Hough, Alexander J. (2013) Photochemical control of pyramidal inversion and photoactivation of antimicrobial agents. PhD thesis, University of Warwick.

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Abstract

Control of molecular motion is an important step towards the envisaged development
of molecular scale devices and machines. A large amount of research has been
documented regarding the control of molecular rotation and shuttling processes, but
relatively few examples of control over nitrogen pyramidal inversion exist and so far
no examples that require solely physical inputs such as light and heat have been
reported. The first part of this thesis describes attempts to control nitrogen pyramidal
inversion in aziridines and azetidines, using only light and heat to switch between
two states with differing rates of inversion. Three avenues of research utilising
anthracene photochemistry are discussed. The strategies employed include
modifying ring strain by fused macrocycle formation; introduction of ring strain via
small ring formation; and disruption of transition state stabilising hydrogen bonds
through macrocycle formation. Finally, and more successfully, azobenzene
photochemistry was used to modify a π-system adjacent to an aziridine nitrogen
centre resulting in different inversion rates in the cis and trans azobenzene isomers.
The experimentally derived inversion rates were supported by ab initio calculations.
The second part of this thesis outlines attempts to develop photoactivated β-lactam
antimicrobial agents. Two families of compounds were synthesised, based on amine
linked bis-anthracene, and 2-pyridone isomerisations. Their antimicrobial activity
was evaluated against B. Subtilis and E. Coli using the Kirby-Bauer disk diffusion
method. One β-lactam produced by anthracene photodimerisation displayed modest
activity against B. Subtilis. However, control experiments suggested the acyclic
precursor possessed higher levels of antimicrobial activity.

Item Type:	Thesis (PhD)
Subjects:	Q Science > QD Chemistry
Library of Congress Subject Headings (LCSH):	Photochemistry, Anti-infective agents
Official Date:	February 2013
Dates:	Date Event February 2013 Submitted
Institution:	University of Warwick
Theses Department:	Department of Chemistry
Thesis Type:	PhD
Publication Status:	Unpublished
Supervisor(s)/Advisor:	Shipman, Michael
Sponsors:	Warwick Postgraduate Research Scholarship (WPRS)
Extent:	215 leaves : illustrations.
Language:	eng

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