Applications of isothioureas in surface chemistry : modification of self-assembled monolayers and immobilisation on polymer supports
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Date
11/05/2017Author
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Abstract
The research outlined in this thesis describes the development of organocatalytic methodology
for the modification of self-assembled monolayers on silicon dioxide surfaces and its extension
towards an asymmetric protocol and immobilisation of isothiourea organocatalysts to polystyrene
supports.
Chapter 1 aims to describe the fundamental aspects of self-assembled monolayers and their place
within the wider area of surface chemistry. A recent overview of catalytic surface
functionalisation is discussed as well as the historical context of this project, with respect to
research within the Smith group, is also presented. A statement of the initial aims and objectives
of the research is presented.
Chapter 2 describes the proof-of-concept study undertaken to develop methodology towards the
functionalisation of silicon oxide surfaces using an isothiourea-catalysed organocatalytic Michael
addition-lactonisation process. Subsequent characterisation of the resulting surfaces and a
reaction scope is also carried out in this system.
Chapter 3 describes an extension of the methodology carried out in the previous chapter to allow
for an asymmetric protocol. The sense of enantioenduction of the resulting surfaces was then
examined using chemical force microscopy using a novel AFM probe with the results show that
chiral discrimination can be achieved using this methodology. Control experiments were also
undertaken by depositing enantiopure starting materials on a surface and measuring the adhesion
forces confirming the presence of a chiral surface.
Chapter 4 describes the immobilisation (R)-BTM and (2R,3S)-HyperBTM analogues onto
polystyrene supports and their evaluation in several different reaction classes previously
investigated within the Smith group. Results show that the polymer-supported catalyst (2R,3S)-
HyperBTM can be recycled up to 8 times without any major loss in yield or selectivity.
Chapter 5 offers a brief summary of the work undertaken in this PhD and some of the conclusions
that can be drawn from it as well as an insight into the potential future developments of this
research and areas where it could possibly expand and develop.
Type
Thesis, PhD Doctor of Philosophy
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