Thesis
Copper-catalysed autocatalytic reactions
- Abstract:
-
The work contained within this thesis describes the development and study of self-reproducing systems, created from simple chemical building blocks, that exhibit emergent, life-like properties. Several different autocatalytic systems that are driven by copper-catalysed azide-alkyne cycloaddition (CuAAC) reactions are reported.
Chapter 1 introduces the fundamental concepts relevant to the bottom-up construction of minimal living systems and highlights relevant synthetic advances in the field of systems chemistry. The following two chapters describe an autocatalytic system where surfactant formation from phase-separated components is linked to a CuAAC reaction.
In Chapter 2, the influence of product seed on the rate of the reaction and the impact of surfactant tail length on the kinetics of the reaction is investigated. Chapter 3 expands upon this system by exploiting the link between the secondary catalyst and the autocatalytic cycle to drive new reaction outcomes. A mechanistic model is formulated that rationalises the kinetic profiles based on the phase behaviour of the coupling partners and the catalyst.
Chapter 4 presents an out-of-equilibrium self-reproducing protocell system that models biological cells more faithfully. Selection and inhibition processes are observed between competing replicators and orthogonal downstream chemical reactivity is incorporated.
Chapter 5 describes the ongoing development of an asymmetric autocatalytic CuAAC reaction through formation of enantioenriched polytriazole ligands via dynamic kinetic resolution of allylic azides. An initial finding shows that this new class of chiral ligand induces chirality in asymmetric CuAAC reactions.
Finally, Chapter 6 offers concluding remarks and details future work that may improve upon the reported systems.
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Authors
Contributors
- Institution:
- University of Oxford
- Division:
- MPLS
- Department:
- Chemistry
- Sub department:
- Organic Chemistry
- Research group:
- Fletcher Group
- Oxford college:
- Keble College
- Role:
- Supervisor
- ORCID:
- 0000-0001-7629-0997
- Funder identifier:
- http://dx.doi.org/10.13039/501100000781
- Funding agency for:
- Post, E
- Grant:
- 681491
- Programme:
- Consolidator Grant
- Type of award:
- DPhil
- Level of award:
- Doctoral
- Awarding institution:
- University of Oxford
- Language:
-
English
- Keywords:
- Deposit date:
-
2021-01-16
Terms of use
- Copyright holder:
- Post, E
- Copyright date:
- 2020
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