Study of colossal magnetoresistance and pressure effects in La2/3Ca1/3MnO2 thin films /

The main purpose of this thesis is to study properties of La2/3Cai/3Mn03, both polycrystalline ceramics and thin films. This material has striking related electrical and magnetic properties. Thin films show colossal negative magnetoresistance (CMR) near transition from an insulating to a metallic state accompanied closely by transition from a paramagnetic to a ferromagnetic state. The double exchange mechanism (DE) and the Jahn-Teller deformations play an important role in CMR effect. Applied pressure has a very similar effect as does an applied magnetic field, except, at low temperatures (T

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Investigation of molecular polarizabilities and derivatives in halomethanes

The research undertaken was to obtain absolute Raman intensities for the symmetric stretching vibrations of the methyl halides, CH3X with (X=F, CI, Br), by experiment and theory. The intensities were experimentally measured using the Ar+ ion gas laser as excitation source, a Spex 14018 double monochromator and a RCA C-31034 photomultiplier tube as detector. These intensities arise from changes in the derivative of the polarizability (8 a'), with respect to vibration along a normal coordinate (8qi). It was intended that these derivatives obtained with respect to normal coordinates would be converted to derivatives with respect to internal coordinates, for a quantitative comparison with theory. Theoretical numerical polarizability derivatives for the stretching vibrations are obtained using the following procedure. A vibration was simulated in the molecule by increasi.ng and decreasing the respective bond by the amount ±o.oosA for the C-H bonds and ±o.oIA for the C-X (X=F, CI, Br) bond. The derivative was obtained by taking the difference in the polarizability for the equilibrium geometry and the geometry when a particular bond is changed. This difference, when divided by the amount of change in each bond and the number of bonds present results in the derivative of the polarizability with respect to internal coordinate i.e., !1u/!1r. These derivatives were obtained by two methods: I} ab initio molecular orbital calculation and 2} theory of atoms in molecules (AIM) analysis. Due to errors in the experimental setup only a qualitative analysis of the results was undertaken relative to the theory. Theoretically it is predicted that the symmetric carbonhalogen stretch vibrations are more intense than the respective carbon-hydrogen stretch, but only for the methyl chloride and bromide. The carbon fluorine stretch is less intense than the carbon-hydrogen stretch, a fact which is attributed to the small size and high electronegativity of the fluorine atom. The experimental observations are seen to agree qualitatively with the theory results. It is hoped that when the experiment is repeated, a quantitative comparison can be made. The analysis by the theory of atoms in molecules, along with providing polarizabilities and polarizability derivatives, gives additional information outlined below. The theory provides a pictorial description of the main factors contributing to the molecular polarizability and polarizability derivative. These contributions are from the charge transfer and atomic dipole terms i.e., transfer of charge from one atom to another and the reorganization of atomic electronic charge distribution due to presence of an electric field. The linear relationship between polarizability and molecular volume was also observed.

Size regulation of double and half embryos in the mice musculus

Genetic chimeras made by aggregating early mouse embryos have many uses in developmental biology and have also provided insights into embryonic growth regulation. There is an indication that the embryo can regulate for an increase in size because although aggregation chimeras are twice as big as normal embryos when made, they are born of normal size. Upward regula..... tion of size reduced embryos is also possible. Half embryos made by the isolation or destruction of one of the blastomeres of a 2-cell embryo are also born of normal size. Little is known about the timing or the mechanism of this size regulation. In this study, the timing of size regulation in double and half embryos was clearly established by comparison of cell numbers derived from serial reconstruction of light microscope sections of control and experimental embryos. It was shown that size regulation in double embryos occurred around 6dl6h and in half embryos by 7dOh. Size regulation occurred in all tissues at the same time indicating a single control mechanism for the entire embryo. More detailed examination of the growth of double embryos revealed that size regulation occurred by alteration in cell cycle length~ No excessive cell death was found in double embryos compared to the controls and continuous labelling with [3H] thymidine showed no large non-dividing cell population in double embryos. However, a comparison of the mitotic index of double and control embryos after colcemid treatment, revealed a large difference between the two around 5dl6h to 6d16h. During this period, control embryos underwent a proliferative burst not shown by the double embryos. The mechanism for cell cycle control is not clear; it may be intrinsic to the embryo or determined by the uterine environment. Evidence was found suggesting that differentiation in the postimplantation embryo was cell number dependent. The timing of differentiative events was examined in half, double and control embryos. Proamnion formation, which occurs prior to size regulation, occurs at the same cell number but at different times in the three groups of embryos. However mesoderm which appears after size regulation was seen at the same time in all grollps of embryos.

Buddy films and gender identity : representing the bonds of masculinity /

The study examines the buddy film genre and the representation of masculinity in relation to the homosocial and the homoerotic. As a genre, the buddy films focus on male relationships, thematically seeking to mediate the boundaries surrounding the homosocial continuum and the intimacy and eroticism implicit in male bonding. Theories of genre, gender and identity are used to analyze the construction of masculine identity within the films. By providing a qualitative analysis of films from the 1960s to contemporary times, the research establishes a relationship between social changes, attitudes toward men and depictions of men. The buddy films adapt to address changes in the representation of masculinity, embodied in the difference between the male couple in the films. The early films of the 1960s served as templates that deconstructed traditional representations of male identity through articulating the tension within homosocial relationships. However, in the later films this tension became a refle~ive convention, acting to undermine the eroticism onto a displaced Other. The buddy film genre highlights the tension inherent to the male masquerade. This tension is situated in the need to represent the protagonist's homosocial relationship, while disavowing the eroticism that surrounds homosocial bonding. The structure of the buddy film genre, which focuses on the exploration of masculinity and representing the bonds of homosocial intimacy, makes these films a significant site for investigating the cultural construction of masculine identities.

