Title:
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Synthesis and evaluation of novel ligands for quantum dot stabilisation and polymerisation studies
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This thesis describes the design and synthesis of a variety of functionalised phosphine oxides and
sulfides, based on the structure of trioctylphosphine oxide, synthesised for the purpose of surface
mO(ilification of quantum dots. The ability ofthe ligands to modify the surface chemistry via
displacement ofthe original hexadecylamine capping layer of quantum dots was evaluated. Finally
the surface modified quantum dots were investigated for enhancement in their inherent properties
and improved compatibility with the various applications for which they were initially designed.
Upon the commencement of research involving quantum dots it became apparent that more
information on their behaviour and interaction with the environment was required. The limits of the
inherent stability of hexadecylamine capped quantum dots were investigated by exposure to a
number of different environments. The effect upon the stability ofthe quantum dots was monitored
by changes in the photoluminescence ability oftheir cores. Subtle differences between different
batches of quantum dots were observed and the necessity to account for these in future applications
noted. Lastly the displacement ofthe original hexadecylamine coating with the "designer"
functionalised ligands was evaluated to produce a set of conditions that would result in the best
possible surface modification. A general procedure was elucidated however it was discovered that
each displacement still required slight adjustment by consideration of the other factors such as the
difference in ligand structure and the individuality ofthe various batches of quantum dots.
This thesis also describes a procedure for the addition of a protective layer to the surface of
quantum dots by cross-linking the functionalised ligands bound to the surface via an acyclic diene
metathesis polymerisation. A detailed description ofthe problems encountered in the analysis of
these materials combined with the use of novel techniques such as diffusion ordered spectroscopy is
provided as a means to overcome the limitations encountered. Finally a demonstration ofthe
superior stability, upon exposure to a range of aggressive environments of these protected materials
compared with those before cross-linking provided physical proof ofthe cross-linking process and
the advantages of the cross-linking modification.
Finally this thesis includes the presentation of initial work into the production of luminescent
nanocrystal encoded resin beads for the specific use in solid phase combinatorial chemistry.
Demonstration of the successful covalent incorporation of quantum dots into the polymeric matrices
of non-functionalised and functionalised resin beads is described. Finally by preliminary work to
address and overcome the possible limitations that may be encountered in the production and
general employment of these materials in combinatorial techniques is given.
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