Chemistry Commons^™

Biofuels: A Hands-On Approach, Learning The Potential Of Utilizing Non-Food Sources, Alexandra Ham, Gabrielle Pecora, Hoaithuong Bui, Timothy Camarella, Victor Pham, Marc Ting

Student Research Posters

The global energy economy is huge and thoughts of replacing large amounts of petroleum based fuels by massive levels of fermentation of grains are not realistic. On an energy basis what global agriculture produces for food will almost cover the energy demands if all of it is redirected to the production of fuels—either as alcohols for gasoline or as fat derivatives for diesel fuel. This means that chemical processes need to be developed that allow inclusion of non-food based agricultural and urban wastes as well as forest debris into the energy economy. These represent opportunities to capture new sources of …

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 …

Chasing Μ, Joseph P. Cannon

Doctoral Dissertations

Conducting and semiconducting, π-conjugated polymers are promising materials for micro- and nano-optoelectronic applications because of their widely tunable physical, electrical, and optical properties. These polymers have been used to fabricate a number of electronic devices including field-effect transistors, light-emitting diodes, and photovoltaic cells. However, widespread commercial application of these devices has yet to be realized, due in part to poor electronic transport characteristics and device degradation.

Nanostructuring of conjugated polymers by various methods has demonstrated marked improvements in molecular ordering and electronic transport. In this research, nanoscale, tubular structures of semiconducting polymers fabricated by template wetting nanofabrication procedures are explored. …

Computational Study Of Pristine And Titanium-Doped Sodium Alanates For Hydrogen Storage Applications, Gopi Krishna Phani Dathar

Doctoral Dissertations

The emphasis of this research is to study and elucidate the underlying mechanisms of reversible hydrogen storage in pristine and Ti-doped sodium aluminum hydrides using molecular modeling techniques. An early breakthrough in using complex metal hydrides as hydrogen storage materials is from the research on sodium alanates by Bogdanovic et al., in 1997 reporting reversible hydrogen storage is possible at moderate temperatures and pressures in transition metal doped sodium alanates. Anton reported titanium salts as the best catalysts compared to all other transition metal salts from his further research on transition metal doped sodium alanates. However, a few questions remained …

Kinetic Studies On Enzyme-Catalyzed Reactions: Oxidation Of Glucose, Decomposition Of Hydrogen Peroxide And Their Combination, Zhimin Tao, Ryan A. Raffel, Abdul-Kader Souid, Jerry Goodisman

Chemistry - All Scholarship

The kinetics of the glucose oxidase-catalyzed reaction of glucose with O2, which produces gluconic acid and hydrogen peroxide, and the catalase-assisted breakdown of hydrogen peroxide to generate oxygen, have been measured via the rate of O2 depletion or production. The O2 concentrations in air-saturated phosphate-buffered salt solutions were monitored by measuring the decay of phosphorescence from a Pd phosphor in solution; the decay rate was obtained by fitting the tail of the phosphorescence intensity profile to an exponential. For glucose oxidation in the presence of glucose oxidase, the rate constant determined for the rate-limiting step was k = (3.0 ± …

Optical Properties Of Multilayer-Polyelectrolyte Films With Incorporated Gold Nanomaterials (Solid Nanoparticles And Hollow Nanoshells), Robert Watson Day

Honors Theses

The growth of various multilayer‐polymer multilayer‐nanoparticle films was successfully achieved. Multilayer‐polymer multilayer‐nanoparticle films with 1, 3, and 5 polymer layers between nanoparticle layers exhibit significantly different optical properties due to the differences in magnitude of particle plasmon coupling. These film systems were also successfully extended to hollow gold nanoshells, which have significantly enhanced optical properties in comparison to solid gold nanoparticles of similar sizes. A proposal for utilizing this increased sensitivity of the gold nanoshells to explore the ‘microenvironments’ for optimizing potential sensing applications is also presented.

