The field of spintronics offers perspectives for seamless integration of coupled and inter-tunable electrical and magnetic properties in a single device. For integration of the spin degree of freedom with current electronic technology, new semiconductors are needed that show electrically-tunable magnetic properties at room temperature and above. Dilute magnetic semiconductors derived from III-V compounds, like GaMnAs and InMnAs, show coupled and tunable magnetic, transport, and optical properties, due to the fact that their ferromagnetism is hole-mediated. These unconventional materials are ideal systems for manipulating the magnetic order by changing the carrier polarization, population density, and energy band distribution of the complementary subsystem of holes. This is the main theme we cover in this thesis. In particular, we develop a unique setup by use of ultraviolet pump, near-infrared probe femtosecond laser pulses, that allows for magneto-optical Kerr effect (MOKE) spectroscopy experiments. We photo-excite transient carriers in our samples, and measure the induced transient magnetization dynamics. One set of experiments performed allowed us to observe for the first time enhancement of the ferromagnetic order in GaMnAs, on an ultrafast time scale of hundreds of picoseconds. The corresponding transient increase of Curie temperature (Tc, the temperature above which a ferromagnetic material loses its …

Thesis analyzing a lead-glass photon spectrometer and its use in studying the absorption of photons and antinucleons.

Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.

This dissertation describes a measurement of the neutrino oscillation parameters #1;{Delta}m{sup 2}{sub 21}, θ{sub 12} and constraints on θ{sub 13} based on a study of reactor antineutrinos at a baseline of ∼ 180 km with the KamLAND detector. The data presented here was collected between April 2002 and November 2009, and amounts to a total exposure of 2.64 � 0.07 � 10{sup 32} proton-years. For this exposure we expect 2140 � 74(syst) antineutrino candidates from reactors, assuming standard model neutrino behavior, and 350�88(syst) candidates from background. The number observed is 1614. The ratio of background-subtracted candidates observed to expected is (N{sub Obs} − N{sub Bkg})/N{sub Exp} = 0.59 � 0.02(stat) � 0.045(syst) which confirms reactor neutrino disappearance at greater than 5σ significance. Interpreting this deficit as being due to neutrino oscillation, the best-fit oscillation parameters from a three-flavor analysis are #1;{Delta}m{sup 2}{sub 21} = 7.60{sup +0.20}{sub −0.19}�10{sup −5}eV{sup 2}, θ{sub 12} = 32.5 � 2.9 degrees and sin{sup 2} θ{sub 13} = 0.025{sup +0.035}{sub −0.035}, the 95% confidence-level upper limit on sin{sup 2} θ{sub 13} is sin{sup 2} θ{sub 13} < 0.083. Assuming CPT invariance, a combined analysis of KamLAND and solar neutrino data yields best-fit values: #1;{Delta}m{sup 2}{sub 21} …

Organic chemistry has served as a solid foundation for interdisciplinary research areas, such as molecular biology and medicinal chemistry. An understanding of the biological activities and structural elucidations of natural products can lead to the development of clinically valuable therapeutic options. The advancements of modern synthetic methodologies allow for more elaborate and concise natural product syntheses. The theme of this study centers on the synthesis of natural products with particularly challenging structures and interesting biological activities. The synthetic expertise developed here will be applicable to analog syntheses and to other research problems.

Superaustenitic stainless steels constitute a group of Fe-based alloys that are compositionally balanced to have a purely austenitic matrix and exhibit favorable pitting and crevice corrosion resistant properties and mechanical strength. However, intermetallic precipitates such as sigma and Laves can form during casting or exposure to high-temperature processing, which degrade the corrosion and mechanical properties of the material. The goal of this study was to accurately characterize the solid-solid phase transformations seen in cast superaustenitic stainless steels. Heat treatments were performed to understand the time and temperature ranges for intermetallic phase formations in alloys CN3MN and CK3MCuN. Microstructures were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and energy and wavelength dispersive spectroscopy (EDS, WDS). The equilibrium microstructures, composed primarily of sigma and Laves within purely austenitic matrices, showed slow transformation kinetics. Factors that determine the extent of transformation, including diffusion, nucleation, and growth, are discussed.

