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Molecularly imprinted polymers (MIP) are gaining increasing interest thanks to their low cost of manufacturing, robustness and stability compared to their bio-analogues such as antibodies. The molecular imprinting process can be defined as the generation of molecular recognition sites in a synthetic polymer. The template-derived sites thus created within the polymeric matrix allow MIPs (often referred as plastic antibodies, due to their synthetic nature) to selectively recognise and bind the target molecule. In light of these properties, MIPs have been successfully applied in sensors, assays and separation applications. Due to their small size, MIP nanoparticles (NPs or nanoMIPs) can be used in biomedicine, since the nanoscale format is potentially suitable for cellular or in vivo applications. The aim of this work is to demonstrate the suitability of the nanoMIPs as tools for imaging in cells. For this purpose, the choice of appropriate fluorescent moieties to be included in the nanoMIPs is crucial and depends on the intended application. Several fluorescent monomers were characterised and chosen as imaging functionalities to be employed in the synthesis of MIP NPs (Chapter 2). The innovative solid-phase approach used in this work enables the synthesis of nanoMIPs both in organics (for small templates) and in water (for peptides and proteins), with the possibility to tailor the particle’s surface chemistry according to the intended use. (Chapter 3 and 4). Only few examples of MIP NPs for cellular imaging have been reported so far. Such nanosystems should be biocompatible and physiochemically stable under physiological conditions, as demonstrated in Chapter 5 and 6. Thanks to their good biocompatibility and recognition properties, MIP NPs were successfully applied as membrane-targeted diagnostic tools (Chapter 7) in both cancer and senescent cells, thus paving the way for their in vivo use as diagnostic and imaging tools.

This thesis concerns the NMR investigations of supramolecular metallo-nanocages as hosts for host-guest chemistry. The research is based on metallo-nanocages constructed from cyclotriveratrylene (CTV)-derivatives The host-guest interaction between the [Pd6(L1)8]⋅12(BF4) stella octangula cage and sodium alkyl sulfate guests have been characterised by 1H 1 D, DOSY and 2-D ROESY NMR and ESI-MS. The host-guest stoichiometry was determined at 1:2 by Job’s plot analysis. The shorter the length of the guest’s alkyl tail, the more tightly bound it was to the host cage. The self-assembly and self-sorting of the [Pd6(L1)8]⋅12(BF4) stella octangula cage were also investigated. d6-DMSO competed with the L1 ligand for the palladium(II) cation. The rate of self-sorting of the [Pd6(L1)8]⋅12(BF4) stella octangula cage was found to be affected by concentration, with lower concentrations resulting in cage systems that self-sorted in to homochiral cages at a faster rate. The novel FL1 ligand was characterised by 1H and 19F NMR spectroscopy in d6 DMSO and d3 MeCN and was used to produce stella octangula cage assemblies. The self-assembly of this system in d6 DMSO was observed and found to require an excess of palladium to form. This FL1 system was also investigated for host-guest interactions with sodium dodecyl sulfate (SDS). It formed a system that exhibited weaker binding than L1. The FL1 ligand formed quantitative cages in d3 MeCN. This system was characterised by 1H and 19F NMR spectroscopy, 2-D ROESY NMR, ESI-MS and X-ray crystallography. The L1 and FL1 ligands were used to form cryptophanes with [1,3 bis(diphenylphosphino)propane] in d6 DMSO, d3 MeCN and d3 MeNO2. These were characterised by 1H, 19F, 31P NMR spectroscopy, 2-D ROESY NMR, ESI-MS and X-ray crystallography. Both ligands showed a strong preference for anti cryptophane isomers in solution, although a small amount of syn isomer was observed in the L1 systems. The syn isomer was predominant species in the solid state.

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The Oil Pollution Diagnostic System (OPDS) is a proof of concept prototype pattern recognition system designed to assist chemists in assessing the type and source of refined oil spills that occur in freshwater. The pollution of inland waters by refined oils can cause damage to the local environment that takes many months to repair since oils are toxic to many of the flora and fauna often found in these habitats. The issue of assessing the exact type and source of the spill based on chemical analysis are separate but closely linked problems. The lesser of the two problems relates to the reliable identification of the oil type based upon distinctive patterns contained in the analysis data. The problem of identifying the likely source is more challenging however and the work describes an approach where the patterns contained in small sections of the analysis data are used as the basis of a match. Manual methods of analysing chemical data to determine the type and source of a spill have existed for some time. However in a courtroom situation where the analysis is presented as evidence in the attempt to secure a prosecution, manual methods of matching could be seen as subjective and unreliaole and possibly be exploited by the defence. The OPDS was developed as an alternative to the manual methods already in use. The system illustrates the advantages of transformable oil type templates, the advantages of automatic calibration to reduce the impact of retention time drift and the use of the lesser peaks between the major peaks for oil source fingerprinting. The major contribution in this section of the development project was to incorporate all the features mentioned in a system dedicated to the matching of gas cl1romatograms (GC), and furthermore to incorporate the facility to allow the system to automatically match GCs with minimal input from the user. The template based approach for type matching required the construction of a dynamic type template for each oil type to be identified. The template modelled a collection of distinctive features identified from the weathered information provided by the Environment Agency (of England and Wales). The templates were dynamic since they model the way the distinctive features are altered by the effects of weathering. This ability to negate the effects of weathering from the pattern together with some calibration allowing for instrument variation allowed the comparison of a sample to a set of templates via a metric based on the Euclidean distance between matched peaks. A similar approach was adopted with the problem of source identification where the emphasis was more on matching small collections of GC peaks that are present between the major features. This approach was based on a suggestion contained in the feasibility study. The EA provided a number of GCs relating to actual pollution incidents and these formed the basis of a set of case studies which were then used to develop and test the source matching system. Tests carried out on the type matching component of the system using independent test data produced correct classification figures of greater than 90% and kappa values of greater than 0.9. The source matching testing was less extensive than that done on the type matching component however a correct classification figure of 88% was observed. This thesis contains an explanation of the problems caused by spills of refined m inland waters, an explanation of the teclmiques used to analyse oil spills, a review of pattern recognition and chemometric tecrwiques, at1 overview of the software design and development the results achieved and the conclusions that can be drawn from these.

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No description available.