Row width and density effects on yield, growth, and light interception in soybeans.

Thesis (M.S.

Diffeomorphisms of Time

According to Newton, time is a consistent and reliable tool used to measure various physical quantities. According to Einstein, time is subjective and dependent on a number of external factors. There are many ways to analyze and bridge the gab between the two theories, one being mathematically. In this project, I examine three specific notions of time by representing time as a line, using projecive geometry to relate the line to a circle, transforming the circle, and analyzing the physical implications of these transformations

Valerie Willcott, voice; Leslee Heys, piano

Valerie Willcott, voice; Leslee Heys, pianoPresented in partial fulfilment of the requirements for Music 440B

State level corruption: an empirical study of the effects of state level corruption on firm performance in the United States

Over the past 30 years considerable work scrutiny has been undertaken in the area of corruption and its effect on many facets of society. In business, efforts to measure corruption have been frequently debated and models have been proposed to reflect different firm characteristics in the presence of corruption. Based on these measures, research usually considers single variable measures over time, generally cross-nationally. This study constructs a new model incorporating multiple different variables working in concert over the period from 2000-2015, to postulate a variety of different relationships and firm characteristics at the state level in the United States. In doing so, the model is constructed to limit biases that a single variable can have on the data. The model analyzes state level firm financial performance by utilizing ROA and Tobin’s Q as well as comparing high corruption state data to low corruption state data. The study finds that the presence of corruption increases the firm’s financial performance at the state level. These data are then used to conduct univariate testing with Ordinary Least Squares modelling to examine fixed firm effects as well as time lagged data. Significance is found to hold for these constraints and that firm financial performance is enhanced in high corruption states for most of the sample constructs. Supplementary models are subsequently constructed to test the robustness against significant economic events and legislative changes. The model is found to provide additional evidence when these tests are applied, thereby maintaining significance. The evidence from these tests are discussed and the conclusion reached is that corruption provides the opportunity for firms to enhance their financial performance, particularly for large firms, value firms, and firms with low leverage. It is also concluded that the benefits in performance from corruption are more beneficial in the short term

Receptor versus counterion: capability of N,N′‐Bis(2‐aminobenzyl)‐diazacrowns for giving endo‐ and/or exocyclic coordination of ZnII

[Abstract] The structure of ZnII complexes with receptors L1 and L2[L1 = N,N′‐bis(2‐aminobenzyl)‐1,10‐diaza‐15‐crown‐5 and L2 = N,N′‐bis(2‐aminobenzyl)‐4,13‐diaza‐18‐crown‐6] was studied both in the solid state and in acetonitrile solution. Both receptors form mononuclear ZnII complexes in this solvent, while no evidence for the formation of dinuclear complexes was obtained. This is in contrast with previous investigations that demonstrated the formation of dinuclear complexes of L2 with first‐row transition metals such as NiII, CoII and CuII. Compounds of formula [Zn(L1)](ClO4)2 (1), [Zn(L1)](NO3)2·2CH3CN (2), [Zn(L2)](ClO4)2 (3) and [Zn(L2)(NO3)2] (4) were isolated and structurally characterised by X‐ray diffraction analyses. L1 forms seven‐coordinate ZnII complexes in the presence of both nitrate and perchlorate anions, as a consequence of the good fit between the macrocyclic cavity and the ionic radius of the metal ion. The ZnII ion is deeply buried into the receptor cavity and the anions are forced to remain out of the metal coordination sphere. The cation [Zn(L1)]2+ present in 1 and 2 is one of the very few examples of seven‐coordinate Zn complexes. Receptor L2 provides a very rare example of a macrocyclic receptor allowing endocyclic and exocyclic coordination on the same guest cation, depending on the nature of the anion present. Thus, in 3 the ZnII ion is endocyclically coordinated, placed inside the crown hole coordinated to four donor atoms of the ligand in a distorted tetrahedral environment, whereas in 4, the presence of a strongly coordinating anion such as nitrate results in an exocyclic coordination of ZnII, which is directly bound only to the two primarily amine groups of L2 and two nitrate ligands. Spectrophotometric titrations of [Zn(L2)]2+ with tetrabutylammonium nitrate in acetonitrile solution demonstrate the stepwise formation of 1:1 and 1:2 adducts with this anion in acetonitrile solution. The [Zn(L1)]2+, [Zn(L2)]2+ and [Zn(L2)(NO3)2] systems were characterised by means of DFT calculations (B3LYP model). The calculated geometries show an excellent agreement with the experimental structures obtained from X‐ray diffraction analyses. Calculated binding energies of the macrocyclic ligands to ZnII are also consistent with the experimental data.Xunta de Galicia; PGIDIT03TAM10301P

Evaluating the thermal vinylcyclopropane rearrangement (VCPR) as a practical method for the synthesis of difluorinated cyclopentenes : experimental and computational studies of rearrangement stereospecificity

