and elucidates the drastic chain collapses. The stepwise folding process using orthogonal self-assembling supramolecular interactions results in a compartmentalized single-chain polymeric nanoparticle (SCPN) comprising different segregated do-mains, mimicking two secondary structuring elements in proteins. Using SCPN’s with catalytically active groups in the interior, we were able to perform enzyme-like catalysis in solvents normally unsuitable for these catalysts, but due to the compartmentalization, this enzyme-like behavior was achieved. Further research is aimed for introducing these novel technologies into industrially relevant processes.
In conclusion, the ERC Advanced grant has enabled the group and its group members to perform at the frontiers of science with ample possibility for technological breakthroughs.