Expanding the Synthetic Methodology of N-Heterocyclic Carbene Gold Nanoclusters And Tailoring their Properties for Biomedical Application
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Authors
Sullivan, Angus I
Date
2025-02-05
Type
thesis
Language
eng
Keyword
Chemistry , Gold Nanocluster , N-heterocyclic carbene
Alternative Title
Abstract
Atomically precise gold nanoclusters (AuNCs) are an exciting and growing class of nanomaterials with applications in catalysis and biomedicine. Recently, AuNCs fully protected with N-heterocyclic carbenes (NHCs) have garnered attention due to their high stability and favourable optical properties when compared to nanoclusters stabilized by traditional thiolate and phosphine ligands. This thesis describes work developing the synthesis of these NHC-protected AuNCs.
In chapter 3, synthetic protocols are expanded to synthesize new nanoclusters. Au11 nanoclusters with unique and useful properties are synthesized by altering traditional reaction conditions, opening up new methods for the production of AuNCs. It is shown that reaction outcomes are significantly different depending on reagent choice. In chapter 7, traditional nanocluster synthesis conditions are also examined using real-time reaction monitoring to gain insight into the mechanism of nanocluster formation.
In chapter 4, the NHC ligand is altered to impart desirable properties to prepared nanocluster products. NHC-protected AuNCs have attracted interest as radiosensitizers in radiation therapy. The eventual use of these materials for this application requires water solubility. AuNCs with water soluble triethylene glycol monomethyl ether groups are synthesized. The impact of NC structure on stability in biological media is examined, and the water soluble nanoclusters are shown to have improved renal clearance. These clusters are also shown to be highly luminescent and thermally stable.
Multiple methods of functionalization of water soluble AuNCs are developed which will be crucial for the addition of cancer targeting molecules in radiation therapy. Azide groups available for click chemistry and carboxylic acid groups available for coupling chemistry are both added to the ligand shell of these NHC-protected AuNCs. Carboxylic acid groups are added to the ligand shell via post-synthetic ligand exchange reactions with Au NCs, which are developed and analyzed in chapter 6.
Overall, this thesis details significant advances in the synthesis and application of NHC-protected AuNCs.
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ProQuest PhD and Master's Theses International Dissemination Agreement
Intellectual Property Guidelines at Queen's University
Copying and Preserving Your Thesis
This publication is made available by the authority of the copyright owner solely for the purpose of private study and research and may not be copied or reproduced except as permitted by the copyright laws without written authority from the copyright owner.
Attribution 4.0 International