UNT Libraries - 126 Matching Results

Search Results

Effect of Fluorine and Hydrogen Radical Species on Modified Oxidized Ni(pt)si

Description: NiSi is an attractive material in the production of CMOS devices. The problem with the utilization of NiSi, is that there is no proper method of cleaning the oxide on the surface. Sputtering is the most common method used for the cleaning, but it has its own complications. Dry cleaning methods include the reactions with radicals and these processes are not well understood and are the focus of the project. Dissociated NF3 and NH3 were used as an alternative and XPS is the technique to analyze the reactions of atomic fluorine and nitrogen with the oxide on the surface. A thermal cracker was used to dissociate the NF3 and NH3 into NFx+F and NHx+H. There was a formation of a NiF2 layer on top of the oxide and there was no evidence of nitrogen on the surface indicating that the fluorine and hydrogen are the reacting species. XPS spectra, however, indicate that the substrate SiO2 layer is not removed by the dissociated NF3 and NiF2 growth process. The NiF2 over layer can be reduced to metallic Ni by reacting with dissociated NH3 at room temperature. The atomic hydrogen from dissociated ammonia reduces the NiF2 but it was determined that the atomic hydrogen from the ammonia does not react with SiO2.
Date: May 2010
Creator: Gaddam, Sneha Sen

Microwave-Assisted Synthesis, Characterization, and Photophysical Properties of New Rhenium(I) Pyrazolyl-Triazine Complexes

Description: The reaction of the chelating ligand 4-[4,6-bis(3,5-dimethyl-1H-pyrazol-1-yl)-1,3,5-triazin-2-yl]-N,N-diethyl-benzenamine, L, with pentacarbonylchlororhenium by conventional heating method produces the complexes fac-[ReL(CO)3Cl2] and fac-[Re2L(CO)6Cl2] in a period of 48 hours. The use of microwaves as the source of heat and the increase in the equivalents of one of the reactants leads to a more selective reaction and also decreases the reaction time to 1 hour. After proper purification, the photophysical properties of fac-[ReL(CO)3Cl] were analyzed. The solid-state photoluminescence analysis showed an emission band at 628 nm independent of temperature. However, in the solution studies, the emission band shifted from 550 nm in frozen media to 610 nm when the matrix became fluid. These results confirm that this complex possess a phenomenon known as rigidochromism.
Date: May 2010
Creator: Salazar Garza, Gustavo Adolfo

Computational Study of Small Molecule Activation via Low-Coordinate Late First-Row Transition Metal Complexes

Description: Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers is discussed. For (β-diket)Fe-N2 complexes, the additional influence of diketiminate donor atom (N(H) vs. S) is briefly addressed. The remainder of the chapter expands upon the treatment of β-diketiminate complexes. First, the activation and relative stabilities of side-bound and end-bound N2 isomers in monometallic ((β-diket)M-N2) and bimetallic ((β-diket)M-N2-M(β-diket)) first row transition metal complexes are addressed. Second, the thermodynamics of H/H+/H- addition to (β-diket)Fe-bound N2, followed by subsequent H additions up to release of ammonia, is discussed, for which two mechanisms (distal and alternating) are considered. Finally, the chapter concludes with partial distal and alternating mechanisms for H addition to N2 ...
Date: May 2010
Creator: Pierpont, Aaron

Sensitization of Lanthanides and Organic-Based Phosphorescence via Energy Transfer and Heavy-Atom Effects

