Chemistry Commons^™

Design, Synthesis, And Characterization Of A Tetraamide Macrocyclic Ligand And Its Fe- Complex For Green Oxidation Chemistry, Shane Z. Sullivan

Theses and Dissertations

This work presents the spectroscopic characterization and catalytic investigation of a FeIII-complex of a tetraamidomacrocyclic ligand. Under catalytic conditions the complex is soluble in aqueous solutions and rapidly activates hydrogen peroxide under mild reaction conditions. Both the kinetics and extent of water-soluble dye and paper effluent H2O2-bleaching catalyzed was found to be comparable to known FeIII-TAML complexes. As an additional application, the complex showed potential for the synthesis of a variety of Noxides from their corresponding amines as demonstrated by its high turnover number and essentially stoichiometric yield in selected amines. Electrospray ionization-mass spectrometry of the complex reveals a peak …

Synthesis, Kinetic And Photocatalytic Studies Of Porphyrin-Ruthenium-Oxo Complexes, Yan Huang

Masters Theses & Specialist Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in Nature, namely the cytochrome P450 enzymes. Ruthenium porphyrin complexes have been the center of the research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes. This study focuses on kinetic and photocatalytic studies of oxidation reactions with wellcharacterized high-valent ruthenium-oxo porphyrin complexes.
The trans-dioxoruthenium(VI) porphyrins have been among the best characterized metal-oxo intermediates and their involvement as …

Molecular Characterization Of The Soluble Fraction Of Atmospheric Particulate Matter Obtained By Chemical Oxidation With Nitric Acid, Amanda Susan Priest

Chemistry & Biochemistry Theses & Dissertations

The availability of information regarding the composition of ambient atmospheric particulate matter and the transformations that these compounds may undergo upon atmospheric transit is surprisingly absent. Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry is used in this study to rapidly evaluate the composition of the water-soluble organic fraction of standard and collected atmospheric particulate matter samples, and the changes that these mixtures undergo upon oxidation with nitric acid. The standard samples include representative particulate matter collected over the course of a year in Washington, D.C. and particulate matter from the exhaust of a diesel-powered engine. The collected sample …

Oxidation Of Dibenzothiophene To Dibenzothiophene Using Metal Nanoparticles Supported On Silica, Karina Castillo

Open Access Theses & Dissertations

Silica and nanoparticles of Pt, Au, and Ag supported on silica were tested for the ability to oxidize dibenzothiophene (DBT) to sulfone. High performance liquid chromatography was used to study the removal of DBT from solution. In addition, X- ray diffraction, infrared spectroscopy and Raman Spectroscopy were used to characterize the product of the oxidation reaction. Further studies involved the use X-ray absorption spectroscopy to characterize the nanoparticle catalysts before and after the oxidation reaction.

To better understand the reaction, silica was synthesized at different pHs using three different acids. The acids used to synthesize the silica were HCl, HNO3, …

Kinetic Studies Of The Sulfoxidation Of Aryl Methyl Sulfides By Trans-Dioxoruthenium(Vi) Porphyrin Complexes, Chris Abebrese

Masters Theses & Specialist Projects

The development of an efficient, catalytically active, biomimetic model for cytochrome P-450 enzymes has been an area of intense research activity. Ruthenium porphyrin complexes have been the center of this research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes, the epoxidation of alkenes and aromatic rings, and the N-oxidation of amines, among others. In this project, the kinetics of two-electron sulfoxidation of para-substituted phenyl methyl sulfides to the corresponding sulfoxides with well-characterized trans-dioxoruthenium(VI) porphyrin complexes were studied by rapid stopped-flow spectroscopy. The substituent effect in sulfides and in dioxoruthenium(VI) complexes were …

Enhanced [Ru(Bpy)3]2+-Mediated Oxidation Of Guanine Prompted By Dhp, Bao-Lian Zhang, Wei Hong, Bao-Yi Lu, Hong Li