Arynes are among the most intensively studied systems in chemistry. However, many aspects of the chemistry of these reactive intermediates are not well understood yet and their use as reagents in synthetic organic chemistry has been somewhat limited, due to the harsh conditions needed to generate arynes and the often uncontrolled reactivity exhibited by these species. Recently, o-silylaryl triflates, which can generate the corresponding arynes under very mild reaction conditions, have been found very useful in organic synthesis. This thesis describes several novel and useful methodologies by employing arynes, which generate from o-silylaryl triflates, in organic synthesis. An efficient, reliable method for the N-arylation of amines, sulfonamides and carbamates, and the O-arylation of phenols and carboxylic acids is described in Chapter 1. Amines, sulfonamides, phenols, and carboxylic acids are good nucleophiles, which can react with arynes generated from a-silylaryl triflates to afford the corresponding N- and O-arylated products in very high yields. The regioselectivity of unsymmetrical arynes has also been studied. A lot of useful, functional groups can tolerate our reaction conditions. Carbazoles and dibenzofurans are important heteroaromatic compounds, which have a variety of biological activities. A variety of substituted carbazoles and dibenzofwans are readily prepared in good to excellent …

This thesis consists of six sections. The first section gives the basic research background on the ionic conduction mechanism in glass, polarization in the glass, and the method of determining the mobile carrier density in glass. The proposed work is also included in this section. The second section is a paper that characterizes the structure of MI + M{sub 2}S + (0.1 Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2}) (M = Li, Na, K and Cs) glasses using Raman and IR spectroscopy. Since the ionic radius plays an important role in determining the ionic conductivity in glasses, the glass forming range for the addition of different alkalis into the basic glass forming system 0.1 Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2} was studied. The study found that the change of the alkali radius for the same nominal composition causes significant structure change to the glasses. The third section is a paper that investigates the ionic conductivity of MI + M{sub 2}S + (0.1Ga{sub 2}S{sub 3} + 0.9 GeS{sub 2}) (M = Li, Na, K and Cs) glasses system. Corresponding to the compositional changes in these fast ionic conducting glasses, the ionic conductivity shows changes due to the induced structural changes. …

Left unprotected, both transmissive and reflective final optics in a laser-driven inertial fusion power plant would quickly fail from melting, pulsed thermal stress, or degradation of optical properties as a result of ion implantation. One potential option for mitigating this threat is to magnetically deflect the ions such that they are directed to a robust energy dump. In this paper we detail integrated studies that have been carried out to assess the viability of this approach for protecting final optics.

In this work, they try to understand the protein folding problem using pair-wise hydrophobic interaction as the dominant interaction for the protein folding process. They found a strong correlation between amino acid sequences and the corresponding native structure of the protein. Some applications of this correlation were discussed in this dissertation include the domain partition and a new structural threading method as well as the performance of this method in the CASP5 competition. In the first part, they give a brief introduction to the protein folding problem. Some essential knowledge and progress from other research groups was discussed. This part includes discussions of interactions among amino acids residues, lattice HP model, and the design ability principle. In the second part, they try to establish the correlation between amino acid sequence and the corresponding native structure of the protein. This correlation was observed in the eigenvector study of protein contact matrix. They believe the correlation is universal, thus it can be used in automatic partition of protein structures into folding domains. In the third part, they discuss a threading method based on the correlation between amino acid sequences and ominant eigenvector of the structure contact-matrix. A mathematically straightforward iteration scheme provides …

Organic electronic materials are a new class of emerging materials. Organic light emitting devices (OLEDs) are the most promising candidates for future flat panel display technologies. The photophysical characterization is the basic research step one must follow to understand this new class of materials and devices. The light emission properties are closely related to the transport properties of these materials. The objective of this dissertation is to probe the relation between transport and photophysical properties of organic semiconductors. The transport characteristics were evaluated by using thermally stimulated current and thermally stimulated luminescence techniques. The photoluminescence detected magnetic resonance and photoluminescence quantum yield studies provide valuable photophysical information on this class of materials. OLEDs are already in the market. However, detailed studies on the degradation mechanisms are still lacking. Since both optically detected magnetic resonance and thermal activation spectroscopy probe long-lived defect-related states in organic semiconductors, the combined study generates new insight on the OLED operation and degradation mechanisms.

