Chemistry Commons^™

Method And Apparatus For Jet-Assisted Drilling Or Cutting, David A. Summers, Klaus Woelk, Kenneth Doyle Oglesby, Greg Galecki

Mining Engineering Faculty Research & Creative Works

An abrasive cutting or drilling system, apparatus and method, which includes an upstream supercritical fluid and/or liquid carrier fluid, abrasive particles, a nozzle and a gaseous or low-density supercritical fluid exhaust abrasive stream. The nozzle includes a throat section and, optionally, a converging inlet section, a divergent discharge section, and a feed section.

Spectroscopy And Dynamics Of The Predissociated, Quasi-Linear S₂ State Of Chlorocarbene, Chong Tao, Craig A. Richmond, Calvin Mukarakate, Scott H. Kable, George B. Bacskay, Eric C. Brown, Richard Dawes, Phalgun Lolur, Scott A. Reid

Chemistry Faculty Research & Creative Works

In this work, we report on the spectroscopy and dynamics of the quasi-linear S₂ state of chlorocarbene, CHCl, and its deuterated isotopologue using optical-optical double resonance (OODR) spectroscopy through selected rovibronic levels of the S₁ state. This study, which represents the first observation of the S₂ state in CHCl, builds upon our recent examination of the corresponding state in CHF, where pronounced mode specificity was observed in the dynamics, with predissociation rates larger for levels containing bending excitation. In the present work, a total of 14 S₂ state vibrational levels with angular momentum 1 were observed …

Dynamical Reaction Pathways In Eley-Rideal Recombination Of Nitrogen From W(100), Ernesto Quintas-Sánchez, P. Larrégaray, C. Crespos, L. Martin-Gondre, J. Rubayo-Soneira, J. C. Rayez

Chemistry Faculty Research & Creative Works

The scattering of atomic nitrogen over a N-pre-adsorbed W(100) surface is theoretically described in the case of normal incidence off a single adsorbate. Dynamical reaction mechanisms, in particular Eley-Rideal (ER) abstraction, are scrutinized in the 0.1-3.0 eV collision energy range and the influence of temperature on reactivity is considered between 300 and 1500 K. Dynamics simulations suggest that, though non-activated reaction pathways exist, the abstraction process exhibits a significant collision energy threshold (0.5 eV). Such a feature, which has not been reported so far in the literature, is the consequence of a repulsive interaction between the impinging and the pre-adsorbed …

Templated Synthesis Of Nylon Nucleic Acids And Characterization By Nuclease Digestion, Yu Liu, Risheng Wang, Liang Ding, Roujie Sha, Nadrian C. Seeman, James W. Canary

Chemistry Faculty Research & Creative Works

Nylon nucleic acids containing oligouridine nucleotides with pendent polyamide linkers and flanked by unmodified heteronucleotide sequences were prepared by DNA templated synthesis. Templation was more efficient than the single-stranded synthesis; coupling step yields were as high as 99.2%, with up to 7 amide linkages formed in the synthesis of a molecule containing 8 modified nucleotides. Controlled digestion by calf spleen phosphodiesterase enabled the mapping of modified nucleotides in the sequences. a combination of complete degradation of nylon nucleic acids by snake venom phosphodiesterase and dephosphorylation of the resulting nucleotide fragments by bacterial alkaline phosphatase, followed by LCMS analysis, clarified the …

Separation And Liquid Chromatography Using A Single Carbon Nanotube, Riju Singhal, Vadym Mochalin, Maria R. Lukatskaya, Gary Friedman, Yury G. Gogotsi

Chemistry Faculty Research & Creative Works

Use of a single template-grown carbon nanotube as a separation column to separate attoliter volumes of binary mixtures of fluorescent dyes has been demonstrated. The cylindrical nanotube walls are used as stationary phase and the surface area is increased by growing smaller multi-walled carbon nanotubes within the larger nanotube column. Liquid-liquid extraction is performed to separate selectively soluble solutes in a solvent, and chromatographic separation is demonstrated using thin, long nanotubes coated inside with iron oxide nanoparticles. The setup is also used to determine the diffusion coefficient of a solute at the sub-micrometer scale. This study opens avenues for analytical …

Neutron Repulsion, Oliver Manuel

Chemistry Faculty Research & Creative Works

Earth is connected gravitationally, magnetically and electrically to its heat source and the source of its chemical elements - a neutron star obscured from view by waste products in the photosphere. Neutron repulsion makes the solar core like the hot filament in an incandescent light bulb. Excited neutrons are emitted from the pulsar, decay to hydrogen, and partially fuse into the helium now trapped with it in the photosphere, like a frosted light bulb. Neutron repulsion is the overlooked source of energy, the keystone of an arch that locks together many earlier, puzzling observations: 1.) Excess ¹³⁶Xe accompanied primordial …

Histological Evaluation Of The Biocompatibility Of Polyurea Crosslinked Silica Aerogel Implants In A Rat Model: A Pilot Study, Firouzeh Sabri, J. D. Boughter Jr., D. Gerth, O. Skalli, T. C. N. Phung, G. R. M. Tamula, Nicholas Leventis