Description: The major topics discussed are the phosphorescence sensitization in the lanthanides via energy transfer and in the organics by heavy atom effects. The f-f transitions in lanthanides are parity forbidden and have weak molar extinction coefficients. Upon complexation with the ligand, ttrpy (4'-p-Tolyl-[2,2':6',2"]-terpyridine) the absorption takes place through the ligand and the excitation is transferred to the lanthanides, which in turn emit. This process is known as "sensitized luminescence." Bright red emission from europium and bright green emission from terbium complexes were observed. There is ongoing work on the making of OLEDs with neutral complexes of lanthanide hexafluoroacetyl acetonate/ttrpy, studied in this dissertation. Attempts to observe analogous energy transfer from the inorganic donor complexes of Au(I) thiocyanates were unsuccessful due to poor overlap of the emissions of these systems with the absorptions of Eu(III) and Tb(III). Photophysics of silver-aromatic complexes deals with the enhancement of phosphorescence in the aromatics. The heavy atom effect of the silver is responsible for this enhancement in phosphorescence. Aromatics such as naphthalene, perylene, anthracene and pyrene were involved in this study. Stern Volmer plots were studied by performing the quenching studies. The quenchers employed were both heavy metals such as silver and thallium and lighter metal like potassium. Dynamic quenching as the predominant phenomenon was noticed.
Date: May 2010
Creator: Arvapally, Ravi K.

Podcast Effectiveness as Scaffolding Support for Students Enrolled in First-Semester General Chemistry Laboratories

Description: Podcasts covering essential first-semester general chemistry laboratory techniques and central concepts that aid in experimental design or data processing were prepared and made available for students to access on an as-needed basis on iPhones- or iPod touches-. Research focused in three areas: the extent of podcast usage, the numbers and types of interactions between instructors and research teams, and student performance on graded assignments. Data analysis indicates that the podcast treatment research teams accessed a podcast 2.86 times on average during each week that podcasts were available. Comparison of interaction data for the lecture treatment research teams and podcast treatment research teams reveals that interactions with instructors were statistically significantly fewer for teams that had podcast access rather than a pre‐laboratory lecture. The implication of the results is that student research teams were able to gather laboratory information more effectively when it was presented in an on-demand podcast format. Finally, statistical analysis of data on student performance on graded assignments indicates no significant differences between outcome measures for the treatment groups when compared as cohorts. The only statistically significant difference is between students judged to be highly motivated; for this sub‐group the students in the podcast treatment group earned a course average that was statistically significantly higher than those in the lecture treatment group. This research study provides some of the first data collected on the effectiveness of podcasts delivered as needed in a first-semester general chemistry laboratory setting.
Date: August 2010
Creator: Powell, Mary Cynthia Barton

Triimine Complexes of Divalent Group 10 Metals for Use in Molecular Electronic Devices

Description: This research focused on the development of new metal triimine complexes of Pt(II), Pd(II), and Ni(II) for use in three types of molecular electronic devices: dye sensitized solar cells (DSSCs), organic light-emitting diodes (OLEDs), and organic field effect transistors (OFETs). Inorganic complexes combine many advantages of their chemical and photophysical properties and are processable on inexpensive and large area substrates for various optoelectronic applications. For DSSCs, a series of platinum (II) triimine complexes were synthesized and evaluated as dyes for nanocrystalline oxide semiconductors. Pt (II) forms four coordinate square planar complexes with various co-ligands and counterions and leads to spanning absorption across a wide range in the UV-Vis-NIR regions. When those compounds were applied to the oxide semiconductors, they led to photocurrent generation thus verifying the concept of their utility in solar cells. In the OLEDs project, a novel pyridyl-triazolate Pt(II) complex, Pt(ptp)2 was synthesized and generated breakthrough OLEDs. In the solution state, the electronic absorption and emission of the square planar structure results in metal-to-ligand charge transfer (MLCT) and an aggregation band. Tunable photoluminescence and electroluminescence colors from blue to red wavelengths have been attained upon using Pt(ptp)2 under different experimental conditions and OLED architectures. In taking advantage of these binary characteristics for both monomer and excimer emissions, cool and warm white OLEDs suitable for solid-state lighting have been fabricated. The OFETs project represented an extension of the study of pyridyl-triazolate d8 metal complexes due to their electron-transporting behavior and n-type properties. A prescreening step by using thermogravimetric calorimetry has demonstrated the stability of all three M(ptp)2 and M(ptp)2(py)2 compounds and their amenability to sublimation. Preliminary current-voltage measurements from simple diodes has achieved unidirectional current from a Pt(ptp)2 neat layer and demonstrated its n-type semiconducting behavior.
Date: August 2010
Creator: Chen, Wei-Hsuan

