Physical Sciences and Mathematics Commons^™

Expanding The Scope Of Clickable Azide-Functionalized Nanoclusters To Include Au144, Johanna A. De Jong

Electronic Thesis and Dissertation Repository

Thiolate-protected Au₁₄₄ nanoclusters (NCs) are an intriguing member of the gold NC family. Their geometric structure, distinct electrochemical features, and susceptibility to structural rearrangement under the duress of ligand exchange have been studied. However, there are currently no established protocols for surface modification or tuning of their ligand shells post synthesis. Here, the direct synthesis of three regioisomers of azide-modified Au₁₄₄ NCs with 60 azide moieties, i.e., Au₁₄₄(SC₂H₄C₆H₄-N₃)₆₀, is reported, in which the azide functionality is located at the ortho-, meta-, or …

Nanoorthogonal Surface Modifications Of Gold Nanoparticles And Nanoclusters Through Strain-Promoted Cycloaddition Chemistry, Praveen N. Gunawardene

Electronic Thesis and Dissertation Repository

This thesis explores the preparation of thiolated gold nanoparticles (AuNPs) and thiolated gold nanoclusters (AuNCs) capable of undergoing post-assembly surface modifications using two common “bioorthogonal” click reactions: the strain-promoted alkyne-azide cycloaddition (SPAAC) reaction (which occurs between a strained-alkyne and an azide) and the strain-promoted alkyne-nitrone cycloaddition (SPANC) reaction (which occurs between a strained-alkyne and a nitrone). Due to their rapid and modifiable reaction kinetics, high chemoselectivity, and stability of the reactive partners, these reactions were originally designed to tether functional substrates to biologically sensitive biomolecules, without altering their structure or perturb the biologically sensitive environments in which they …

Development Of Bioorthogonal Molecular Tools On Gold Nanoparticles, Wilson Luo

Electronic Thesis and Dissertation Repository

This thesis describes the development of bioorthogonal chemical tools — originally designed to form bonds cleanly and selectively in living systems — on gold nanoparticles (AuNPs) as a model reactive nanomaterial template to showcase chemical modifications in a facile and robust manner. To achieve this goal, new methodologies to cleanly incorporate strained alkyne (SA) and cargo-bearing triarylphosphine derivatives onto AuNPs were developed. The protocols described herein provide well-defined reactive AuNP interfaces that undergo bioorthogonal bond-forming and breaking reactions cleanly, selectively, and rapidly to enable chemical tuning of their properties and function.

In order to circumvent the high reactivity of SAs, …

Synthesis Of Metal-Containing Phosphines And Their Use In Coordination, Polymer, And Materials Chemistry, Amir Rabiee Kenaree

Electronic Thesis and Dissertation Repository

This thesis describes the investigation of a novel strategy for the synthesis of metal-containing small molecules, polymers, and nanomaterials. In this context, a new family of air-stable, homo- and heterometallic primary, secondary, and tertiary phosphines were prepared via the radical-initiated hydrophosphination reaction of PH₃ with vinylferrocene and/or vinylruthenocene. The full characterization of the phosphines confirmed their targeted structures and proved that the properties of the starting metallocenes are reflected in those of the resulting phosphines.

To study the coordination behavior of this family of phosphines, primary, secondary, and tertiary ethylferrocene phosphines were reacted with Group 6 metal carbonyl adducts …

Doped Tio2 Nanowires For Applications In Dye Sensitized Solar Cells And Sacrifical Hydrogen Production, Qasem Alsharari

Electronic Thesis and Dissertation Repository

This thesis explores the synthesis of metal oxide 1-D nanowires using a sol-gel method in supercritical carbon dioxide (sc-CO₂), as an environmental friendly enabling solvent. Porous nanowires were synthesized and their performance was tested in dye sensitized solar cell and sacrifical hydrogen production. Titanium isopropoxide (TIP) was used as a precursor for titania synthesis while copper, bismuth and indium were examined as dopants, respectively. The sol-gel reactions were catalyzed by acetic acid in CO₂ at a temperature of 60 °C and pressure of 5000 psi. It was observed that acetic acid/monomer ratio > 4 produced nanowires while a …