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Mulrooney PhD thesis.pdf14.74 MBAdobe PDFView/Open
Title: Analyte sensing with luminescent quantum dots.
Authors: Mulrooney, Ray
Supervisors: Callan, John F.
Issue Date: 2009
Publisher: The Robert Gordon University
Abstract: Semiconducting nanocrystals otherwise known as Quantum Dots (QDs) have attracted considerable attention over the last number of years due to their unique optical properties and potential applications. Their narrow size-tunable emission spectra, broad absorption spectra, resistance to photobleaching and long fluorescent lifetimes make them ideal for sensing ions and small molecules. This thesis explores the potential of QDs to function as the emissive unit in fluorescent probes. Primarily, the focus of the work is to develop QD-based sensors that operate through an electron transfer mechanism. Chapter 3 discusses the synthesis and characterisation of CdSe and CdSe/ZnS QDs. Three different sized QDs were prepared each with distinct emission wavelengths. The sizes of these nanoparticles were determined by three methods, transmission electron microscopy (TEM), dynamic light scattering (DLS) and by a UV-vis method. Surface functionalisation of these synthesised QDs (chapter 4) with mercaptosuccinic acid rendered them water soluble and were shown to display selectivity for Cu2+ over a number of biologically relevant metal ions. The negatively charged surface of the QDs and the position of copper in the Irving-William series were believed to be responsible for this interaction. Positively charged CdSe/ZnS QDs were also prepared and were shown to detect ATP and to a much lesser extent GTP over the other nucleotides screened. The greater net negative charge of the ATP and GTP when compared to their mono and diphosphate analogues was the likely cause of this discrimination. In chapter 5 the relatively unexplored field of anion sensing with QDs was examined using charge neutral urea and thiourea receptors. Based on a design by Gunnlaugsson et al, a CdSe/ZnS QD with a thiourea receptor anchored to its surface displayed similar PET-mediated fluorescence quenching as an organic dye sensor containing the same receptor. A ferrocenyl urea receptor was also anchored to a QD surface and shown to “switch off” the QD’s fluorescence emission. On addition of fluoride ions the emission was restored, most likely due to a modulation of the ferrocene’s redox activity. In chapter 6 the assembly of Schiff base receptors on the surface of preformed CdSe/ZnS QDs were shown to arrange in such a way to enable the simultaneous detection of Cu2+ and Fe3+. The intriguing aspect of this study was that the receptors themselves displayed no selectivity for any metal ion until they were assembled on the QDs. Recognition was also confirmed by a distinct colour change visible to the naked eye.
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