Synthesis and Screening of a Combinatorial Peptide Library for Ligands to Target Transferrin: Miniaturizing the Library

Description: Combinatorial libraries are used in the search for ligands that bind to target proteins. Fmoc solid-phase peptide synthesis is routinely used to generate such libraries. Microwave-assisted peptide synthesis was employed here to decrease reaction times by 80-90%. Two One-Bead-One-Compound combinatorial libraries were synthesized on 130μm beads (one containing 750 members and the other 16, 807). The use of smaller solid supports would have many important practical advantages including; increased library diversity per unit mass, smaller quantities of library needed to generate hits, and screening could be conducted by using a standard flow cytometer. To this end, a miniaturized peptide library was synthesized on 20 μm beads to demonstrate proof of principle. A small sample from the 16,807-member library was screened against transferrin-AlexaFluro 647, a protein responsible for iron transport in vivo. A number of hits were identified and sequenced using techniques coupling nanomanipulation with nanoelectrospray mass spectrometry.
Date: August 2010
Creator: Brown, Jennifer Marie

The Pure Rotational Spectra of Diatomics and Halogen-Addition Benzene Measured by Microwave and Radio Frequency Spectrometers

Description: Two aluminum spherical mirrors with radii of 203.2 mm and radii of curvature also of 203.2 mm have been used to construct a tunable Fabry-Perót type resonator operational at frequencies as low as 500 MHz. The resonator has been incorporated into a pulsed nozzle, Fourier transform, Balle-Flygare spectrometer. The spectrometer is of use in recording low J transitions of large asymmetric molecules where the spectra are often greatly simplified compared to higher frequency regions. The resonators use is illustrated by recording the rotational spectra of bromobenzene and iodobenzene. In related experiments, using similar equipment, the pure rotational spectra of four isotopomers of SrS and all three naturally occurring isotopomers of the actinide-containing compound thorium monoxide have been recorded between 6 and 26 GHz. The data have been thoroughly analyzed to produce information pertaining to bond lengths and electronic structures.
Date: August 2010
Creator: Etchison, Kerry C.

Examining and Characterizing Changes in First Year High School Chemistry Curricula

Description: Many students currently entering college are able to solve mathematical problems but often do not understand the chemistry concepts underlying their calculations. High school chemistry teachers from Texas and the United States (US) were surveyed as to what topics they teach in their chemistry classes. A subset of Texas teachers was also interviewed about their instruction. The survey indicated that less-experienced Texas teachers are omitting a number of topics from their chemistry instruction, as compared to more experienced teachers. No differences were seen for those topics among US teachers. Chemistry textbooks from 1930 to the current 2002 Texas state adoptions were analyzed for inclusion of these topics. The only textbooks that were missing topics were from the 1930s. All others contained the topics. In general, textbooks have been increasing numbers of questions and problems for each topic, with the number of quantitative problems increasing at a greater rate than qualitative problems. Analysis of interview transcripts revealed that the main reason for omission of topics by less-experienced Texas chemistry teachers is that these topics are not assessed on the Texas Assessment of Knowledge and Skills science exam. Omitted topics were both qualitative and quantitative; the common factor is that they are not tested. School administrators reportedly reinforce this practice. Archival data regarding textbook usage by general chemistry students showed that students' course grades are not correlated to the amount of time they spend using their textbook. With topics included in textbooks, and no relationship between textbook usage and student grades, observed changes in chemistry courses must be due to changes in classroom instruction. With new course standards adopted by Texas for chemistry and the development of end-of-course exams, these changes should produce graduates who understand chemistry concepts as well as they solve mathematical chemistry problems. Repeating this study in 5 years ...
Date: August 2010
Creator: Holley, Kerry Kathleen McGee