Frequency And Isostericity Of Rna Base Pairs, Craig L. Zirbel, Jesse Stombaugh, Eric Westhof

Chemistry Faculty Publications

Most of the hairpin, internal and junction loops that appear single-stranded in standard RNA secondary structures form recurrent 3D motifs, where non-WatsonCrick base pairs play a central role. Non-WatsonCrick base pairs also play crucial roles in tertiary contacts in structured RNA molecules. We previously classified RNA base pairs geometrically so as to group together those base pairs that are structurally similar (isosteric) and therefore able to substitute for each other by mutation without disrupting the 3D structure. Here, we introduce a quantitative measure of base pair isostericity, the IsoDiscrepancy Index (IDI), to more accurately determine which base pair substitutions can …

N- And C-Terminal Domains In Human Holocarboxylase Synthetase Participate In Substrate Recognition, Yousef I. Hassan, Hideaki Moriyama, Lars J. Olsen, Xin Bi, Janos Zempleni

Hideaki Moriyama Publications

Holocarboxylase synthetase (HCS) catalyzes the binding of the vitamin biotin to carboxylases and histones. Carboxylases mediate essential steps in macronutrient metabolism. For example, propionyl- CoA carboxylase (PCC) catalyzes the carboxylation of propionyl-CoA in the metabolism of oddchain fatty acids. HCS comprises four putative domains, i.e., the N-terminus, the biotin transfer/ATP binding domain, a putative linker domain, and the C-terminus. Both N- and C-termini are essential for biotinylation of carboxylases by HCS, but the exact functions of these two domains in enzyme catalysis are unknown. Here we tested the hypothesis that N- and C-termini play roles in substrate recognition by HCS. …

Inside Unlv, Shane Bevell, Diane Russell, Michelle Mouton, Gian Galassi

Inside UNLV

No abstract provided.

Volume 02, Joseph A. Mann, Kathryn J. Greenly, Scott E. Jenkins, Andrew E. Puckette, Daniel M. Honey, Jeffery P. Ravenhorst, Jamie Elizabeth Mesrobian, Thomas Scott, Jay Crowell, Sarah Spangenberg, Amy S. Eason, Kenny Wolfe, Liz Hale, Rachel Bouchard, Will Semonco, Carley York, Ryan Higgenbothom, Adrienne Heinbaugh, Melissa Dorton, Madeline Hunter, June Ashmore, Clark Barkley, Jay Haley

Incite: The Journal of Undergraduate Scholarship

Introduction from Dean Dr. Charles Ross

Mike's Nite: New Jazz for an Old Instrument by Joseph A. Mann

Investigation of the use of Cucumis Sativus for Remediation Of Chromium from Contaminated Environmental Matrices: An Interdisciplinary Instrumental Analysis Project by Kathryn J. Greenly, Scott E. Jenkins, and Andrew E. Puckette

Development of GC-MS and Chemometric Methods for the Analysis of Accelerants in Arson Cases by Scott Jenkins

Building and Measuring Scalable Computing Systems by Daniel M. Honey and Jeffery P. Ravenhorst

Nomini Hall: A Case Study in the Use of Archival Resources as Guides for Excavation at An Archaeological Site by …

Microwave-Assisted Ruthenium Trichloride-Catalyzed Synthesis Of Pyrrole Fused With Indole System In Water, Debasish Bandyopadhyay, Antara Banik, Sahil Bhatta, Bimal K. Banik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

A simple and efficient microwave-induced ruthenium trichloride-catalyzed synthesis of pyrrole fused with indole system in water is developed by reacting commercially available isatin and 4-hydroxyproline.

Variation Of Benzyl Anions In Mgal-Layered Double Hydroxides: Fire And Thermal Properties In Pmma, Calistor Nyambo, Dan Chen, Shengpei Shu, Charles A. Wilkie

Chemistry Faculty Research and Publications

Magnesium aluminum layered double hydroxides (MgAl-LDHs) intercalated with a range of benzyl anions were prepared using the coprecipitation method. The benzyl anions differ in functionality (i.e. carboxylate, sulfonate, and phosphonate) and presence or absence of an amino substituent. Various methods for preparing LDHs (i.e. ion exchange, coprecipitation and rehydration of the calcined LDH methods) have been compared with the MgAl-benzene phosphonate and their effect on fire and thermal properties was studied. After characterization, the MgAl-LDHs were melt-blended with poly(methyl methacrylate) (PMMA) at loadings of 3 and 10% by weight to prepare composites. Characterization of the LDHs and the PMMA composites …

The Role Of The Trivalent Metal In An Ldh: Synthesis, Characterization And Fire Properties Of Thermally Stable Pmma/Ldh Systems, Charles Manzi-Nshuti, Dongyan Wang, Jeanne Hossenlopp, Charles A. Wilkie

Chemistry Faculty Research and Publications

Two layered double hydroxides (LDHs), calcium aluminum undecenoate (Ca₃Al) and calcium iron undecenoate (Ca₃Fe), have been prepared by the co-precipitation method. XRD analysis of these LDHs reveals that they are layered materials and FT-IR and TGA confirmed the presence of the undecenoate anions in the material produced. The PMMA composites were prepared by bulk polymerization and the samples were characterized by XRD, TEM, TGA and cone calorimetry. Both additives greatly enhance the thermal stability of PMMA, while the calcium aluminum LDH gives better results when the fire properties were examined using the cone calorimeter.

