Use this URL to cite or link to this record in EThOS:
Title: Out-of-equilibrium replication and the amplification of chirality
Author: Morrow, Sarah
ISNI:       0000 0004 7966 2540
Awarding Body: University of Oxford
Current Institution: University of Oxford
Date of Award: 2018
Availability of Full Text:
Access from EThOS:
Full text unavailable from EThOS. Please try the link below.
Access from Institution:
This thesis explores physical autocatalysis, or the replication of supramolecular aggregates of surfactants such as micelles. There is a focus on the out-of-equilibrium and non-linear behaviours that can be extracted from a process of physical autocatalysis and which characterise lifelike dynamics and properties. Chapter 2 describes a study of reversibly-formed surfactants which form micelles within a dynamic combinatorial library. Though the system does not demonstrate a process of replication, the study of surfactants containing reversibly-formed bonds is of use towards the design of an out-of-equilibrium replicator. Thus, Chapter 3 describes the development of a physical replicator constructed by thiol-disulfide exchange which can persist, out-of-equilibrium, by the consumption of a chemical fuel, mimicking dissipative biological structures. The second half of this thesis introduces an ambitious design for a process of physical autocatalysis with amplification of chirality. Chapters 5 and 6 detail two experimental attempts. Chapter 5 describes the study of a chiral surfactant constructed by a native chemical ligation reaction, which shows interesting differences in reactivity between homogeneous and biphasic reaction conditions. However, a process of replication is not observed, nor the amplification of chirality. A more successful system is the study in Chapter 6 on the formation of a chiral surfactant based on the autocatalytic reaction studied in Chapter 3. An interesting sense of asymmetry is established; the chiral surfactant appears to be autocatalytic and partitions into a precipitate of enhanced ee and a solution phase of diminished ee.
Supervisor: Fletcher, Stephen ; Kukura, Philipp Sponsor: EPSRC
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Chemistry, Organic