This dissertation comprises two main research projects. The first project, presented in Chapter 1, involves the synthesis and thermochemistry of germacyclobutanes (germetanes). Four new germetanes (spirodigermetane, diallylgermetane, dichlorogermetane, and germacyclobutane) have been synthesized using a modified di-Grignard synthesis. Diallylgermetane is shown to be a useful starting material for obtaining other germetanes, particularly the parent germetane, germacyclobutane. The gas-phase thermochemistries of spirodigermetane, diallylgermetane and germacyclobutane have been explored via pulsed stirred-flow reactor (SFR) studies, showing remarkable differences in decomposition, depending on the substitution at the germanium atom. The second project investigates the thermochemical, photochemical, and catalytic additions of several digermanes to acetylenes. The first examples of thermo- and photochemical additions of Ge-Ge bonds to C{triple_bond}C are demonstrated. Mechanistic investigations are described and comparisons are made to analogous disilane addition reactions, previously studied in their group.

The objectives of this research were to further characterize exotic by adapted corn inbreds by studying the impact of environment on their starch thermal properties, and investigating the development of starch thermal properties during kernel maturation by using differential scanning calorimetry (DSC). A method to expedite identification of unusual starch thermal traits was investigated by examining five corn kernels at a time, instead of one kernel, which the previous screening methods used. Corn lines with known thermal functions were blended with background starch (control) in ratios of unique starch to control starch, and analyzed by using DSC. Control starch was representative of typical corn starch. The values for each ratio within a mutant type were unique ({alpha} < 0.01) for most DSC measurements. These results supported the five-kernel method for rapidly screening large amounts of corn germplasm to identify unusual starch traits. The effects of 5 growing locations on starch thermal properties from exotic by adapted corn and Corn Belt lines were studied using DSC. The warmest location, Missouri, generally produced starch with greater gelatinization onset temperature (T{sub oG}), narrower range of gelatinization (R{sub G}), and greater enthalpy of gelatinization ({Delta}H{sub G}). The coolest location, Illinois, generally resulted in starch …

Organic Light-Emitting Devices (OLEDs), both small molecular and polymeric have been studied extensively since the first efficient small molecule OLED was reported by Tang and VanSlyke in 1987. Burroughes' report on conjugated polymer-based OLEDs led to another track in OLED development. These developments have resulted in full color, highly efficient (up to {approx} 20% external efficiency 60 lm/W power efficiency for green emitters), and highly bright (> 140,000 Cd/m{sup 2} DC, {approx}2,000,000 Cd/m{sup 2} AC), stable (>40,000 hr at 5 mA/cm{sup 2}) devices. OLEDs are Lambertian emitters, which intrinsically eliminates the view angle problem of liquid crystal displays (LCDs). Thus OLEDs are beginning to compete with the current dominant LCDs in information display. Numerous companies are now active in this field, including large companies such as Pioneer, Toyota, Estman Kodak, Philipps, DuPont, Samsung, Sony, Toshiba, and Osram, and small companies like Cambridge Display Technology (CDT), Universal Display Corporation (UDC), and eMagin. The first small molecular display for vehicular stereos was introduced in 1998, and polymer OLED displays have begun to appear in commercial products. Although displays are the major application for OLEDs at present, they are also candidates for nest generation solid-state lighting. In this case the light source needs …

In this dissertation, they have undertaken the challenge to understand the unusual propagation properties of the photonic crystal (PC). The photonic crystal is a medium where the dielectric function is periodically modulated. These types of structures are characterized by bands and gaps. In other words, they are characterized by frequency regions where propagation is prohibited (gaps) and regions where propagation is allowed (bands). In this study they focus on two-dimensional photonic crystals, i.e., structures with periodic dielectric patterns on a plane and translational symmetry in the perpendicular direction. They start by studying a two-dimensional photonic crystal system for frequencies inside the band gap. The inclusion of a line defect introduces allowed states in the otherwise prohibited frequency spectrum. The dependence of the defect resonance state on different parameters such as size of the structure, profile of incoming source, etc., is investigated in detail. For this study, they used two popular computational methods in photonic crystal research, the Finite Difference Time Domain method (FDTD) and the Transfer Matrix Method (TMM). The results for the one-dimensional defect system are analyzed, and the two methods, FDTD and TMM, are compared. Then, they shift their attention only to periodic two-dimensional crystals, concentrate on their …