Thermal Stability And Flammability Characteristics Of Ethylene Vinyl Acetate (Eva) Composites Blended With A Phenyl Phosphonate-Intercalated Layered Double Hydroxide (Ldh), Melamine Polyphosphate And/Or Boric Acid, Calistor Nyambo, Everson Kandare, Charles A. Wilkie

Chemistry Faculty Research and Publications

A phenyl phosphonate-intercalated MgAl–LDH (MgAl–PPh), melamine polyphosphate (MP), and boric acid (BA) were independently and concomitantly added to neat ethylene vinyl acetate (EVA) copolymer at loading fractions of 10% (w/w). The structural morphology of MgAl–PPh was established via powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM) while the presence of phenyl phosphonate in the galleries was confirmed by Fourier transform infrared (FTIR). Thermogravimetric analysis (TGA) and cone calorimetry were used to evaluate the thermal stability and flammability behavior of EVA and its composites. While time-to-ignition is greatly reduced for EVA composites compared to the virgin polymer, there are remarkable …

Layered Double Hydroxides Intercalated With Borate Anions: Fire And Thermal Properties In Ethylene Vinyl Acetate Copolymer, Calistor Nyambo, Charles A. Wilkie

Chemistry Faculty Research and Publications

Fire and thermal properties of ethylene vinyl acetate (EVA) composites prepared by melt blending with layered double hydroxides (LDH) have been studied. Two types of LDHs intercalated with borate anion were prepared using the coprecipitation method and the metals Mg²⁺, Zn²⁺ and Al³⁺. Characterization of the LDHs and the EVA composites was performed using X-ray diffraction, thermogravimetric analysis, and cone calorimetry. Thermal analyses show that the addition of LDHs improves the thermal stability of EVA. Fire properties evaluated using the cone calorimeter were significantly improved in the EVA/LDH composites. The peak heat release rate was …

Biodiesel: Tomorrow's Fuel, Today's Solution, Roberto J. Molina, Racheal A. Persuad

Undergraduate Research Conference

Study of physical and chemical properties of biodiesel fuels derived from poultry and plant fats.

Stereospecific Enzyme Isolation From Carrots, Jacqueline Greer, Eileen Rigsby

Undergraduate Research Conference

No abstract provided.

Spectroscopic Studies Of Fluoranthene And 3-Nitrofluoranthene, Matthew Parks

Undergraduate Research Conference

Polycyclic aromatic hydrocarbons (PAHs) are known byproducts of anthropogenic sources including incomplete combustion of fossil fuels. They are known to be teratogenic, mutagenic and carcinogenic. This study investigated the spectral properties of fluoranthene and 3- nitrofluoranthene using NMR, UV-Vis and infrared techniques. The acquisition of spectral data provides a means to identify these compounds in mixtures and can be used which to develop model formulae for quantitation. A 2-D NMR method (HMQC ) was used for assigning 13C peaks. The infrared spectrum for 3-nitrofluoranthene showed characteristic strong absorption peaks at 1323 and 1516 cm-1 assigned to symmetric/asymmetric nitro stretches, respectively. …

Light-Regulated Sampling Of Protein Kinase Activity (Ii), Collaborative Project

Dyson College- Seidenberg School of CSIS : Collaborative Projects and Presentations

This entry adheres to the use of the quad chart template to provide a succinct description only of the current research project undertaken by the participants. It provides for the following information

1. Participants and Affiliations
2. Overall Project Goals
3. Illustrative picture
4. Specific research/artistic/pedagogic foci

Mammaglobin As A Potential Molecular Target For Breast Cancer Drug Delivery, Lian Zuo, Ly Li, Qian Wang, Timothy P. Fleming, Shaojin You

Faculty Publications

Background Mammaglobin (MAM) has been used as a specific molecular marker for breast cancer diagnosis. Recently, several groups of researchers proposed a number of therapeutic strategies targeting this molecule. Some of the strategies are based upon an essential but not demonstrated hypothesis - mammaglobin is associated with the surface of breast cancer cells, which strongly disputes the therapeutic strategies. Results We conducted a computer-based predictive analysis and identified a small fragment at the N-end of MAM as a potential transmembrane domain. We provided several evidences to demonstrate the presence of the membrane-associated MAM. We isolated the membrane protein components from …

