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Articles 1 - 7 of 7
Full-Text Articles in Physical Sciences and Mathematics
Vibrational Spectroscopy Of Intermediates Of C-H Bond Activation By Transition Metal Oxide Cations, Gokhan Altinay
Vibrational Spectroscopy Of Intermediates Of C-H Bond Activation By Transition Metal Oxide Cations, Gokhan Altinay
Open Access Dissertations
Direct, efficient oxidation of alkanes is a long-standing goal of catalysis. Gas phase FeO+ can convert methane to methanol and benzene to phenol under thermal conditions. Two key intermediates of these reactions are the [HO-Fe-R]+ insertion intermediate and Fe+(ROH) (R=CH3 or C6H5) exit channel complex. This work describes measurements of the vibrational spectra of these intermediates and electronic structure theory calculations of the potential energy surfaces for the reactions. They help to characterize the mechanism for these reactions. Chapter 1 describes previous studies of methane-to-methanol and benzene-to-phenol conversion by gas-phase transition metal oxide cations. Spectra of gas-phase reaction intermediates are …
Charge And Energy Transport In Single Quantum Dot/Organic Hybrid Nanostructures, Kevin Thomas Early
Charge And Energy Transport In Single Quantum Dot/Organic Hybrid Nanostructures, Kevin Thomas Early
Open Access Dissertations
Hybrid quantum dot /organic semiconductor systems are of great interest in optoelectronic and photovoltaic applications, because they combine the robust and tunable optical properties of inorganic semiconductors with the processability of organic thin films. In particular, cadmium selenide (CdSe) quantum dots coordinated with oligo-(phenylene vinylene) ligands have displayed a number of hybrid optical properties that make them particularly well-suited to these applications. When probed on an individual particle level, these so-called CdSe-OPV nanostructures display a number of surprising photophysical characteristics, including strong quenching of fluorescence from coordinating ligands, enhanced emission from the CdSe quantum dot core, suppression of fluorescence intermittency, …
Field Portable Methods For The Determination Of Arsenic In Environmental Samples, James Kalman Kearns
Field Portable Methods For The Determination Of Arsenic In Environmental Samples, James Kalman Kearns
Open Access Dissertations
Arsenic contamination of the environment is a worldwide health hazard. This research project focused on four areas: development and testing of low cost, field portable devices capable of measuring levels of arsenic at 10 μg L-1 or less; specific chemical techniques for such testing; creation of educational tools and techniques to allow operators who lack advanced chemistry training to perform accurate testing; and the determination and use of a biomarker in DNA as a cancer predictor in individuals exposed to environmental arsenic. The analytical techniques explored include: (1) the Gutzeit method of arsenic determination though arsine gas production, which was …
Time Resolved Single Molecule Spectroscopy Of Semiconductor Quantum Dot/Conjugated Organic Hybrid Nanostructures, Michael Yemoh Odoi
Time Resolved Single Molecule Spectroscopy Of Semiconductor Quantum Dot/Conjugated Organic Hybrid Nanostructures, Michael Yemoh Odoi
Open Access Dissertations
Single molecule studies on CdSe quantum dots functionalized with oligo-phenylene vinylene ligands (CdSe-OPV) provide evidence of strong electronic communication that facilitate charge and energy transport between the OPV ligands and the CdSe quantum dot core. This electronic interaction greatly modify, the photoluminescence properties of both bulk and single CdSe-OPV nanostructure thin film samples. Size-correlated wide-field fluorescence imaging show that blinking suppression in single CdSe-OPV is linked to the degree of OPV coverage (inferred from AFM height scans) on the quantum dot surface. The effect of the complex electronic environment presented by photoexcited OPV ligands on the excited state property of …
Structural Characterization Of The Pre-Amyloid Oligomers Of Β-2-Microglobulin Using Covalent Labeling And Mass Spectrometry, Vanessa Leah Castillo Mendoza
Structural Characterization Of The Pre-Amyloid Oligomers Of Β-2-Microglobulin Using Covalent Labeling And Mass Spectrometry, Vanessa Leah Castillo Mendoza
Open Access Dissertations
The initial steps involved in the assembly of normally soluble proteins into amyloid fibrils remain unclear, yet over 20 human diseases are associated with proteins that aggregate in this manner. Protein surface modification is a potential means of mapping the interaction sites in early oligomers that precede amyloid formation. This dissertation focuses on the use of covalent labeling combined with mass spectrometry to elucidate the structural features of Cu(II)-induced β-2-microglobulin (β2m) amyloid formation. An improved covalent modification and MS-based approach for protein surface mapping has been developed to address the need for a reliable approach that ensures protein structural integrity …
Quaternary Structure Of Chemoreceptors In Active Signaling Complexes Differs From Crystal Structure Of Isolated Fragments: Evidence From Solid-State Nmr, Daniel John Fowler
Quaternary Structure Of Chemoreceptors In Active Signaling Complexes Differs From Crystal Structure Of Isolated Fragments: Evidence From Solid-State Nmr, Daniel John Fowler
Open Access Dissertations
The receptor dimers that mediate bacterial chemotaxis form high-order signaling complexes with CheW and the kinase CheA. From the packing arrangement in two crystal structures of different receptor cytoplasmic fragments, two different models have been proposed for receptor signaling arrays: the trimers-of-dimers and hedgerow models. We identified an interdimer distance that differs substantially in the two models, labeled the atoms defining this distance through isotopic enrichment, and measured it with 13C-19F REDOR. This was done in two types of receptor samples: first, isolated bacterial membranes containing overexpressed, intact receptor, and second, soluble receptor fragments reconstituted into kinase-active signaling complexes. In …
Structural And Mechanistic Studies Of Alpha-Galactosidase A And Pharmacological Chaperones, Abigail Ida Guce
Structural And Mechanistic Studies Of Alpha-Galactosidase A And Pharmacological Chaperones, Abigail Ida Guce
Open Access Dissertations
Human α-galactosidase (α-GAL; EC 3.2.1.22) is a lysosomal enzyme that hydrolyzes of terminal alpha-linked galactosyl residue of glycosphingolipids. Deficiencies in α-GAL leads to Fabry disease, which is characterized by the build-up of globotriaosylceramide and other neutral substrates in cells, ultimately leading to a multi-systemic organ failure in patients. Hundreds of distinct mutations have been found in the α-GAL gene of Fabry disease patients. One current treatment for Fabry disease is Enzyme Replacement Therapy (ERT), which restores the missing α-GAL function. An alternative treatment, called Pharmacological Chaperone Therapy (PCT), utilizes a small molecule substrate analogue, 1-deoxygalactonojirimycin (DGJ). In order to better …