Use this URL to cite or link to this record in EThOS: http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.689551
Title: Controlling macromolecular conformation for the nanoscale transmission of information
Author: Le Bailly, Bryden
ISNI:       0000 0004 5919 4743
Awarding Body: University of Manchester
Current Institution: University of Manchester
Date of Award: 2015
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Abstract:
Helical oligomers made up of the achiral amino acid Aib (2-aminoisobutyric acid) have great potential in relaying stereochemical information over nanometre distances by control of their macromolecular conformation. In a synthetic signalling pathway, the helical domain acts as a transducer, mediating the information flow between an input and an output. This thesis describes the advancement of these helical systems into functioning, dynamic transduction pathways capable of nanoscale information processing by a variety of different means. Through studying the effect of C-terminal chiral amino acids, alanine was found to give maximal control over the helical screw-sense. It was also discovered that the hydrogen bonding preference of the terminal group (ester, amide etc.) determined the screw-sense direction. By modifying the terminus, this directional preference was inverted using light or pH as secondary stimuli. Non-covalent interactions with solvent were found to be important in controlling the flow of information through the helical domain. In less polar solvents (THF, chloroform) a single screw sense can prevail for up to 200 monomers, leading to very low signal loss. A zinc binding site was developed to allow a chiral ligand to act as the input in the signalling process. Both amino and phosphoric acids led to remarkable levels of screw-sense induction. Using the reversible ligand binding interaction a pH switch was set up to moderate the binding of these two ligands, creating a ternary information switch. Significant progress was also made towards a light switch using a spiropyran as a competing ligand. Finally, a novel light-responsive switch capable of releasing a signalling molecule in solution was conceived and developed.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID: uk.bl.ethos.689551  DOI: Not available
Keywords: helix ; conformation ; stereochemical information
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