Chemistry Faculty Research & Creative Works

Background: Aerogels are a versatile group of nanostructured/nanoporous materials with physical and chemical properties that can be adjusted to suit the application of interest. In terms of biomedical applications, aerogels are particularly suitable for implants such as membranes, tissue growth scaffolds, and nerve regeneration and guidance inserts. The mesoporous nature of aerogels can also be used for diffusion based release of drugs that are loaded during the drying stage of the material. From the variety of aerogels polyurea crosslinked silica aerogels have the most potential for future biomedical applications and are explored here. Methodology: This study assessed the short and …

N-Acetyl-L-Cysteine Amide Protects Retinal Pigment Epithelium Against Methamphetamine-Induced Oxidative Stress, Nuran Ercal, Joshua W. Carey, Shakila Tobwala, Xinsheng Zhang, Atrayee Banerjee, Eylem Y. Pinarci, Humeyra Karacal

Chemistry Faculty Research & Creative Works

Methamphetamine (METH), a highly addictive drug used worldwide, induces oxidative stress in various animal organs. Recent animal studies indicate that methamphetamine also induces oxidative stress in the retina, which is an em- bryonic extension of the forebrain. The aim of this study, therefore, was to evaluate the pro- tecttive effects of N-acetylcysteine amide (NACA) against oxidative stress induced by METH in retinal pigment epithelium (RPE) cells. Our stud- ies showed that NACA protected against METH- induced oxidative stress in retinal pigment epithelial cells. Although METH significantly de- creased glutathione (GSH) levels and increased reactive oxygen species (ROS) and malondial- dehyde …

Organic And Composite Aerogels Through Ring Opening Metathesis Polymerization (Romp), Dhairyashil Mohite

Doctoral Dissertations

"Aerogels are open-cell nanoporous materials, unique in terms of low density, low thermal conductivity, low dielectric constants and high acoustic attenuation. Those exceptional properties stem from their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles), but they also come at a cost: low mechanical strength. This issue has been resolved by crosslinking silica aerogels with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework by covalent bridging elementary building blocks. However, "assuming" is not enough: for correlating nanostructure with bulk material properties, it is important to know …

X-Ray Crystallography For The Study Of Nickel And Iron Salicylaldimines, Carla Schmiesing Eribal

Doctoral Dissertations

"X-ray diffraction of single crystals has developed dramatically over the last century by combining fundamental theories of light, diffraction, and statistics to generate the complete, geometric structure of molecules. The quality of the resulting X -ray structure data are reported in R₁ < 5%, wR2 < 12% and a goodness of fit value of one. This technique was applied specifically to the evaluation of the spin crossover (SCO) compound [Fe(salpm)₂]BF₄ʺ0.5EtOH and how the molecule's geometry changed during a two-step thermal LS-HS conversion. The crystal structure was measured at 100,175,225, and 296 K to yield final R₁ values of 0.047, 0.054, 0.051, and 0.058, respectively. The coordination bond lengths show the spin transitions occur between 100-175K at one crystallographically unique Fe and between 175-225K at the other Fe site. No strong long range interactions are found, suggesting a gradual spin transition. Reaction ofNi(Nalkyl-sal)₂ complexes with Ni(N0₃)₂ form either nickel dimeric, [Ni₃(Rsal)(N0₃)(MeOH)]₂ or trinuclear complexes, Ni₃(Rsal)₄(N0₃)₂. The binuclear complexes, with orthogonal bridging ligands, show overall ferromagnetic interactions. The crystal structures for Ni₃(Rsal)₄(N0₃)₂ from methyl to benzyl were solved and indicate no steric restriction on formation for the series. The trinuclear compounds form an isosceles triangle of metal atoms with the isopropyl analog showing an overall antiferromagnetic interaction with J=+11.386 and J23=-13.891. Lastly, xanthene spirolactam derivatives were structurally analyzed to determine binding modes for their selective and sensitive (µM) detection of metals Cr³⁺, Fe³⁺, Ni²⁺, Co²⁺ and the nerve gas mimic, dichlorophosphate"--Abstract, page iii.

Nano-Particles Induced Oxidative Stress In Immortalized Human Brain Endothelial Cells, Xinsheng Zhang

Doctoral Dissertations

"Nanoparticles are engineered structure with at least one dimension of 100 nanometers or less. These materials are increasingly being used for commercial purposes such as catalyst, semiconductor, cosmetics, microelectronic, and drug carrier. However, the toxicological impact of these materials has not yet been studied in detail, thereby limiting their use. In our present study, we use human brain endothelial cell line as a blood-brain barrier (BBB) model to investigate if two kinds of nanoparticles [ 1). Diesel exhaust particles (DEPs) and 2). single wall carbon nanotube (CNT) ] induced oxidative stress in cell model. Our studies showed that DEPs or …

Investigation Of Polyurea-Crosslinked Silica Aerogels As A Neuronal Scaffold: A Pilot Study, Firouzeh Sabri, Judith A. Cole, M. Cody Scarbrough, Nicholas Leventis