Journal of Electrochemistry

The effects of dihexadecyl phosphate(DHP) and multi-walled carbon nanotubes(MWNTs) on the oxidation of guanine mediated by[Ru(bpy)₃]²⁺ on the ITO electrode have been investigated by cyclic voltammetry and differential pulse voltammetry.The results showed that [Ru(bpy)₃]²⁺ can mediate the oxidation.In the range from 0.01 to 0.15 mmol·L^-1,peak currents for guanine oxidation mediated by [Ru(bpy)₃]²⁺ increased with the rise of DHP concentrations.On the contrary,cationic surfactant HTAC has the ability to weaken the mediated oxidation of guanine.In addition,the oxidative mechanism of guanine mediated by [Ru(bpy)₃]²⁺ with the participation of DHP …

The Mechanism Of Electrochemical Testing Method Under Synergistic Effect Of Nacl And Water Vapor At 600℃, Li Liu, Ying Li, Fu-Hui Wang

Journal of Electrochemistry

The existence of electrochemical reaction during the corrosion process of pure Fe under a deposit of solid NaCl in water vapor at above 400 ℃ had been detected by measuring the corrosion current using double-layer electrode.In EIS measurement,only one capacitive loop was obtained on the pure metals and this gave the information of oxide layer on them.The electrochemical impedance spectroscopy(EIS) and scanning-electron microscopy(SEM) results testified that there is a good relationship between the resistance of oxide layer Rox and the corresion reaction rate for pure metals with different oxidation times.The electrochemical technique is an effective method for studying corrosion performance …

A Theoretical Study Of Methanol Oxidation Mechanisms By Methanol Dehydrogenase Enzymes For Fuel Cell Applications, Nagesh B. Idupulapati

Doctoral Dissertations

Enzymes are considered for electrochemical generation of power in fuel cells. Methanol dehydrogenase (MDH) is one such enzyme, which has been used as an anodic catalyst for a methanol-fed biofuel cell producing enough power for small electronic device applications. In practice, however, there are power output limitations associated with this MDH fuel cell, which may potentially be eliminated or reduced if the reactivity of this enzyme during the oxidation of methanol at the molecular level is clearly understood.

Two mechanisms for the methanol oxidation process by MDH have been proposed in the literature, Addition-Elimination (A-E) and Hydride Transfer (H-T), but …

Kinetics Of Co Oxidation Over Pt-Ceo_X Supported On Air-Oxidized Activated Carbon, Berri̇n Gülyüz, Şeyma Özkara Aydinoğlu, Ahmet Erhan Aksoylu, Zeynep İlsen Önsan

Turkish Journal of Chemistry

Kinetics of low-temperature CO oxidation was studied under atmospheric pressure at 383 K in the initial rates region over 1wt%Pt-1wt%CeO_x supported on air-oxidized activated carbon (AC2). Feed concentrations of 1-5 mol% CO and 1-2.5 mol% O_2 with balance He were used for CO oxidation in the absence of hydrogen. A simple power-function rate expression was obtained with reaction orders of -0.24 in CO and 0.98 in O_2, and a plausible LHHW expression compatible with mechanisms reported in the literature was proposed. Feed concentrations of 5 mol% CO and 2.5 mol% O_2 were used for investigating the effect of the presence …

A Lab To Stemulate Undergraduate Students Into Science, Technology, Engineering And Mathematics Majors, Nicole Lynn Speelman

Browse all Theses and Dissertations

The central focus is the development and implementation of a research/lab module for first year chemistry courses. Electrochemical techniques are utilized to study oxidation and reduction reactions of neurotransmitters with a poly(2,2'-Bithiophene) modified electrode. The goal is to excite students about chemistry and encourage them to continue studies in Science, Technology, Engineering, and Mathematics (STEM) during their undergraduate education. The lab module was created for Project REEL (Research Experiences to Enhance Learning) and will be illustrated with results typically obtained by students. The experiment is inquiry-based, which includes challenging questions students have to do collaboration and research to answer, as …

Comparison Of The Electrochemical Properties Of Ethanol In Perchloric Acid And Ionic Liquids, Sandra Felix-Balderrama

Browse all Theses and Dissertations

1-Ethyl-3-Methylimidazolium Tetrafluroborate (EMImBF₄) and 1-Ethyl-3-Methylimidazlium Bis(trifluoromethanesulfonyl)imide (EMImTFSI) ionic liquids were synthesized and characterized in order to study the electrochemical oxidation of ethanol in these ionic liquids on a platinum surface electrode.