Functionalization, Characterization, And Applications Of Diamond Particles, Modification Of Planar Silicon, And Chemoetrics Analysis Of Ms Data, Li Yang

Theses and Dissertations

In spite of the stablility (lack of reactivity) of diamond powder, I have developed a method for tethering alkyl chains and polymers to deuterium/hydrogen-terminated diamond. One method is through ether linkages via thermolysis of di-tert-amyl peroxide (DTAP). This reaction with DTAP has also been applied to grow polymers on the diamond surface. The other method is atom transfer radical polymerization (ATRP), which was applied to grow polystyrene at the surface of diamond. Both polystyrene-modified diamond and sulfonated polystyrene-modified diamond can be prepared by either method, and can be used for solid phase extraction. Diamond stationary phases are stable under basic …

The First Attachment And Post-Functionalization Of Polybutadiene And Thio-Click Functionalized Polybutadiene On H-Terminated Si(111), Todd Devere Wickard

Theses and Dissertations

I report the attachment of polymers with pendant vinyl groups to hydrogen-terminated silicon(111) (Si(111)-H) under mild conditions. 1,2-addition polybutadiene (Mw 3200-3500) was attached to Si(111)-H at room temperature with visible light. I also report the partial functionalization, in solution, of 1,2-addition polybutadiene with various thiols using thiol-click chemistry. These compounds bind to Si(111)-H via visible light activation. The partially functionalized polybutadienes allow further functionalization at the surface through unreacted carbon-carbon double bonds. Surfaces were characterized with contact angle goniometry, spectroscopic ellipsometry, X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and atomic force microscopy (AFM).

An Evaluation Of The Natural Radionuclides, Be-7, Pb-210, Po-210, And Bi-210, As Tracers Of Atmospheric Aerosols, Gunawan Gunawan

Theses and Dissertations

The natural radionuclides (7Be, 210Pb, 210Bi, 210Po) in fine aerosols are useful tracers to understand their tropospheric transport and removal. Aerosol samples were collected at UALR and The University of Chicago. The concentrations and ratios of 7Be and 210Pb in atmospheric aerosols vary seasonally consistent with their sources. The 7Be shows stronger correlation with black carbon than the 210Pb. In contrast, the 210Pb shows stronger correlation with the rain levels than the 7Be. The distribution coefficient (Kd) was used to evaluate the binding strength between the natural radionuclides and atmospheric aerosols in water to mimic atmospheric washout. The Kd values …

Tobacco Mosaic Virus Templated Synthesis Of One Dimensional Inorganic–Polymer Hybrid Fibres, Jianhua Rong, Fiona Oberbeck, Xinnan Wang, Xiaodong Li, Jerry Oxsher, Zhongwei Niu, Qian Wang

Faculty Publications

Inorganic–polymer hybrid nanofibres were prepared by using a rod-like tobacco mosaic virus (TMV) as a template. With tetraethylorthosilicate (TEOS) as a precursor, long silica-coated TMVfibres were formed via a head-to-tail assembly, which showed a substantial increase of the elastic modulus. Furthermore, homogenous titania–TMV hybrid fibres could be prepared using polyaniline-coated TMV fibres as a template, which were used to form a composite film that was able to sense liquefied petroleum gases.

Inactivation Of [Fe-Fe]-Hydrogenase By O2. Thermodynamics And Frontier Molecular Orbitals Analyses, Daniela Dogaru, Stefan Motiu, Valentin Gogonea

Chemistry Faculty Publications

The oxidation of H-cluster in gas phase, and in aqueous enzyme phase, has been investigated by means of quantum mechanics (QM) and combined quantum mechanics–molecular mechanics (QM/MM). Several potential reaction pathways (in the above-mentioned chemical environments) have been studied, wherein only the aqueous enzyme phase has been found to lead to an inhibited hydroxylated cluster. Specifically, the inhibitory process occurs at the distal iron (Fed) of the catalytic H-cluster (which isalso the atom involved in H2 synthesis). The processes involved in the H-cluster oxidative pathways are O2 binding, e− transfer, protonation, and H2O removal. We found that oxygen binding is …

Catena-Poly[[(Pyridine-Κn)Copper(Ii)]-Μ3-Pyridine-2,6-Dicarboxylato-Κ3o2:O2′,N,O6:O6′], Manoj Trivedi, Daya Pandey, Nigam Rath