Nanoparticles Engineered to Bind Serum Albumin: Microwave Assisted Synthesis, Characterization, and Functionalization of Fluorescently-Labeled, Acrylate-Based, Polymer Nanoparticles

Description: The potential use of polymeric, functionalized nanoparticles (NPs) as drug delivery vectors was explored. Covalent conjugation of albumin to the surface of NPs via maleimide chemistry proved problematic. However, microwave assisted synthesis of NPs was not only time efficient, but enabled the exploration of size control by changing the following parameters: temperature, microwave power, reaction time, initiator concentration, and percentage of monomer used. About 1.5 g of fluorescently-labeled, carboxylic acid-functionalized NPs (100 nm diameter) were synthesized for a total cost of less than $1. Future work will address further functionalization of the NPs for the coupling of albumin (or other targeted proteins), and tests for in vivo biodistribution.
Date: August 2010
Creator: Hinojosa, Barbara R.

Affordances of Instrumentation in General Chemistry Laboratories

Description: The purpose of this study is to find out what students in the first chemistry course at the undergraduate level (general chemistry for science majors) know about the affordances of instrumentation used in the general chemistry laboratory and how their knowledge develops over time. Overall, students see the PASCO™ system as a useful and accurate measuring tool for general chemistry labs. They see the probeware as easy to use, portable, and able to interact with computers. Students find that the PASCO™ probeware system is useful in their general chemistry labs, more advanced chemistry labs, and in other science classes, and can be used in a variety of labs done in general chemistry. Students learn the affordances of the probeware through the lab manual, the laboratory teaching assistant, by trial and error, and from each other. The use of probeware systems provides lab instructors the opportunity to focus on the concepts illustrated by experiments and the opportunity to spend time discussing the results. In order to teach effectively, the instructor must know the correct name of the components involved, how to assemble and disassemble it correctly, how to troubleshoot the software, and must be able to replace broken or missing components quickly. The use of podcasts or Web-based videos should increase student understanding of affordances of the probeware.
Date: August 2010
Creator: Sherman, Kristin Mary Daniels

Free Radical Chemistries at the Surface of Electronic Materials

Description: The focus of the following research was to (1) understand the chemistry involved in nitriding an organosilicate glass substrate prior to tantalum deposition, as well as the effect nitrogen incorporation plays on subsequent tantalum deposition and (2) the reduction of a native oxide, the removal of surface contaminants, and the etching of a HgCdTe surface utilizing atomic hydrogen. These studies were investigated utilizing XPS, TEM and AFM. XPS data show that bombardment of an OSG substrate with NH3 and Ar ions results in the removal of carbon species and the incorporation of nitrogen into the surface. Tantalum deposition onto a nitrided OSG surface results in the initial formation of tantalum nitride with continued deposition resulting in the formation of tantalum. This process is a direct method for forming a thin TaN/Ta bilayer for use in micro- and nanoelectronic devices. Exposure to atomic hydrogen is shown to increase the surface roughness of both air exposed and etched samples. XPS results indicate that atomic hydrogen reduces tellurium oxide observed on air exposed samples via first-order kinetics. The removal of surface contaminants is an important step prior to continued device fabrication for optimum device performance. It is shown here that atomic hydrogen effectively removes adsorbed chlorine from the HgCdTe surface.
Date: August 2010
Creator: Wilks, Justin

Free Radical Induced Oxidation, Reduction and Metallization of NiSi and Ni(Pt)Si Surfaces