It was found that pure EMImBF₄ exhibits an electrochemical window of 4.4 V,while EMImTFSI exhibits an electrochemical window of 5.0 V.

Electrochemical study of ethanol in perchloric acid showed that the oxidation of ethanol strongly depends on the concentration of ethanol and on the temperature of the solution. The poisoning of the platinum electrode only depends on the concentration of ethanol. At a low concentration of …

Study Of Corrosion Of Materials In The Sulfur-Iodine Hydrogen Production Cycle, Thao Trung Ho

UNLV Theses, Dissertations, Professional Papers, and Capstones

Hydrogen is of great interest since the availability of traditional fossil fuels is in decline. Strictly speaking, hydrogen is not a primary source of energy but is an energy carrier, since energy typically must be used from another source (electricity, natural gas, coal, etc.) to produce it. Of hydrogen production techniques, the Sulfur-Iodine thermochemical water splitting process (S-I cycle), which was proposed by General Atomics (GA), is promising with its simplicity and high efficiency. Most of the chemicals are recycled except water. However, the S-I cycle operates in a harsh, corrosive environment in the presence of a mixture of iodine …

Synthesis And First X-Ray Structures Of Cobalt(Ii) And Cobalt(Iii) Complexes Bearing 2,4-Dioxo-Alkanoic Acid Dialkylamide Ligands, Brian Pagenkopf, Jian Wang, Nicholas A. Morra, Hongda Zhao, Vincent Lynch, Robert Mcdonald, John F. Reichwein

Chemistry Publications

The aerobic oxidation of 5-hydroxy pentenes to trans-tetrahydrofurans (THFs), the Mukaiyama oxidation, has in recent years emerged as a powerful tool in synthetic chemistry. In this report we describe the first crystal structures of 2,4-dioxo-alkanoic acid dialkylamide complexes for both Co(II) and Co(III) salts. The Co(II) structures show an unprecedented arrangement of atoms, with a central Co(II)(H₂O)₆ flanked by two Co(II) atoms each coordinated with three anionic chelating ligands. The dimeric Co(III) structures show two anionic chelating ligands and bridging hydroxyl groups.

Mass Spectrometry-Based High Throughput Approach For Identification Of Molecular Modification Of Oxidative Process In Respiratory Diseases, Wei Song

ETD Archive

Eosinophil peroxidase (EPO) and myeloperoxidase (MPO) have been implicated in generating reactive species and promoting oxidative modifications in numerous diseases. The detection and identification of potential pathways has been proven extremely challenge due to evanescence nature of these reactive species. An alternative approach to study the involvement of oxidative modification is to detect and quantify the stable molecular fingerprints, like oxidized tyrosine species, in biological matrices. Previously reported analytical methods for quantifying oxidized amino acids have typically been limited by: low sensitivity, specificity and the failure of detection potential oxidation products generated during sample handling. Using GC/MS in combination with …

Reactivity Of (2-Alkenyl-3-Pentene-1,5-Diyl)Iron Complexes: Preparation Of Functionalized Vinylcyclopropanes And Cycloheptadienes, Rajesh K. Pandey, Lizhu Wang, Nathaniel J Wallock, Sergey V. Lindeman, William A. Donaldson

Chemistry Faculty Research and Publications

The reactivity of (2-alkenyl-3-pentene-1,5-diyl)iron complexes toward olefin metathesis, cycloaddition, and mild oxidations (MnO₂ or mCPBA) was examined. Cycloaddition reactions were observed to occur with modest diastereoselectivity (33−63% de). Decomplexation of the (3-pentenediyl) ligand may be accomplished by oxidation with either CAN or alkaline hydrogen peroxide to afford vinylcyclopropanecarboxylates or divinylcyclopropanecarboxylates. Reduction of the latter, followed by Cope rearrangement generates cycloheptadienylmethanols. These studies demonstrate that (2-alkenyl-3-pentene-1,5-diyl)iron complexes can serve as organometallic scaffolds for the preparation of a wide variety of structural motifs containing up to 5 contiguous stereocenters.

