Dynamic combinatorial synthesis of donor-acceptor catenanes
Cougnon, Fabien B. L.
Sanders, Jeremy K. M.
University of Cambridge
Department of Chemistry
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Cougnon, F. B. L. (2012). Dynamic combinatorial synthesis of donor-acceptor catenanes (doctoral thesis).
Dynamic combinatorial chemistry (DCC) is a powerful method for synthesising complex molecules and identifying unexpected receptors. Chapter 1 gives an overview of the concept of DCC and its applications, and discusses its evolution to date. Chapter 2 describes the discovery of a new generation of donor-acceptor catenanes in aqueous dynamic combinatorial systems. The assembly of these catenanes is promoted by a high salt concentration (1 M NaNO3), which raises the ionic strength and encourages hydrophobic association. More importantly, a mechanism that explains and predicts the structures formed is proposed, giving a fundamental insight into the role played by hydrophobic effect and donor-acceptor interactions in this process. Building on these results, Chapter 3 describes the assembly in high salt aqueous libraries of a larger structure: a catenane. Remarkably, the catenane exhibits strong binding interactions with a biologically relevant target – spermine – in water under near-physiological conditions. Its synthesis is improved if the salt is replaced by a sub-mM concentration of spermine, acting as a template. Chapter 4 explores in further detail how subtle variations in the building block design influence the selective formation of either  or catenanes. This last section underlines both the advantages and the limitations of the method developed in Chapter 3. After a short conclusion (Chapter 5), Chapter 6 gives experimental details.
Supramolecular chemistry, Catenane, Molecular recognition, Self-assembly
This work was supported by EPSRC.
This record's URL: http://www.dspace.cam.ac.uk/handle/1810/241659