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Full-Text Articles in Chemistry

Identification Of An Active Site-Bound Nitrile Hydratase Intermediate Through Single Turnover Stopped-Flow Spectroscopy, Natalie Gumataotao, Misty L. Kuhn, Natalia Hajnas, Richard C. Holz Dec 2014

Identification Of An Active Site-Bound Nitrile Hydratase Intermediate Through Single Turnover Stopped-Flow Spectroscopy, Natalie Gumataotao, Misty L. Kuhn, Natalia Hajnas, Richard C. Holz

Richard C. Holz

Stopped-flow kinetic data were obtained for the iron-type nitrile hydratase from Rhodococcus equi TG328-2 (ReNHase) using methacrylonitrile as the substrate. Multiple turnover experiments suggest a three-step kinetic model that allows for the reversible binding of substrate, the presence of an intermediate, and the formation of product. Microscopic rate constants determined from these data are in good agreement with steady state data confirming that the stopped-flow method used was appropriate for the reaction. Single turnover stopped-flow experiments were used to identify catalytic intermediates. These data were globally fit confirming a three-step kinetic model. Independent absorption spectra acquired between 0.005 …


The Critical Role Of Water At The Gold-Titania Interface In Catalytic Co Oxidation, Johnny Saavedra, H. Doan, Christopher J. Pursell, L. C. Grabow, Bert D. Chandler Sep 2014

The Critical Role Of Water At The Gold-Titania Interface In Catalytic Co Oxidation, Johnny Saavedra, H. Doan, Christopher J. Pursell, L. C. Grabow, Bert D. Chandler

Chemistry Faculty Research

We provide direct evidence of a water-mediated reaction mechanism for room-temperature CO oxidation over Au/TiO2 catalysts. A hydrogen/deuterium kinetic isotope effect of nearly 2 implicates O-H(D) bond breaking in the rate-determining step. Kinetics and in situ infrared spectroscopy experiments showed that the coverage of weakly adsorbed water on TiO2 largely determines catalyst activity by changing the number of active sites. Density functional theory calculations indicated that proton transfer at the metal-support interface facilitates O2 binding and activation; the resulting Au-OOH species readily reacts with adsorbed Au-CO, yielding Au-COOH. Au-COOH decomposition involves proton transfer to water and was suggested to be …


Kinetics Of Solid Phase Crystallization Of A-Ge Thin Films, John D. Graham May 2014

Kinetics Of Solid Phase Crystallization Of A-Ge Thin Films, John D. Graham

Macalester Journal of Physics and Astronomy

A method was developed to investigate the solid-phase crystallization (SPC) reaction undergone by germanium thin films. Amorphous films were grown by the radio-frequency (RF) magnetron sputtering and then annealed for a maximum of 6 hours at two temperatures: 446°C and 460°C. Crystallinity was measured by resistivity measurements, as well as crystal peak height and area taken from X-ray diffractometer (XRD) data. Initial data shows qualitative agreement with a nucleation-growth model for the observed kinetic process. However, observed peak narrowing phenomena suggests a comprehensive model of XRD measurements of polycrystalline thin films is needed for a rigorous interpretation of the results.


Kinetics Of Formation And Oxidation Of 8-Oxo-7,8-Dihydroguanine (8oxog), Derrick Ampadu Boateng May 2014

Kinetics Of Formation And Oxidation Of 8-Oxo-7,8-Dihydroguanine (8oxog), Derrick Ampadu Boateng

Electronic Theses and Dissertations

8-oxo-7,8-dihydroguanine (8oxoG) is one of the most important base lesions formed during oxidative damage of DNA. The aim of the present research was to investigate the effects of DNA concentration, G content, and the nature of oxidizing species on the kinetics of 8oxoG in model DNA solutions by using HPLC. The experimentally obtained yields of 8oxoG were typically in the range of 2-2.5% of total concentration of guanine. The ratios of the rate constant of hole diffusion in DNA to the rate constant of conversion of the hole into 8oxoG (kd/kr) were calculated from the experimental …


From Micro- To Nano-Scale: Applications Of Solid-Phase Enzymatic Reactors For Biopolymer Disassembly, Nyote J. Calixte Jan 2014

From Micro- To Nano-Scale: Applications Of Solid-Phase Enzymatic Reactors For Biopolymer Disassembly, Nyote J. Calixte

LSU Doctoral Dissertations

The process of immobilizing enzymes onto solid supports for bioreactions has some compelling advantages compared to their solution-based counterpart including the facile separation of enzyme from products, elimination of enzyme autodigestion, and increased enzyme stability and activity. We report in this work, the immobilization of λ-exonuclease onto poly(methylmethacrylate) (PMMA) micro- and nano-pillars populated within a fluidic devices for the micro and nanoscale on-chip digestion of double-stranded DNA. Enzyme immobilization in both studies was successfully accomplished using 3-(3-dimethylaminopropyl) carbodiimide/N-hydroxysuccinimide (EDC/NHS) coupling to carboxylic acid functionalized PMMA micropillars. Our micro-scale results suggest that the reaction efficiency for the catalysis of dsDNA digestion …