Description: NiSi and Ni(Pt)Si, and of the effects of dissociated ammonia on oxide reduction was carried out under controlled ultrahigh vacuum (UHV) conditions. X-ray photoelectron spectroscopy (XPS) has been used to characterize the evolution of surface composition. Vicinal surfaces on NiSi and Ni(Pt)Si were formed in UHV by a combination of Ar+ sputtering and thermal annealing. Oxidation of these surfaces in the presence of either O+O2 or pure O2 at room temperature results in the initial formation of a SiO2 layer ~ 7 Å thick. Subsequent exposure to O2 yields no further oxidation. Continued exposure to O+O2, however, results in rapid silicon consumption and, at higher exposures, the kinetically-driven oxidation of the transition metal(s), with oxides >35Ǻ thick formed on all samples, without passivation. The addition of Pt retards but does not eliminate oxide growth or Ni oxidation. At higher exposures, in Ni(Pt)Si surface the kinetically-limited oxidation of Pt results in Pt silicate formation. Substrate dopant type has almost no effect on oxidation rate. Reduction of the silicon oxide/metal silicate is carried out by reacting with dissociated NH3 at room temperature. The reduction from dissociated ammonia (NHx+H) on silicon oxide/ metal silicate layer shows selective reduction of the metal oxide/silicate layer, but does not react with SiO2 at ambient temperature.
Date: August 2010
Creator: Manandhar, Sudha

Synthetic, Mechanistic, and Structural Studies of Polynuclear Metal Clusters and Hydrazido-Substituted Tantalum(V) Compounds

Description: A combined experimental and computational study on the reversible ortho-metalation exhibited by the triosmium cluster Os3(CO)10(dppm) (dppm = 1,1-bis(diphenylphosphino)methane is reported. The conversion of nonacarbonyl cluster HOs3(CO)9[-PhP(C6H4)CH2PPh2] to Os3(CO)10(dppm) is independent of added CO and exhibits a significant inverse equilibrium isotope effect (EIE). Reductive coupling of the C-H bond in HOs3(CO)9[-PhP(C6H4)CH2PPh2] leads to the formation of agostic C-H and two distinct aryl-π species prior to the rate-limiting formation of the unsaturated cluster Os3(CO)9(dppm). Heating the unsaturated dimer H2Re2(CO)8 with Cp*Rh(CO)2 (Cp* = 1,2,3,4,5-pentamethylcyclopentadiene) at elevated temperature affords the new trimetallic clusters H2RhRe2Cp*(CO)9 and HRh2ReCp*2(CO)6, and the spiked-triangular cluster HRhRe3Cp*(CO)14. H2Re2(CO)8 reacts with Cp*2Rh2(CO)2 under identical conditions to furnish H2RhRe2Cp*(CO)9 and HRh2ReCp*2(CO)6 as the principal products, in addition to the tetrahedral cluster H2Rh2Re2Cp*2(CO)8. H2RhRe2Cp*(CO)9 undergoes facile fragmentation in the presence of halogenated solvents and the thiols RSH (where R = H, C6H4Me-p) to afford the structurally characterized products Cp*Rh(-Cl)3Re(CO)3, S2Rh3Cp*(CO)4, Cp*Rh(-Cl)(-SC6H4Me-p)2Re(CO)3, and Cp*Rh(-SC6H4Me-p)3Re(CO)3. The new hydrazido-substituted compounds TaCl(NMe2)3[N(TMS)NMe2] (TMS = tetramethylsilyl) and Ta(NMe2)4[N(TMS)NMe2] have been synthesized and their structures established by X-ray crystallography. The latter product represents the first structurally characterized octahedral tantalum(V) complex containing a single hydrazido(I) ligand in an all-nitrogen coordinated environment about the metal center. The fluxional properties of the amido and hydrazido ligands in these new compounds have been established by VT 1H NMR spectroscopy (VT = variable temperature). Preliminary data using Ta(NMe2)4[N(TMS)NMe2] as an ALD (ALD = atomic layer deposition) precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.
Date: December 2010
Creator: Huang, Shih-huang

Soft Landing Ion Mobility Mass Spectrometry: History, Instrumentation and an Ambient Pressure Application

