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Photochemistry Of A Series Of Weakly Coupled Dinuclear Ruthenium(Ii) Complexes, Latisha Michelle Puckett

Graduate Theses and Dissertations

An improved synthetic method was developed for symmetric ruthenium(II) polypyridine complexes with the form L2Ru(diphen)RuL2. The scope of the reaction was investigated in regards to the ligands, bridging ligands, and starting materials. Several ligands were successful in the synthesis, including 2,2’-bipyridine (bpy), 4,4’-dimethyl-2,2’-dipyridyl (dmb), 1,10-phenanthroline (phen), 4,7-diphenyl-1,10-phenanthroline (dpphen), and 3,4,7,8-tetramethyl-1,10-phenanthroline (tmphen). Ligands that did not react to form symmetric dimeric complexes were 2,2’-bipyrazine, bpz, and 2,2’-bipyrimidine, bpm.

Dpp, 2,3-bis(2-pyridyl)-pyrazine, effectively replaced diphen as the bridging ligand to produce (phen)2Ru(dpp)Ru(phen)24+. However, replacing the [Ru(CO)2Cl2]n with Ru(DMSO)4Cl2 did not prove successful. The newly developed synthesis was also applied to the synthesis of …

Photochemical Tools For Fluorescent Labeling Of Endogenous Proteins, Stephen T. Mccarron

Doctoral Dissertations

The study of the dynamic movements of membrane bound proteins is typically achieved through an exogenously applied fluorescent tag or genetic modification of a receptor of interest to spatiotemporally monitor protein location. Techniques often used for labeling proteins include overexpression of a fluorescent protein such as GFP fused to a target protein or the application of antibodies. These methods benefit from superb specificity towards a receptor of interest, but may impose unforeseen consequences when studying natural protein movements. Thus, it is advantageous to development small, modular probes that would allow for visualization of endogenous membrane bound receptors in a minimally …

Strategies For Photochemical And Thermal Modification Of Materials, Sara Ghiassian

Electronic Thesis and Dissertation Repository

The modification of materials/surfaces is central to numerous applications ranging from opto-electronic devices to biomedical implants and drug delivery. Thus, there exists a high motivation for improving the methodologies which can be employed in order to modify surfaces in a selective and efficient fashion. One of the major goals of surface engineering is to control the chemical composition at the material interface. The fine control of the surface properties is a field of intense research as the performance of functional materials is strongly related to the processes and interactions that are occurring at the materials’ interface.

In general, the modification …

The Synthesis And Characterization Of Ferritin Bio Minerals For Photovoltaic, Nanobattery, And Bio-Nano Propellant Applications, Trevor Jamison Smith

Theses and Dissertations

Material science is an interdisciplinary area of research, which in part, designs and characterizes new materials. Research is concerned with synthesis, structure, properties, and performance of materials. Discoveries in materials science have significant impact on future technologies, especially in nano-scale applications where the physical properties of nanomaterials are significantly different than their bulk counterparts. The work presented here discusses the use of ferritin, a hollow sphere-like biomolecule, which forms metal oxo-hydride nanoparticles inside its protein shell for uses as a bio-inorganic material.Ferritin is capable of forming and sequestering 8 nm metal-oxide nanoparticles within its 2 nm thick protein shell. A …

Development Of An Optical Method For The Detection Of Homocysteine As A Disease Biomarker Using Fluorescein-Aldehydes, Aabha Barve

Dissertations and Theses

Homocysteine is a natural occurring aminothiol. It is an intermediate product in the metabolism of methionine. Methionine is an essential amino acid required for protein synthesis. Metabolic irregularities disrupt homocysteine levels in plasma. Elevated homocysteine levels are directly linked to folate and cobalamin (vitamin B12) deficiencies, and are an independent risk factor for cardiovascular diseases. High homocysteine levels have also been associated with Alzheimer's, osteoporosis, renal failure, cancer, birth defects and pregnancy complications. The association of elevated homocysteine levels with cardiovascular disease and other diseases has generated great interest in the detection of homocysteine.

An optical method for the detection …

Photogenerated O-Azaxylylenes: Mechanistic Studies And Synthetic Applications, William Cole Cronk

Electronic Theses and Dissertations

This research sets out to build upon excited state o-azaxylylene cycloaddition. The mechanism behind the excitation and cycloaddition process of photogenerated o-azaxylylenes was determined experimentally. Time-correlated single-photon counting, steady-state spectroscopy, triplet quenching experiments, and quantum yield studies provided evidence suggesting that excited state intramolecular proton transfer is followed by intersystem crossing and stepwise addition to the tethered unsaturated pendant.

In keeping with the principles of diversity oriented synthesis, a modular approach was taken to gain access to a diverse array of N,O,S-Polyheterocycles which were modified postphotochemically via Suzuki coupling to yield fused biaryls. Cycloaddition products, outfitted with halogens …

Versatility Of N-Peptidyl And N-Glycopeptidyl Nitroindolines For The Formation Of Peptide/Glycopeptide Acids, Amides, And Thioesters, Luis Alfonso Barrera

Open Access Theses & Dissertations

N-acyl-7-nitroindolines are photoreactive compounds that are known to acylate a number of nucleophiles in inert aprotic solvents under neutral conditions when illuminated at 350 nm. We have assembled a MUC1-derived peptide and Tn or STn-containing MUC1 glycopeptides with a C-terminal photoreactive 7-nitroindoline linker attached to Sieber amide resin by solid phase peptide synThesis using the Fmoc strategy. This type of construction allows for the cleavage of fully protected photoreactive peptides/glycopeptides from the resin with dilute trifluoroacetic acid, or for the direct photorelease of protected peptide/glycopeptide derivatives. Here we demonstrate that N-peptidyl and N-glycopeptidyl 7-nitrindolines can be photochemically converted into their …

I. Synthesis Of Ascarosides For Biological Evaluation And Ii. Development Of Visible Light-Promoted Selenofunctionalization And Grafting Of Aryl Iodides, Elizabeth Susan Conner Balapitiya

LSU Doctoral Dissertations

This dissertation focuses on analog synthesis for biological evaluation and visible light promoted method development. Chapter 1 centers upon the synthesis of Caenorhabditis elegans dauer pheromone analogs. C. elegans is a nematode which, in times of environmental stress, enters a dauer stage. Two highly conserved pathways, which play important roles in some diseases in higher organisms, monitor dauer formation: TGF-β and IGF-1. Dauer formation is triggered by the nematode’s chemosensation of the dauer pheromone, consisting of a group of previously-isolated ascarosides. These compounds differ in chain length, saturation, terminal functionality of side chain, ω vs. ω-1 oxygenation and presence of …

I. Synthesis Of Ascarosides For Chemical Biology Studies In Caenorhabditis Elegans, Ii. A Photochemical Approach To Delavayine, And Iii. Remote Hydroxylation By Radical Translocation And Polar Crossover, Kyle Allen Hollister

LSU Doctoral Dissertations

The foci of this dissertation are the synthesis of analogs for chemical biology studies, synthetic chemistry method development (with an emphasis on photochemistry), and the application of these methods toward total synthesis. Chapter 1 outlines the synthesis of an array of pheromone analogs that are derivatives of the dideoxy sugar ascarylose. Referred to as ascarosides, such compounds have recently been shown to influence important biological processes in the model organism Caenorhabditis elegans. C. elegans secretes ascarosides into its environment, where the compounds then act as signaling molecules by providing information on factors like population density. Chapter 2 describes the biological …