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Dynamic combinatorial synthesis of donor-acceptor catenanes 10.17863/CAM.16286 Cougnon, Fabien B. L. 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 [2]catenanes in aqueous dynamic combinatorial systems. The assembly of these [2]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 [3]catenane. Remarkably, the [3]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 [2] or [3]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. University of Cambridge 2012-01-10 Thesis Doctoral Doctor of Philosophy (PhD) eng This work was supported by EPSRC. http://www.dspace.cam.ac.uk/handle/1810/241659 https://www.repository.cam.ac.uk/handle/1810/241659 https://www.repository.cam.ac.uk/bitstreams/cc86ff15-d9e2-4c0d-a96c-f38b9275d723/download d1eafa6fa0bea14e3d0eb56e82c6cbc6 https://www.repository.cam.ac.uk/bitstreams/3628be77-819a-4b4f-8014-1196b6d64984/download 48dcdf38f646da27e5e4bc6c1893d4fc https://www.rioxx.net/licenses/all-rights-reserved/ Supramolecular chemistry Catenane Molecular recognition Self-assembly