Description: Preparative mass spectrometry is an important method for the synthesis of new materials. Recently, soft landing mass spectrometry has been used to land ions on surfaces to coat or otherwise alter them. Commercial soft landing instruments do not yet exist, and the physical phenomenon of soft landing has not yet been fully described. For future ion mobility soft landing research, the theory of ion mobility, ion optics and soft landing is discussed, and 2 soft landing instruments have been built and described, along with proof of concept experiments for both instruments. Simulations of the process of ion mobility and ion optics for use in these instruments, as well as some preliminary results for the optics are included. Surfaces described include copper on mica and iron on silicon. Self assembly of soft landed ions is observed on the surfaces. The instruments constructed will be useful for future soft landing research, and soft landing can be used for future materials research with special attention focused on the self-assembly of the landed ions.
Date: December 2010
Creator: Birdwell, David

Syntheses, X-ray Diffraction Structures, and Kinetics on New Formamidinate-Substituted Triosmium Clusters

Description: The reaction between the formamidine ligand PriN=CHNHPri and the activated cluster Os3(CO)10(MeCN)2 has been studied. A rapid reaction is observed at room temperature, yielding the hydride clusters HOs3(CO)9[μ-OCNPriC(H)NPri] and HOs3(CO)10[μ-NPriC(H)NPri] as the principal products. The spectroscopic data and X-ray diffraction structures of those formamidinate-substituted clusters will be present. The thermal reactivity of the clusters has been investigated, with the face-capped cluster HOs3(CO)9[μ-NPriC(H)NPri] found as the sole observable product. The relationship between these three clusters has been established by kinetic studies, the results of which will be discussed.
Date: December 2010
Creator: Yang, Li

Examination and Development of the Correlation Consistent Composite Approach

Description: The primary focus of this dissertation is the advancement of the correlation consistent composite approach (ccCA) methodology from its original formulation to the current implementation. Although for large main group test sets which contained both first- (Li-Ne) and second-row (Na-Ar) species ccCA produced chemical accuracy (generally estimated as a deviation of ~1 kcal mol-1 from reliable experiment), the second-row species were smaller in molecular size in comparison to their corresponding first-row species. Previous theoretical work has shown that the accuracy for theoretical calculations involving second-row species (specifically sulfur-containing species) are more basis set dependent than first-row species. Therefore, an analysis of the accuracy of ccCA for sulfur-containing species is warranted. The ccCA methodology is used to evaluate both enthalpies of formation and bond dissociation energies of sulfur-containing species as well as examine isomerization energies for three sets of sulfur-containing isomers. During the testing of ccCA for sulfur-containing species two observations were made which led to further investigations. First, there is no agreement between different theoretical methodologies on the lowest energetic isomer between SNO and NSO. In fact, G3 and G3B3 which differ only by the geometry of the single-point calculations do not agree on the lowest isomer. For this reason, larger, more complete theoretical treatments of SNO and NSO are investigated. Second, for open-shell sulfur-containing systems the accuracy of the ccCA methodology begins to degrade when spin-contamination becomes non-negligible. Therefore, we investigate the accuracy of the ccCA methodology when spin-contamination is removed from the wavefunction. Finally, the ccCA methodology is utilized in a multilayer ONIOM approach as the high level of theory in conjunction with density functional theory as the low level for the C-H bond dissociation energies of anthracene and fluorene analogues.
Date: December 2010
Creator: Williams, T. Gavin

Forensic Science Applications Utilizing Nanomanipulation-Coupled to Nanospray Ionization-Mass Spectrometry for the Analysis of Ultra-Trace Illicit Drugs

Description: Presented in this thesis are two methods that are coupled to the instrumentation for the recovery and analysis of ultra-trace illicit drug residues. The electrostatic dust lifting process is coupled with nanomanipulation-nanospray ionization to retrieve drug particles off of hard surfaces for analysis. For the second method, drug residues from fingerprint impressions are extracted followed by analysis. The methodology of these hyphenated techniques toward forensic science applications is applied as to explore limits of detection, sensitivity, and selectivity of analytes as well as immediacy and efficiency of analysis. The application of nanomanipulation-coupled to nanospray ionization-mass spectrometry toward forensic science based applications is considered as future improvements to trace and ultra-trace analysis.
Date: December 2010
Creator: Wallace, Nicole