Low Temperature Co Oxidation Kinetics Over Activated Carbon Supported Pt-Sno_X Catalysts, Fatma Soyal Baltacioğlu, Berri̇n Gülyüz, Ahmet Erhan Aksoylu, Zeynep İlsen Önsan

Turkish Journal of Chemistry

The kinetics of low temperature CO oxidation were studied over sequentially impregnated 1wt%Pt-0.25wt%SnO_x supported on HNO_3-oxidized activated carbon (AC3) using a wide range of CO (1-10 mol%) and O_2 (1-4 mol%) concentrations. Intrinsic kinetic data were obtained in the initial rates region at 383 K in the absence and presence of 5-45 mol% H_2 in the feed. A power-function rate expression with positive dependence on CO (0.96) and negative dependence on oxygen (--0.31) was obtained for the low temperature oxidation of CO. The effect of H_2 on CO oxidation rates was also investigated under similar conditions.

The Synthesis Of 2-(Chloromethyl)-6-Hydroxy-2h-Pyran-3 (6h)-One Via Achmatowicz Rearrangement, Zuhal Gerçek

Turkish Journal of Chemistry

Achmatowicz rearrangement was carried out with 2-chloro-1-(furan-2-yl) ethanol, which was synthesized starting from 1-(furan-2-yl) ethanone. It was shown that the oxidation of 2-chloro-1-(furan-2-yl) ethanol with m-CPBA produced 2-(chloromethyl)-6-hydroxy-2H-pyran-3 (6H)-one in good yield (70%).

Biochemical Investigations Of Macular Degeneration: The Significance Of Protein Oxidation Including Novel Methods For Its Study, Sarah Warburton

Theses and Dissertations

The retinal pigment epithelium (RPE) is a monolayer of cells located directly behind the photoreceptor cells in the retina. These cells are involved in a variety of functions that support the visual process in the eye, namely 1) they form a blood-retina barrier which separates the neural retina from the choroid's blood supply, 2) the apical processes of RPE cells diurnally phagocytose the outer segments of photoreceptor cells, and 3) they participate in the renewal of the photopigment 11-cis retinal. Age-related macular degneration (AMD) is the leading cause of blindness in people over the age of 50 years in North …

Oxidative Damage Caused By Iron Loading Into Ferritin, Talina Christensen Watts

Undergraduate Honors Capstone Projects

Ferritin is the iron storage protein found in humans, animals, plants, fungi and bacteria. We are interested in how iron is loaded and stored in mammalian ferritin. Ferrous iron must be oxidized to ferric iron in order to be stored in ferritin. It is generally believed that ferritin does the loading itself, dependant upon a "ferroxidase activity." Oxidation of iron can result in the production of the hydroxyl radical which can cause oxidative damage to surrounding proteins and other biomolecules. An indicator of oxidative damage to proteins is the formation of carbonyl groups. Using only the H subunit of human …

Origin Of Enantioselection In Chiral Alcohol Oxidation Catalyzed By Pd[(–)-Sparteine]Cl2, J. A. Mueller, Anne Cowell, Bert D. Chandler, M. S. Sigman

Chemistry Faculty Research

A kinetic investigation into the origin of enantioselectivity for the Pd[(–)-sparteine]Cl₂-catalyzed aerobic oxidative kinetic resolution (OKR) is reported. A mechanism to account for a newly discovered chloride dissociation from Pd[(–)-sparteine]Cl₂ prior to alcohol binding is proposed. The mechanism includes (1) chloride dissociation from Pd[(–)-sparteine]Cl₂ to form cationic Pd(–)-sparteine]Cl, (2) alcohol binding, (3) deprotonation of Pd-bound alcohol to form a Pd-alkoxide, and (4) β-hydride elimination of Pd–alkoxide to form ketone product and a Pd–hydride. Utilizing the addition of (–)-sparteine HCl to control the [Cl^–] and [H⁺] and the resulting derived rate law, …