Bonds away : baseball mythology and the 2007 home run chase

In 2007, Barry Bonds hit his 75 6th home run, breaking Hank Aaron's all-time record for most home runs in a Major League career. While it would be expected that such an accomplishment would induce unending praise and adulationfor the new record-holder, Bonds did not receive the treatment typically reserved for a beloved baseball hero. The purpose of this thesis is to assess media representations of the 2007 home run chase in order to shed light upon the factors which led to the mixed representations which accompanied BOlTds ' assault on Aaron's record. Drawingfrom Roland Barthes ' concept of myth, this thesis proposes that Bonds was portrayed in predominantly negative ways because he was seen as failing to embody the values of baseball's mythology. Using a qualitative content analysis of three major American newspapers, this thesis examines portrayals of Bonds and how he was shown both to represent and oppose elements from baseball's mythology, such as youth, and a distant, agrarian past. Recognizing the ways in which baseball is associated with American life, the media representations of Bonds are also evaluated to discern whether he was portrayed as personifYing a distinctly American set of values. The results indicate that, in media coverage of the 2007 home run chase, Bonds was depicted as a player of many contradictions. Most commonly, Bonds' athletic ability and career achievements were contrasted with unflattering descriptions of his character, including discussions of his alleged use of performance-enhancing substances. However, some coverage portrayed Bonds as embodying baseball myth. The findings contribute to an appreciation of the importance of historical context in examining media representations. This understanding is enhanced by an analysis of a selection of articles on Mark McGwire 's record-breaking season in 1998, and careful consideration of, and comparison to, the context under which Bonds performed in 2007. Findings are also shown to support the contemporary existence of a strong American baseball mythology. That Bonds is both condemned for failing to uphold the mythology and praised for personifYing it suggests that the values seen as inherent to baseball continue to act as an American cultural benchmark.

Forecasting the Yield Curve of Government Bonds: A Comparative Study

For the past 20 years, researchers have applied the Kalman filter to the modeling and forecasting the term structure of interest rates. Despite its impressive performance in in-sample fitting yield curves, little research has focused on the out-of-sample forecast of yield curves using the Kalman filter. The goal of this thesis is to develop a unified dynamic model based on Diebold and Li (2006) and Nelson and Siegel’s (1987) three-factor model, and estimate this dynamic model using the Kalman filter. We compare both in-sample and out-of-sample performance of our dynamic methods with various other models in the literature. We find that our dynamic model dominates existing models in medium- and long-horizon yield curve predictions. However, the dynamic model should be used with caution when forecasting short maturity yields

Chemoenzymatic Total Synthesis of Morphine alkaloids: Synthesis of Dihydrocodeine and Hydrocodone via a Double Claisen Strategy and ent-Hydromorphone via an Oxidative Dearomatization/intramolecular [4+2] Cycloaddition

This thesis describes the chemoenzymatic synthesis of three morphine alkaloids. The total synthesis of dihydrocodeine and hydrocodone was accomplished starting from bromobenzene in 16 and 17 steps, respectively. The key steps included a microbial oxidation of bromobenzene by E. coli JM109 (pDTG601A), a Kazmaier-Claisen rearrangement of glycinate ester to generate C-9 and C-14 stereo centers, a Johnson-Claisen rearrangement to set the C-13 quaternary center, and a C-10/C-11 ring closure via a Friedel-Crafts reaction. In addition, the total synthesis of ent-hydromorphone starting from β-bromoethylbenzene in 12 steps is also described. The key reactions included the enzymatic dihydroxylation of β-bromoethylbenzene to the corresponding cis-cyclohexadienediol, a Mitsunobu reaction, and an oxidative dearomatization followed by an intramolecular [4+2] cycloaddition.

Double Rail Restrainer for Handling Beef Cattle

The summary of the article reads "A new double rail conveyor restrainer for handling cattle at the slaughter plant is described. It has improved safety and ergonomics compared to the V restrainer conveyor it replaces. Cattle ride astride a moving conveyor. This design could also be adapted for veterinary work."

Form letter: a printed, 2 1/2 page copy of Jarvis Conklin and Co. Mortgage, Loans and Municipal Bonds letter to S.D. Woodruff, signed by James Conklin

Form letter: a printed, 2 1/2 page copy of Jarvis Conklin and Co. Mortgage, Loans and Municipal Bonds letter to S.D. Woodruff, signed by James Conklin, n.d.

Printed blank to S.D. Woodruff from Jarvis, Conklin and Co. regarding enclosure of coupons for bonds

Printed blank to S.D. Woodruff from Jarvis, Conklin and Co. regarding enclosure of coupons for bonds, Jan. 24, 1885.

Printed blank of Statement of Security Form naming the bond as Jones County Texas Bonds for the purpose of building a courthouse

Printed blank of Statement of Security Form naming the bond as Jones County Texas Bonds for the purpose of building a courthouse. It is made out to S.D. Woodruff and dated June 12, 1885. An envelope addressed to Mr. S.D. Woodruff is also included. The postmarks are Kansas, 1885 and St. Catharines, June 13, 1885.

Notice regarding bonds and shareholders and the rights of the directors of the Long Point Compan

Notice regarding bonds and shareholders and the rights of the directors of the Long Point Company, n.d.