Investigating Molecular Structures: Rapidly Examining Molecular Fingerprints Through Fast Passage Broadband Fourier Transform Microwave Spectroscopy

Description: Microwave spectroscopy is a gas phase technique typically geared toward measuring the rotational transitions of Molecules. The information contained in this type of spectroscopy pertains to a molecules structure, both geometric and electronic, which give insight into a molecule's chemistry. Typically this type of spectroscopy is high resolution, but narrowband ≤1 MHz in frequency. This is achieved by tuning a cavity, exciting a molecule with electromagnetic radiation in the microwave region, turning the electromagnetic radiation o, and measuring a signal from the molecular relaxation in the form of a free induction decay (FID). The FID is then Fourier transformed to give a frequency of the transition. "Fast passage" is defined as a sweeping of frequencies through a transition at a time much shorter (≤10 s) than the molecular relaxation (≈100 s). Recent advancements in technology have allowed for the creation of these fast frequency sweeps, known as "chirps", which allow for broadband capabilities. This work presents the design, construction, and implementation of one such novel, high-resolution microwave spectrometer with broadband capabilities. The manuscript also provides the theory, technique, and motivations behind building of such an instrument. In this manuscript it is demonstrated that, although a gas phase technique, solids, liquids, and transient species may be studied with the spectrometer with high sensitivity, making it a viable option for many molecules wanting to be rotationally studied. The spectrometer has a relative correct intensity feature that, when coupled with theory, may ease the difficulty in transition assignment and facilitate dynamic chemical studies of the experiment. Molecules studied on this spectrometer have, in turn, been analyzed and assigned using common rotational spectroscopic analysis. Detailed theory on the analysis of these molecules has been provided. Structural parameters such as rotational constants and centrifugal distortion constants have been determined and reported for most molecules in ...
Date: May 2011
Creator: Grubbs, Garry Smith, II

Effects of Using Logic and Spatial Cybergames to Improve Student Success Rates in Lower-Division Chemistry Courses

Description: A study was conducted to investigate the relationships between cybergaming treatment groups and the control group (N = 99: ncontrol = 8; nlogic = 29; nspatial = 30; ncombination = 32) with success in the organic chemistry I course as measured by achievement over a 10-week period. The treatment groups included logic training, spatial training, and combination logic-spatial training. Students' ability was measured by pre/post exams using the Group Assessment of Logical Thinking (GALT) to measure logic ability, Purdue Visualizations of Rotations (ROT) test to measure spatial skills, and the General-Organic-Biochemistry (GOB) Exam to measure content attainment. Finally, students' responses about participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. A second study was conducted to evaluate the relationship between the cybergaming treatment and control groups (N = 88: nexperimental = 27; ncontrol = 61) with success in the general chemistry I course as measured by achievement and final course averages and grades. The cybergaming treatment group underwent intensive combination logic-spatial training for 10 weeks. Students' progress was measured using three pre/post instruments: Group Assessment of Logical Thinking (GALT) measured logic ability, Purdue Visualizations of Rotations (ROT) Test measured spatial skills, and the California Chemistry Diagnostic Exam measured content attainment. Finally, students' responses about their participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. Analyses of the data were performed to determine the relationships between cybergaming treatments and control groups in organic chemistry I and general chemistry I courses. In organic chemistry I results showed no statistical or practical significance as to students' success. In general chemistry I results indicated statistical significance and medium practicality for students with an average grade of C and for females over males as to improvement of spatial skills.
Date: May 2011
Creator: Manrique, Carissa Janice

Characterization of Novel Solvents and Absorbents for Chemical Separations

Description: Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models were created to standard deviations of 0.198 and 0.122 logunits for gas-to-PDMS wet and dry, respectively, as well as 0.164 and 0.134 log units for water-to-PDMS wet and dry, respectively. These models are particularly useful in solid phase microextraction separations. Micelles were studied to create predictive models of the measured micelle-water partition coefficient as well as models of measured MEKC chromatographic retention factors for CTAB and SDS. The resultant predictive models were created with standard deviations of 0.190 log units for the logarithm of the mole fraction concentration of water-to-CTAB, 0.171 log units for the combined logarithms of both the ...
Date: May 2011
Creator: Grubbs, Laura Michelle Sprunger