Vinyl cyclopropane rearrangement (VCPR) has been utilised to synthesise a difluorinated cyclopentene stereospecifically and under mild thermal conditions. Difluorocyclopropanation chemistry afforded ethyl 3-(1'(2'2'-difluoro-3'-phenyl)cyclopropyl) propenoate as all four stereoisomers (18a, 18b, 22a, 22b) (all racemic). Trans-E isomer (18a), prepared in 70% yield over three steps, underwent near quantitative VCPR to difluorocyclopentene 23 (99%). Rearrangements were followed by 19F NMR (100-180 °C). While cis/trans cyclopropane stereoisomerisation was facile, favouring trans-isomers by a modest margin, no E/Z alkene isomerisation was observed even at higher temperatures. Neither cis nor trans Z-alkenoates underwent VCPR, even up to much higher temperatures (180 oC). Cis-cyclopropanes underwent [3,3]-rearrangement to afford benzocycloheptadiene species. The reaction stereospecificity was explored using electronic structure calculations and UB3LYP/6-31G* methodology allowed the energy barriers for cyclopropane stereoisomerisation, diastereoisomeric VCPR and [3,3]-rearrangement to be ranked in agreement with experiment

Exceptionally inert lanthanide(III) PARACEST MRI contrast agents based on an 18-membered macrocyclic platform

[Abstract] We report a macrocyclic ligand based on a 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane platform containing four hydroxyethyl pendant arms (L1) that forms extraordinary inert complexes with Ln3+ ions. The [EuL1]3+ complex does not undergo dissociation in 1 M HCl over a period of months at room temperature. Furthermore, high concentrations of phosphate and Zn2+ ions at room temperature do not provoke metal-complex dissociation. The X-ray crystal structures of six Ln3+ complexes reveal ten coordination of the ligand to the metal ions through the six nitrogen atoms of the macrocycle and the four oxygen atoms of the hydroxyethyl pendant arms. The analysis of the Yb3+- and Pr3+-induced paramagnetic 1H NMR shifts show that the solid-state structures are retained in aqueous solution. The intensity of the 1H NMR signal of bulk water can be modulated by saturation of the signals of the hydroxy protons of Pr3+, Eu3+, and Yb3+ complexes following chemical-exchange saturation transfer (CEST). The ability of these complexes to provide large CEST effects at 25 and 37 °C and pH 7.4 was confirmed by using CEST magnetic resonance imaging experiments.Ministerio de Ciencia e Innovación; CTQ2011-24487Ministerio de Economía y Competitividad; CTQ2013-43243-

“It Has Informed My Entire Life”: Event Centrality, Vicarious Traumatization, and Vicarious Post-Traumatic Growth in Loved Ones Indirectly Exposed to Interpersonal Trauma

It is well-known that interpersonal traumatic events can impact the physical and mental health of those indirectly exposed to the events. Less studied are populations of loved ones who have been indirectly exposed to interpersonal trauma. My dissertation first aimed to synthesize the literature related to vicarious traumatization (VT), vicarious posttraumatic growth (VPTG), and event centrality in loved ones indirectly exposed to interpersonal trauma through a scoping review. The Joanna Briggs Institute methodology was used for Study 1. Inclusion criteria included (a) participants were indirectly exposed to the interpersonal trauma of a loved one in adulthood, (b) discussion of VT, VPTG, event centrality, or related terms, (c) published peer-reviewed empirical journal articles, and (d) available in English. We used a three-step search strategy to find relevant articles. Keywords found from the first two steps were entered into PsychINFO, PsycArticles, PubMed, Scopus, and Web of Science databases. Reference lists of the included articles were also examined. The identified articles were then screened using the inclusion and exclusion criteria. Twenty-eight articles met inclusion and exclusion criteria. Twenty-six articles referenced VT or related terms, one referenced VPTG, and one referenced vicarious trauma keywords. No articles referenced event centrality. The results of this study led to the second aim for this dissertation: to understand parents' process of vicarious event centrality for their child's interpersonal traumatic event post-disclosure, as this was a knowledge gap in the literature. Participants in Study 2 were 17 primary caregivers (14 maternal caregivers, 3 paternal caregivers) of 27 victims of child interpersonal trauma (14 males, 13 females) located in Canada. The age of participants ranged from 35 to 75 years (average = 54.5 years) and majority self-identified as Caucasian (70.6%). Grounded theory (GT) was used to analyze the data collected from participant interviews. The resulting model was labelled Vicarious Event Centralization and Decentralization, indicating that parents center their child’s interpersonal trauma across many areas of their lives, which orients them to focus on protecting and healing the child. After the child’s functioning improves, parents are then able to reorient to life beyond the trauma, representing decentralization. The GT consists of three phases, Centralization, Decentralization Gateway, and Decentralization. These results illustrate that parents’ centralization of the trauma may be an adaptive mechanism that promotes child recovery, which in turn allows parents to begin to decentralize the trauma and move towards recovery. This series of studies supports that loved ones are affected by indirect interpersonal trauma exposure in a myriad of ways and require unique services to address their needs. These studies can help practitioners understand the post-trauma experience for loved ones and target areas likely to increase recovery