The implementation of x-ray computerized tomography (CT) on agricultural soils has been used in this research to quantify soil physical properties to be compared with standard laboratory (STD) methods. The overall research objective was to more accurately quantify soil physical properties for long-term management systems. Two field studies were conducted at Iowa State University's Northeast Research and Demonstration Farm near Nashua, IA using two different soil management strategies. The first field study was conducted in 1999 using continuous corn crop rotation for soil under chisel plow with no-till treatments. The second study was conducted in 2001 and on soybean crop rotation for the same soil but under chisel plow and no-till practices with wheel track and no-wheel track compaction treatments induced by a tractor-manure wagon. In addition, saturated hydraulic (K{sub s}) conductivity and the convection-dispersion (CDE) model were also applied using long-term soil management systems only during 2001. The results obtained for the 1999 field study revealed no significant differences between treatments and laboratory methods, but significant differences were found at deeper depths of the soil column for tillage treatments. The results for standard laboratory procedure versus CT method showed significant differences at deeper depths for the chisel plow treatment …

Precipitation and characterization of nickel hydroxide powders were investigated. A comprehensive precipitation model incorporating the metal ion hydrolysis, complexation and precipitation reactions was developed for the production of the powders with urea precipitation method. Model predictions on Ni{sup 2+} precipitation rate were confirmed with precipitation experiments carried out at 90 C. Experimental data and model predictions were in remarkable agreement. Uncertainty in the solubility product data of nickel hydroxides was found to be the large contributor to the error. There were demonstrable compositional variations across the particle cross-sections and the growth mechanism was determined to be the aggregation of primary crystallites. This implied that there is a change in the intercalate chemistry of the primary crystallites with digestion time. Predicted changes in the concentrations of simple and complex ions in the solution support the proposed mechanism. The comprehensive set of hydrolysis reactions used in the model described above allows the investigation of other systems provided that accurate reaction constants are available. the fact that transition metal ions like Ni{sup 2+} form strong complexes with ammonia presents a challenge in the full recovery of the Ni{sup 2+}. On the other hand, presence of Al{sup 3+} facilitates the complete precipitation of Ni{sup …

This thesis was developed to address the following questions for the Pb/Si(111) system: (1) Is it possible to control the nano-structure growth by changing the initial substrate; (2) is the nucleation theory applicable to the case of the 7-step growth mode; and (3) what phase or phases could be formed between coverage 6/5 ML and 4/3 ML? The first question was answered in chapter 2, different growth results were observed for different initial substrate, suggesting the possibility of controlling nano-structure growth by selecting the initial substrate. The applicability of nucleation theory was determined to be unclear in chapter 3, from the results that the saturation island density does not depend on deposition rate, in contrary to the prediction of nucleation theory. Chapter 4 revealed a novel ''devil's staircase'' in Pb/Si(111) within the coverage range 6/5 ML and 4/3 ML. Low temperature deposition experiments showed high order of self-organization in such a system. Theoretical studies are needed to understand such a low temperature behavior. In general, this thesis provides possibilities of controlling nano-structure growth, which can be possibly an indication for future application. It also raises interesting questions in fundamental researches: a modified theory of nucleation is needed, and a detailed …

The research discussed within involves the development of novel applications of real-time imaging of adenosine 5'-triphosphate (ATP). ATP was detected via bioluminescence and the firefly luciferase-catalyzed reaction of ATP and luciferin. The use of a microscope and an imaging detector allowed for spatially resolved quantitation of ATP release. Employing this method, applications in both biological and chemical systems were developed. First, the mechanism by which the compound 48/80 induces release of ATP from human umbilical vein endothelial cells (HUVECs) was investigated. Numerous enzyme activators and inhibitors were utilized to probe the second messenger systems involved in release. Compound 48/80 activated a G{sub q}-type protein to initiate ATP release from HUVECs. Ca{sup 2+} imaging along with ATP imaging revealed that activation of phospholipase C and induction of intracellular Ca{sup 2+} signaling were necessary for release of ATP. Furthermore, activation of protein kinase C inhibited the activity of phospholipase C and thus decreased the magnitude of ATP release. This novel release mechanism was compared to the existing theories of extracellular release of ATP. Bioluminescence imaging was also employed to examine the role of ATP in the field of neuroscience. The central nervous system (CNS) was dissected from the freshwater snail Lymnaea stagnalis. …

