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Full-Text Articles in Physical Sciences and Mathematics

H2 Oxidation Over Supported Au Nanoparticle Catalysts: Evidence For Heterolytic H2 Activation At The Metal-Support Interface, Todd N. Whittaker, K. B. Sravan Kumar, Christine Peterson, Meagan N. Pollock, L. C. Grabow, Bert D. Chandler Dec 2018

H2 Oxidation Over Supported Au Nanoparticle Catalysts: Evidence For Heterolytic H2 Activation At The Metal-Support Interface, Todd N. Whittaker, K. B. Sravan Kumar, Christine Peterson, Meagan N. Pollock, L. C. Grabow, Bert D. Chandler

Chemistry Faculty Research

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H2 oxidation kinetics in the presence of water over Au/TiO2 and Au/Al2O3 catalysts, reaching the following mechanistic conclusions: (i) O2 activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H2O is a strong reaction inhibitor; (iii) fast H2 activation occurs at the MSI, and (iv) H2 activation kinetics are inconsistent with traditional dissociative H2 chemisorption on metals. Density …


Development Of Rapid, Homogeneous Assay For Investigating Isopeptide Bond Formation Using Fluorescence Polarization/Depolarization Measurements, Samuel Patricc Kasson Aug 2018

Development Of Rapid, Homogeneous Assay For Investigating Isopeptide Bond Formation Using Fluorescence Polarization/Depolarization Measurements, Samuel Patricc Kasson

MSU Graduate Theses

Autocatalytic intramolecular isopeptide bonds have been found in nature in certain gram-positive bacterial pilus structures. Recently, splitting of these domains that are capable of autocatalytic intramolecular isopeptide bond formation have been applied to create stable, selective, bio-orthogonal Catcher/Tag systems. The CnaB2 domain found in the FbaB pilus structure of Streptococcus pyogenes, has yielded the Catcher/Tag, Protein/Peptide systems termed SpyCatchter and SpyTag. Recent study has focused on tag optimization, stability and bio-orthogonality evaluation, along with applications in bioconjugation. I have recombinantly expressed SpyCatcher and SpyTag-fused proteins in E.coli, and conjugated them to fluorescent probes in order for use in fluorescence polarization/depolarization …


Kinetics And Activation Energy Parameters For Hydrolysis Of Acetic Anhydride In A Water-Acetone Cosolvent System, Samson Olowoyo May 2018

Kinetics And Activation Energy Parameters For Hydrolysis Of Acetic Anhydride In A Water-Acetone Cosolvent System, Samson Olowoyo

Electronic Theses and Dissertations

The hydrolysis of acetic anhydride is a widely-studied liquid phase reaction studied since 1906. Different approaches have been used to study the kinetics of this reaction. Approaches used by researchers have involved the use of sophisticated experimental set-ups. In this work, the pH technique has been adopted which involves the use of a pH meter to monitor the hydrolysis reaction. Analysis of the hydrolysis reaction has been performed for water/acetone cosolvent systems over a range of temperatures and mole fractions. Eyring analysis was performed under isomole fraction conditions and activation enthalpy, entropy, and Gibbs free energy for hydrolysis of acetic …


Removal Of Chromium(Vi) And Chromium(Iii) Ions From Aqueous Solution Using Bio-Char Generated From Agricultural Waste Products, Diego Fernando Gonzalez May 2018

Removal Of Chromium(Vi) And Chromium(Iii) Ions From Aqueous Solution Using Bio-Char Generated From Agricultural Waste Products, Diego Fernando Gonzalez

Theses and Dissertations

Heavy metals are one of the most persistent and prevalent contaminants in the aquatic environment. The removal of chromium from aqueous solution, especially in the hexavalent form is difficult. New technologies, techniques and/or new materials have been designed in order to effectively and efficiently remove chromium from the aqueous environment. The project focuses on the comparison of the effects of pH, time, temperature, binding capacity on bio-char’ generated from agricultural waste produces vs an amino modified derivative of the bio-char. Pineapple skins were dried, ground, sieved, and pyrolyzed to produce a bio-char material. The bio-char was analyzed using FTIR to …


