Out-of-equilibrium replication and the amplification of chirality
<p>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 d...
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| Format: | Thesis |
| Language: | English |
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2018
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| _version_ | 1817933050190757888 |
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| author | Morrow, SM |
| author2 | Fletcher, S |
| author_facet | Fletcher, S Morrow, SM |
| author_sort | Morrow, SM |
| collection | OXFORD |
| description | <p>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.</p> <p>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.</p> <p>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.</p> |
| first_indexed | 2024-03-07T07:06:03Z |
| format | Thesis |
| id | oxford-uuid:4ac12e8f-a7a3-4db7-b769-05501ac66240 |
| institution | University of Oxford |
| language | English |
| last_indexed | 2024-12-09T03:47:38Z |
| publishDate | 2018 |
| record_format | dspace |
| spelling | oxford-uuid:4ac12e8f-a7a3-4db7-b769-05501ac662402024-12-08T10:22:23ZOut-of-equilibrium replication and the amplification of chiralityThesishttp://purl.org/coar/resource_type/c_db06uuid:4ac12e8f-a7a3-4db7-b769-05501ac66240Chemistry, OrganicEnglishORA Deposit2018Morrow, SMFletcher, SKukura, P<p>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.</p> <p>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.</p> <p>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.</p> |
| spellingShingle | Chemistry, Organic Morrow, SM Out-of-equilibrium replication and the amplification of chirality |
| title | Out-of-equilibrium replication and the amplification of chirality |
| title_full | Out-of-equilibrium replication and the amplification of chirality |
| title_fullStr | Out-of-equilibrium replication and the amplification of chirality |
| title_full_unstemmed | Out-of-equilibrium replication and the amplification of chirality |
| title_short | Out-of-equilibrium replication and the amplification of chirality |
| title_sort | out of equilibrium replication and the amplification of chirality |
| topic | Chemistry, Organic |
| work_keys_str_mv | AT morrowsm outofequilibriumreplicationandtheamplificationofchirality |