Chapters 1 and 2 dealt with the chemistry of superoxo-, hydroperoxo-, and oxo- complexes of chromium, rhodium and cobalt. Chapter 3 dealt with the mechanism of oxygen-atom transfer catalyzed by an oxo-complex of rhenium. In Chapter 1, it was shown that hydroperoxometal complexes of cobalt and rhodium react with superoxochromium and chromyl ions, generating reduced chromium species while oxidizing the hydroperoxometal ions to their corresponding superoxometal ions. It was shown that the chromyl and superoxochromium ions are the more powerful oxidants. Evidence supports hydrogen atom transfer from the hydroperoxometal ion to the oxidizing superoxochromium or chromyl ion as the reaction mechanism. There is a significant H/D kinetic isotope effect. Comparisons to the rate constants of other known hydrogen atom transfer reactions show the expected correlation with bond dissociation energies. In Chapter 2, it was found that the superoxometal complexes Cr{sub aq}OO{sup 2+} and Rh(NH{sub 3}){sub 4}(H{sub 2}O)OO{sup 2+} oxidize stable nitroxyl radicals of the TEMPO series with rate constants that correlate with the redox potentials of both the oxidant and reductant. These reactions fit the Marcus equation for electron transfer near the theoretical value. Acid catalysis is important to the reaction, especially the thermodynamically limited cases involving Rh(NH{sub 3}){sub 4}(H{sub …

Morphological evolution and selection of angular primary silicon is investigated in near-eutectic Al-Si alloys. Angular silicon arrays are grown directionally in a Bridgman furnace at velocities in the regime of 10{sup -3} m/sec and with a temperature gradient of 7.5 x 10{sup 3} K/m. Under these conditions, the primary Si phase grows as an array of twinned bicrystalline dendrites, where the twinning gives rise to a characteristic 8-pointed star-shaped primary morphology. While this primary Si remains largely faceted at the growth front, a complex structure of coherent symmetric twin boundaries enables various adjustment mechanisms which operate to optimize the characteristic spacings within the primary array. In the work presented here, this primary silicon growth morphology is examined in detail. In particular, this thesis describes the investigation of: (1) morphological selection of the twinned bicrystalline primary starshape morphology; (2) primary array behavior, including the lateral propagation of the starshape grains and the associated evolution of a strong <100> texture; (3) the detailed structure of the 8-pointed star-shaped primary morphology, including the twin boundary configuration within the central core; (4) the mechanisms of lateral propagation and spacing adjustment during array evolution; and (5) the thermosolutal conditions (i.e. operating state) at the primary …

The potential of single molecule detection as an analysis tool in biological and medical fields is well recognized today. This fast evolving technique will provide fundamental sensitivity to pick up individual pathogen molecules, and therefore contribute to a more accurate diagnosis and a better chance for a complete cure. Many studies are being carried out to successfully apply this technique in real screening fields. In this dissertation, several attempts are shown that have been made to test and refine the application of the single molecule technique as a clinical screening method. A basic applicability was tested with a 100% target content sample, using electrophoretic mobility and multiple colors as identification tools. Both electrophoretic and spectral information of individual molecule were collected within a second, while the molecule travels along the flow in a capillary. Insertion of a transmission grating made the recording of the whole spectrum of a dye-stained molecule possible without adding complicated instrumental components. Collecting two kinds of information simultaneously and combining them allowed more thorough identification, up to 98.8% accuracy. Probing mRNA molecules with fluorescently labeled cDNA via hybridization was also carried out. The spectral differences among target, probe, and hybrid were interpreted in terms of dispersion …