Dynamics of Small Molecules in Supramolecular Systems

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Supramolecular systems form reversibly from molecular building blocks. My research focuses on understanding the dynamics of supramolecular systems. I have a strong track record in methodology development, and mechanistic understanding is gained from extensive structure-dynamics relationship studies. The fundamental knowledge obtained has impact on how functional supramolecular systems are employed and will aid others in the rational design of functional systems, such as drug delivery, catalysis and sensing. The proposed work focuses on host systems with varying degrees of complexity, ranging from highly dynamic supramolecular aggregates (bile salts), to complex molecular environments (proteins), to simple molecular systems (cucurbit[n]urils). - Bile salt aggregates have different binding sites. Structure-dynamics studies will be extended to investigate intra-aggregate mobility at high guest loading. A new direction will take studies from solution to confined spaces in gels since many of the applications of supramolecular systems will require confinement on surfaces or solids. - Proteins bind guests in multiple sites with very different affinities. We showed that the desired reactivity for a bimolecular reaction was highest when the reagents were bound to protein sites with moderate affinity, which is not the generally expected trend. Photophysical techniques will be applied to specifically address reagents in the most reactive sites. New methodologies are required because traditional techniques, such as X-Ray crystallography, do not provide information on the reagents bound to moderate affinity sites. - Cucurbit[n]urils are hosts that bind guests with very high binding constants, which rival those observed for biological systems. The reasons for these high binding constants are not fully understood. Dynamic information on the guest binding to cucurbit[n]urils is currently limited. Structure-dynamics relationship studies are proposed to provide a comprehensive mechanistic understanding on guest@cucurbit[n]uril systems.