Biochemistry, Biophysics, and Structural Biology Commons^™

Understanding Rapid Intercalation Materials One Parameter At A Time, Wessel Van Den Bergh, Morgan Stefik

Faculty Publications

Demand for fast, energy-dense storage drives the research into nanoscale intercalation materials. Nanomaterials accelerate kinetics and can modify reaction path thermodynamics, intercalant solubility, and reversibility. The discovery of intercalation pseudocapacitance has opened questions about their fundamental operating principles. For example, are their capacitor-like current responses caused by storing energy in special near-surface regions or rather is this response due to normal intercalation limited by a slower faradaic surface-reaction? This review highlights emerging methods combining tailored nanomaterials with the process of elimination to disambiguate cause-and-effect at the nanoscale. This method is applied to multiple intercalation pseudocapacitive materials showing that the timescales …

A Kinetic Model For Blood Biomarker Levels After Mild Traumatic Brain Injury, Sima Azizi, Daniel B. Hier, Blaine Allen, Tayo Obafemi-Ajayi, Gayla R. Olbricht, Matthew S. Thimgan, Donald C. Wunsch

Mathematics and Statistics Faculty Research & Creative Works

Traumatic brain injury (TBI) imposes a significant economic and social burden. The diagnosis and prognosis of mild TBI, also called concussion, is challenging. Concussions are common among contact sport athletes. After a blow to the head, it is often difficult to determine who has had a concussion, who should be withheld from play, if a concussed athlete is ready to return to the field, and which concussed athlete will develop a post-concussion syndrome. Biomarkers can be detected in the cerebrospinal fluid and blood after traumatic brain injury and their levels may have prognostic value. Despite significant investigation, questions remain as …

Visible Light Generation And Mechanistic Investigation Of High-Valent Metal-Oxo Species Supported By Different Ligands, Seth Ellis Klaine

Masters Theses & Specialist Projects

Numerous transition metal catalysts have been designed as biomimetic model compounds for the active site of metalloenzymes found throughout Nature, most notably cytochrome P450 monooxygenases that carry out the oxidative transformations of organic substrates with near-perfect chemo-, regio-, and stereo-selectivity. The primary active oxidants in catalytic and enzymatic cycles are fleeting high-valent metal-oxo intermediates where the oxo ligand can transfer to an organic substrate in a process known as oxygen atom transfer (OAT).

In the present work, porphyrin-manganese(III), salen-chromium(III), and salenmanganese( III) derivatives were successfully synthesized and spectroscopically characterized using 1H NMR and UV-Vis spectroscopies. A facile photochemical approach was …

Leaving Ligand Effects On Reactivity And Solubility Of Monofunctional Platinum(Ii) Anticancer Complexes, Heidi Linn Hruska Millay

Masters Theses & Specialist Projects

Monofunctional platinum(II) complexes, such as phenanthriplatin and pyriplatin, have notably different characteristics from the bifunctional anticancer complexes, such as cisplatin and oxaliplatin, which have detrimental toxicities and resistance associated with them. The unique properties of the monofunctional complexes may be exploited to target cancer cells without producing the toxic side effects associated with the current FDA-approved platinum-based anticancer drugs. To advance the understanding of these monofunctional platinum(II) complexes, this study replaced the chloride leaving ligand with an acetate group, which should increase solubility and alter the rate of reactivity with key amino acid and nucleotide targets. Phenanthriplatin and pyriplatin compounds …

Synthesis, Kinetic And Catalytic Studies Of Manganese Complexes With Corrole And Porphyrin Ligands, Haleh Jeddi

Masters Theses & Specialist Projects

High-valent transition metal-oxo intermediates play a significant role in the catalytic cycle of the ubiquitous cytochrome P450 enzymes and in biomimetic catalytic systems. In this work, manganese(III) porphyrin and corrole systems (2) were synthesized and characterized by UV-vis absorbance and 1H-NMR, matching literaturereported spectroscopic data. Manganese(V)-oxo corroles (3) and a manganese(IV)-oxo porphyrin (4) were successfully generated by chemical oxidation using mchloroperoxybenzoic acid (m-CPBA), and their oxidation reactions with organic reductants were comparatively investigated. Results from single-turnover kinetic studies indicate that in the tris(pentafluorophenyl)corrole system (3a), the active oxidizing intermediate differs in different solvents. The active oxidizing intermediate in acetonitrile is …

Formation And Stability Of Atmospherically Relevant Isoprene-Derived Organosulfates And Organonitrates, Adam I. Darer, Neil C. Cole-Filipiak, Alison E. O'Connor, Matthew J. Elrod

Faculty & Staff Scholarship

Isoprene is the precursor for number of alcohol, organosulfate, and organonitrate species observed in ambient secondary organic aerosol (SOA). Recent laboratory and field work has suggested that isoprene-derived epoxides may be crucial intermediates that can explain the existence of these compounds in SOA. To confirm this hypothesis, the specific hydroxy epoxides observed in gas phase isoprene photooxidation experiments (as well as several other related species) were synthesized and the bulk phase aqueous reactions of these species in the presence of sulfate and nitrate were studied via nuclear magnetic resonance (NMR) techniques. The results indicate that both primary and tertiary organosulfates …

Methyl Septanoside Hydrolysis As A Measure Of Carbohydrate Ring Flexibility: Substrate Synthesis And Kinetics Analysis, Shawn Michael Miller

Honors Scholar Theses

A number of seven-membered ring systems have been found to have promising enzyme inhibiting properties. The common explanation for their efficacy is the apparent improved flexibility that the ring-system has over smaller rings. In an attempt to probe the validity of this hypothesis, unnatural seven-membered ring carbohydrates have been generated and subjected to kinetics analysis using hydrolysis. In particular, methyl α- and β-D-glycero-D-guloseptanoside were subjected to acid-catalyzed hydrolysis and monitored via HNMR experiments. The rate constants of the reactions were determined and compared to the hydrolysis rate constants of comparable pyranose carbohydrates and found to be significantly faster, indicating an …