Chemistry Faculty Research & Creative Works

Background: Polymer crosslinked aerogels are an attractive class of materials for future implant applications particularly as a biomaterial for the support of nerve growth. The low density and nano-porous structure of this material combined with large surface area, high mechanical strength, and tunable surface properties, make aerogels materials with a high potential in aiding repair of injuries of the peripheral nervous system. However, the interaction of neurons with aerogels remains to be investigated. Methodology: In this work the attachment and growth of neurons on clear polyurea crosslinked silica aerogels (PCSA) coated with: poly-L-lysine, basement membrane extract (BME), and laminin1 was …

Electrodeposition And Electrochemical Reduction Of Epitaxial Metal Oxide Thin Films And Superlattices, Zhen He

Doctoral Dissertations

"The focus of this dissertation is the electrodeposition and electrochemical reduction of epitaxial metal oxide thin films and superlattices. The electrochemical reduction of metal oxides to metals has been studied for decades as an alternative to pyrometallurgical processes for the metallurgy industry. However, the previous work was conducted on bulk polycrystalline metal oxides. Paper I in this dissertation shows that epitaxial face-centered cubic magnetite (Fe₃O₄) thin films can be electrochemically reduced to epitaxial body-centered cubic iron (Fe) thin films in aqueous solution on single-crystalline Au substrates at room temperature. This technique opens new possibilities to produce special epitaxial metal/metal oxide …

Quantitative Analysis Of Co-Enzyme A In A Plant Tissues And Cancer Biomarkers In Urine Samples By Using Capillary Electrophoresis And Liquid Chromatography-Mass Spectrometry, Yongqing Jiang

Doctoral Dissertations

"Despite continuous effort and progress in cancer detection and therapy, cancer remains one of our greatest health concerns because of its low survival rate and rapid incidence increase. One reason for this is the late detection and therefore pre-cancer diagnosis is crucial. In pre-cancer studies, cancer biomarkers become significant because of the useful information it contains such as possible cancer type and stage. Separation and detection technique plays an important role in cancer biomarker identification.

Coenzyme A (CoA) facilitates more than 100 chemical reactions in cells. Because of its low abundance accumulated in cells, it is critical to develop a …

Investigation Of Biomarkers For Noninvasive Early Diagnosis Of Cancer, Sanjeewa Bandara Gamagedara

Doctoral Dissertations

"Cancer is the second leading cause of death worldwide, and deaths from cancer worldwide are projected to continue rising, with an estimated 12 million deaths in 2030. Cancer occurs when cells in a part of the body begin to grow out of control. It develops very rapidly, and early diagnosis offers a greater chance of successful treatment and a higher survival rate. Biomarkers are good potential tools for early diagnosis. The main hypothesis of this study is that the levels of certain metabolites present in human urine can indicate the current or future behavior of cancer. Therefore, these studies focused …

Part I: Quantitative Determination Of Total Corrosive Sulfur In Mineral Insulating Oils And Technical Liquids; Part Ii: Development And Validation Of A Broad Spectrum Microbial Disinfectant, Kyle Rodney Anderson

Doctoral Dissertations

"Part one of this dissertation deals with the development and validation of a test method for determination of total corrosive sulfur in mineral insulating oils other technical oils. The method involved reaction of corrosive sulfur compounds in oils with finely divided copper at temperatures ≥ 110 °C. The reaction yielded cuprous sulfide (Cu₂S), Cu₂S was then oxidized to cupric sulfate (CuSO₄), which was determined as sulfate with ion chromatography. The method offers a quantitative assessment of corrosive sulfur compounds in oils and eliminates ambiguities associated with the international standard methods for corrosive sulfur in mineral insulating oils and other technical …

Therapeutic Effects Of N-Acetylcysteine Amide In The Treatment Of Eye Disorders, Joshua W. Carey

Doctoral Dissertations

"The loss of vision from age-related eye diseases now affects over 30 million people in the United States and is expected to reach twice that number within the next couple of decades. Among these disorders, age-related macular degeneration and cataract formation represent the largest percentage of these cases. Therapeutic options available for treating age-related macular degeneration are limited and there is no noninvasive form of treatment for cataracts current available. Several studies have indicated that oxidative stress plays an important role in the pathology of these age-related eye disorders. If oxidative stress is responsible for the initiation and progression of …

Chelating Compounds As Potential Flash Rust Inhibitors And Melamine & Aziridine Cure Of Acrylic Colloidal Unimolecular Polymers (Cups), Jigar K. Mistry

Doctoral Dissertations

Waterborne coatings on ferrous substrates usually show flash rusting which decreases the adhesion of the coating and the corrosion products can form a stain. Chelating compounds were investigated as potential flash rust inhibitors. Compounds being evaluated include amine alcohols, diamines and sulfur containing amines. A new corrosion inhibitor 2,5-bis(thioaceticacid)-1,3,4-thiadiazole (H2ADTZ) was synthesized and its performance characteristics were evaluated. It was noted that the observed structure of 1,3,4-thiadiazolidine-2,5-dithione (also known as 2,5-dimercapto-1,3,4-thiadiazole (DMTD or DMcT)) has been previously reported in three different tautomeric forms including -dithiol and -dithione. The relative stability of each form as well as the synthesis and characterization …