Chemistry & Biochemistry Faculty Works

In the title compound, [Cu(C7H3NO4)(C5H5N)]n, the CuII atom is in a slightly distorted octa­hedral coordination environment. Each CuII atom is bound to two N atoms and one O atom of the pyridine­dicarboxyl­ate (PDA) ligand in a tridentate manner, one N atom of the pyridine mol­ecule and two bridging carboxyl­ate O atoms of adjacent PDA ligands, leading to a linear one-dimensional chain running along the c axis. These chains are further assembled via weak C-H...O and [pi]-[pi] inter­actions into a three-dimensional supra­molecular network structure. The centroid-centroid distance between the [pi]-[pi] inter­acting pyridine rings is 3.9104 (13) Å. The two N atoms …

Polyelectrolyte-Linked Film Assemblies Of Nanoparticles And Nanoshells: Growth, Stability, And Optical Properties, Anne A. Galyean, Justin Malinowski, Robert W. Day, Kevin W. Kittredge, Michael C. Leopold

Chemistry Faculty Publications

Multi-layer films of nanoparticles and nanoshells featuring various polymeric linkage molecules have been assembled and their optical properties characterized. The growth dynamics, including molecular weight effects, and stability of the various nanoparticle film constructions, using both single polymer as well as combinations of alternating charge polyelectrolytes as linking mechanisms, are presented. The polymeric linkers studied include poly-L-lysine, poly-L-arginine, poly(allylamine hydrochloride), and polyamidoamine dendrimers. Significantly air stable films were achieved with the use of multi-layered polymeric bridges between the nanoparticles and nanoshells. Optical sensitivity normally observed with these nanomaterials in solution was observed for their corresponding film geometries, with the nanoshell …

Role Of The Oxyferrous Heme Intermediate And Distal Side Adduct Radical In The Catalase Activity Of Mycobacterium Tuberculosis Katg Revealed By The W107f Mutant, Xiangbo Zhao, Shengwei Yu, Kalina Ranguelova, Javier Suarez, Leonid Metlitsky, Johannes Schelvis, Richard S. Magliozzo

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Catalase-peroxidase (KatG) is essential in Mycobacterium tuberculosis for oxidative stress management and activation of the antitubercular pro-drug isoniazid. The role of a unique distal side adduct found in KatG enzymes, involving linked side chains of residues Met255, Tyr229, and Trp107 (MYW), in the unusual catalase activity of KatG is addressed here and in our companion paper (Suarez, J., Ranguelova, K., Jarzecki, A. A., Manzerova, J., Krymov, V., Zhao, X., Yu, S., Metlitsky, L., Gerfen, G. J., and Magliozzo, R. S. (2009) J. Biol. Chem. 284, in press). The KatG[W107F] mutant exhibited severely reduced catalase activity yet normal peroxidase activity, and …

The Effective Potential Energy Surfaces Of The Nonadiabatic Collision B(2PJA) + H2(1Σ+G,Ν,J) ↔ B(2PJ'A) + H2(1Σ+G,Ν',J'), Matthew B. Garvin

Theses and Dissertations

Effective potential energy surfaces (PESs) are calculated for a nonadiabatic collision . This calculation employed 1 ²A', 2 ²A' and 1 ²A" adiabatic PESs numerically calculated at the state-averaged multiconfigurational self-consistent field (SA-MCSCF)/configuration interaction (CI) level for several values of the H₂ bond length, H₂ orientation angle, and boron distance. The associated nonadiabatic coupling terms (NACTs) were calculated from the SA-MCSCF/CI wave functions using analytic gradient techniques. A line integral through the NACTs was then used to determine the adiabatic-to-diabatic mixing angle required to transform from the 1 ²A' and 2 ²A' …

Q-Switched And Mode Locked Short Pulses From A Diode Pumped, Yb-Doped Fiber Laser, Seth M. Swift

Theses and Dissertations

A diode-pumped, ytterbium (Yb)-doped fiber laser system was designed and demonstrated to operate in continuous wave (cw), passively Q-switched and possibly passively mode locked operation. To our knowledge, this was the first fiber laser oscillator built at the Air Force Institute of Technology. A Cr⁴⁺:YAG (Chromium: Ytterbium Aluminum Garnett) crystal was used as a saturable absorber to generate Q-switched pulses. Attempts to mode lock the laser were performed using a semiconductor saturable absorber mirror (SESAM) and through nonlinear polarization rotation (NPR). The best output power result was 5 Watts (W) while pumping at 8.3 W, yielding 60% efficiency …