Low-Temperature Activation Conditions For Pamam Dendrimer Templated Pt Nanoparticles, Anil Singh, Bert D. Chandler

Chemistry Faculty Research

Surface immobilized polyamidoamine (PAMAM) dendrimer templated Pt nanoparticles were employed as precursors to heterogeneous catalysts. CO oxidation catalysis and in situ infrared spectroscopy were used to evaluate conditions for dendrimer removal. Infrared spectroscopy showed thatPAMAMdendrimer amide bonds begin decomposing at temperatures as low as 75 °C. Although the amide stretches are completely removed after 3 h of oxidation at 300 °C, 16 h were required to reach maximum catalytic activity. Further treatment under oxidizing or reducing atmospheres did not cause substantial changes in activity. Infrared spectroscopy of the activated materials indicated that organic residues, probably surface carboxylates, are formed during …

Fast Oxidation Of Lactams To Cyclic Imides Using Microwave Irradiation, Avat Arman Taherpour, Hamid Reza Mansuri

Turkish Journal of Chemistry

Since polar reactants can adsorb microwave irradiation, chemists can utilize the microwave oven for some organic reactions. In this paper, we report a rapid conversion of lactams to cyclic imides using peracetic acid (CH_3-CO_3H) and manganic chloride (MnCl_2) in ethyl acetate (CH_3-COOEt) as a solvent and under microwave irradiation (90 W, 5 min) in good yields.

Synthesis And Characterization Of Dendrimer Templated Supported Bimetallic Pt-Au Nanoparticles, Huifang Lang, S. Maldonado, K. J. Stevenson, Bert D. Chandler

Chemistry Faculty Research

Bimetallic dendrimer-stabilized nanoparticles (DSNs) were used to prepare supported Pt-Au catalysts within the bulk miscibility gap for this binary system. Hydroxy-terminated generation 5 PAMAM dendrimers were used to prepare Cu0 nanoparticles (NPs). The Cu⁰ NPs were subsequently used to reduce K₂PtCl₄ and HAuCl₄, preparing stabilized bimetallic Pt-Au NPs with a 1:1 stoichiometry. The stabilized NPs were adsorbed onto a high surface area silica support and thermally activated to remove the dendrimers. Transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and infrared spectroscopy of adsorbed CO showed that this preparation route resulted in NPs in …

Characterization And Magnetic Properties Of Core/Shell Structured Fe/Au Nanoparticles, Sung-Jin Cho, Susan M. Kauzlarich, Justin Olamit, Kai Liu, Fernande Grandjean, Leïla Rebbouh, Gary J. Long

Chemistry Faculty Research & Creative Works

Au-coated Fe nanoparticles have been prepared by using a reverse micelle method through reduction of an aqueous solution. Characterizations have been carried out over time to probe the oxidation of Fe. Immediately after synthesis, the samples exhibit metallic conduction and a negative magnetoresistance, consistent with the presence of α-Fe. The temperature dependence of magnetization displays a maximum at a blocking temperature of around 150 K. After a period of 1 month, the samples exhibit insulating behavior, indicating the oxidation of the Fe core. Mössbauer spectroscopy indicates the presence of an α-Fe component and a broad distribution of local environments.

Dendrimer-Encapsulated Nanoparticle Precursors To Supported Platinum Catalysts, Huifang Lang, R Alan May, Brianna L. Iversen, Bert D. Chandler

Chemistry Faculty Research

In this contribution, we report the successful preparation of supported metal catalysts using dendrimer-encapsulated Pt nanoparticles as metal precursors. Polyamidoamine (PAMAM) dendrimers were first used to template and stabilize Pt nanoparticles prepared in solution. These dendrimer-encapsulated nanoparticles were then deposited onto a commercial high surface area silica support and thermally activated to remove the organic dendrimer. The resulting materials are active oxidation and hydrogenation catalysts. The effects of catalyst preparation and activation on activity for toluene hydrogenation and CO oxidation catalysis are discussed.