Kinetics Of Silver(I)-Catalyzed Oxidation Of Allyl Alcohol By Peroxodiphosphate Inacetate Buffers, Priyamvada Sharma, Riya Sailani, Deepmala Pareek, Chandra Lata Khandelwal Jan 2018

Kinetics Of Silver(I)-Catalyzed Oxidation Of Allyl Alcohol By Peroxodiphosphate Inacetate Buffers, Priyamvada Sharma, Riya Sailani, Deepmala Pareek, Chandra Lata Khandelwal

Turkish Journal of Chemistry

The kinetics and mechanism of silver(I)-catalyzed oxidation of allyl alcohol with peroxodiphosphate in acetate buffers have been studied. The rate is independent of allyl alcohol concentration. The effect of other reaction parameters such as hydrogen and acetate ions has also been studied. The rate law accounting for all experimental observations corresponds to the proposed mechanism. The energy and entropy of activation have also been evaluated by employing Eyring plots.


Electrochemical Investigation Of The Kinetics Of Chloride Substitution Upon Reduction Of [Ru(Porphyrin)(No)Cl] Complexes In Thf., Jeremy R. Zink, E G. Abucayon, Anthony R. Ramuglia, Arghavan Fadamin, James E. Eilers, George B. Richter-Addo, Michael J. Shaw Jan 2018

Electrochemical Investigation Of The Kinetics Of Chloride Substitution Upon Reduction Of [Ru(Porphyrin)(No)Cl] Complexes In Thf., Jeremy R. Zink, E G. Abucayon, Anthony R. Ramuglia, Arghavan Fadamin, James E. Eilers, George B. Richter-Addo, Michael J. Shaw

SIUE Faculty Research, Scholarship, and Creative Activity

The electrochemistry of several ruthenium porphyrin nitrosyl chloride complexes [Ru(por)(NO)Cl] have been examined in tetrahydrofuran. The complexes undergo 1-electron irreversible reductions which result in the diffusion-limited substitutions of the chloride ligands for THF. This chloride metathesis is reversible in the presence of added NBu4Cl, and equilibrium constants and rate constants for chloride loss have been estimated. These parameters correlate with the NO stretching frequencies of the parent complexes, with more electron-donating porphyrin ligands favouring chloride loss from the reduced complexes. The [Ru(por)(NO)(THF)] products of the reductions can be detected by IR, EPR and visible spectroscopies. These species undergo …


Experimental And Theoretical Study Of Nh$_{3}$ Adsorption And Desorption Over A Cu-Chabazite Nh$_{3}$-Scr Catalyst, Selmi̇ Eri̇m Bozbağ, Mutlu Şi̇mşek, Onur Demi̇r, Deni̇z Şanli Yildiz, Hüseyi̇n Barkin Özener, Gökhan Hi̇sar, Can Erkey Jan 2018

Experimental And Theoretical Study Of Nh$_{3}$ Adsorption And Desorption Over A Cu-Chabazite Nh$_{3}$-Scr Catalyst, Selmi̇ Eri̇m Bozbağ, Mutlu Şi̇mşek, Onur Demi̇r, Deni̇z Şanli Yildiz, Hüseyi̇n Barkin Özener, Gökhan Hi̇sar, Can Erkey

Turkish Journal of Chemistry

NH$_{3}$ adsorption and desorption behavior of a commercial Cu-chabazite (CHA) NH$_{3}$ selective catalytic reduction (NH$_{3}$-SCR) catalyst was studied in the presence and absence of H$_{2}$O. NH$_{3}$ uptake values at various adsorption temperatures were obtained during various steps of the adsorption and temperature-programmed desorption (TPD) experiments. Total NH$_{3}$ uptake decreased from 4.6 to 1.6 g NH$_{3}$/L catalyst when the adsorption temperature was increased from 50 to 300 $^{\circ}$C. Three major adsorption sites for NH$_{3}$ adsorption could be identified and quantified using TPD experiments, namely loosely, moderately, and strongly bound NH$_{3}$ with peak centers at around 147, 266, and 447 $^{\circ}$C. The …