The Development of an Analytical Microwave Electromagnetic Pulse Transmission Probe and Preliminary Test Results

Description: Within this educational endeavor instrumental development was explored through the investigation of microwave induce stable electromagnetic waves within a non-linear yttrium iron garnet ferromagnetic waveguide. The resulting magnetostatic surface waves were investigated as a possible method of rapid analytical evaluation of material composition. Initial analytical results indicate that the interaction seen between wave and material electric and magnetic fields will allow phase coherence recovery andanalysis leading to enhancement of analytical value. The ferromagnetic waveguide selected for this research was a high quality monocrystalline YIG (yttrium iron garnet) film. Magnetostatic spin waves (MSW) were produced within the YIG thin waveguide. Spin waves with desired character were used to analytically scan materials within the liquid and solid phase.
Date: May 2011
Creator: Griffith, William Francis

Synthesis and Characterization of Copper Releasing Polymer Nanoparticles

Description: Polymeric nanoparticles were synthesized and loaded with Cu²⁺ to explore the therapeutic potential for catically active transition metal ions and complexes other than cisplatin. Two types of nanoparticles were synthesized to show the potential for polymer based vectors. Copper loading and release were characterized via inductively coupled plasma mass spectrometry (ICP MS), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis. Results demonstrated that Cu could be loaded to the nano-sized carriers in an aqueous environment, and that the release was pH-dependent. The toxicity of these particles was measured in HeLa cells where significant toxicity was observed in vitro via dosing of high Cu-loaded nanoparticles. No significant toxicity was observed in cells dosed with Cu-free nanoparticles.
Date: May 2011
Creator: Harris, Alesha N.

Surface Chemical Deposition of Advanced Electronic Materials

Description: The focus of this work was to examine the direct plating of Cu on Ru diffusion barriers for use in interconnect technology and the substrate mediated growth of graphene on boron nitride for use in advanced electronic applications. The electrodeposition of Cu on Ru(0001) and polycrystalline substrates (with and without pretreatment in an iodine containing solution) has been studied by cyclic voltammetry (CV), current-time transient measurements (CTT), in situ electrochemical atomic force microscopy (EC-AFM), and X-ray photoelectron spectroscopy (XPS). The EC-AFM data show that at potentials near the OPD/UPD threshold, Cu crystallites exhibit pronounced growth anisotropy, with lateral dimensions greatly exceeding vertical dimensions. XPS measurements confirmed the presence and stability of adsorbed I on the Ru surface following pre-treatment in a KI/H2SO4 solution and following polarization to at least −200 mV vs. Ag/AgCl. CV data of samples pre-reduced in I-containing electrolyte exhibited a narrow Cu deposition peak in the overpotential region and a UPD peak. The kinetics of the electrodeposited Cu films was investigated by CTT measurements and applied to theoretical models of nucleation. The data indicated that a protective I adlayer may be deposited on an air-exposed Ru electrode as the oxide surface is electrochemically reduced, and that this layer will inhibit reformation of an oxide during the Cu electroplating process. A novel method for epitaxial graphene growth directly on a dielectric substrate of systematically variable thickness was studied. Mono/multilayers of BN(111) were grown on Ru(0001) by atomic layer deposition (ALD), exhibiting a flat (non-nanomesh) R30(3x3) structure. BN(111) was used as a template for growth of graphene by chemical vapor deposition (CVD) of C2H4 at 1000 K. Characterization by LEED, Auger, STM/STS and Raman indicate the graphene is in registry with the BN substrate, and exhibits a HOPG-like 0 eV bandgap density-of-states (DOS).
Date: December 2010
Creator: Bjelkevig, Cameron