Modeling Corrosion In Oxygen Controlled Lbe Systems With Coupling Of Chemical Kinetics And Hydrodynamics - Phase Three, Samir Moujaes, Yitung Chen

Transmutation Sciences Materials (TRP)

The proposed work will combine chemical kinetics and hydrodynamics in target and test-loop lead-bismuth eutectic (LBE) systems to model system corrosion effects. This approach will result in a predicative tool that can be validated with corrosion test data, used to systematically design tests and interpret the results, and provide guidance for optimization in LBE system designs. The task includes two subtasks. The first subtask is to try to develop the necessary predictive tools to be able to predict the levels of oxygen and corrosion products close to the boundary layer through the use of Computational Fluid Dynamics (CFD) modeling. The …

Particle Growth In Urban And Industrial Plumes In Texas, Charles A. Brock, Michael Trainer, Thomas B. Ryerson, J. Andrew Neuman, David D. Parrish, John S. Holloway, Dennis K. Nicks, Gregory J. Frost, Gerhard Hübler, Fred C. Fehsenfeld, J. Charles Wilson, J. Michael Reeves, Bernard G. Lafleur, Henrike Hilbert, Elliot L. Atlas, Stephen G. Donnelly Ph.D., Sue M. Schauffler, Verity R. Stroud, Christine Wiedinmyer

Chemistry Faculty Publications

Particle size distributions and gas-phase particle precursors and tracer species were measured aboard an aircraft in the plumes downwind from industrial and urban sources in the vicinity of Houston, TX during the daytime in late August and early September 2000. Plumes originating from the Parish gas-fired and coal-fired power plant, petrochemical industries along the Houston ship channel, the petrochemical facilities near the Gulf coast, and the urban center of Houston were studied. Most of the particle mass flux advected downwind of Houston came from the industries and electrical utilities at the periphery of the city rather than from sources in …

Application Of Ibx Method For The Synthesis Of Ketones From Carboxylic Acids, H. R. Ferhat Karabulut, Mesut Kaçan, Hasan Özyildirim

Turkish Journal of Chemistry

Methoxy phenyl propionic acid and some derivatives are converted to ketones using a new method. All classical methods to obtain ketones from carboxylic acids via acid halide consistently gave very low yields and regularly generated intermolecular cyclisation products or polymeric materials. However, high ketones yields are obtained by using the new IBX method.

Kinetics And Mechanism Of Oxidation Of L-Isoleucine And L-Ornithine Hydrochloride By Sodium N-Bromobenzenesulphonamide In Perchloric Acid Medium, Hemmige S. Yathirajan, Chapuradoddi R. Raju, Kikkeri N. Mohana, Sheena Shashikanth, Padmarajaiah Nagaraja

Turkish Journal of Chemistry

Kinetic studies of the oxidation of L-isoleucine (ISL) and L-ornithine hydrochloride (ORH) by sodium N-bromobenzenesulphonamide (bromamine-B or BAB) were studied in aqueous perchloric acid medium. The rate shows first-order dependence on both [BAB]_0 and [amino acid]_0 and inverse first-order dependence on [H^+] for ISL and first-order dependence on [H^+] for ORH. The rate of reaction decreased with decreases in the dielectric constant of the medium. The addition of benzenesulphonamide (BSA), which is one of the reaction products, had no significant effect on the reaction rate. The rate remained unchanged with the variation in the ionic strength of the medium for …

Kinetics Of Oxidation Of Pyridylmethylsulphinylbenzimidazole By Cerium(Iv) In An Aqueous Perchloric Acid Medium, Dinesh C. Bilehal, Ravi̇raj M. Kulkarni, Sharanappa T. Nandibewoor

Turkish Journal of Chemistry

The kinetics of oxidation of pyridylmethylsulphinylbenzimidazole [PMSB] by Ce(IV) in an aqueous perchloric acid medium at a constant ionic strength of 1.50 mol dm^{-3} were studied spectrophotometrically. The reaction showed first order kinetics with respect to Ce(IV) concentration and an apparent less than unit order dependence in [PMSB] and a zero order in [H^+]. The initial addition of products has no significant effect on the rate of the reaction. A possible mechanism is proposed here. The reaction constants involved in the mechanism have been computed. There is good agreement between the observed and calculated rate constants under different experimental conditions. …