Alicyclic and Aromatic Carboxylic Acids in Soil Organic Matter: An Investigation of Potential Origin and Association with Plutonium Using Advanced Analytical Techniques

Carboxylic acids are a defining component of soil organic matter, responsible for many of the physical and chemical properties, including metal-organic matter interactions, which govern its role as an important constituent of soils. However, there is a shortage of detailed molecular level information regarding orientation and structural arrangement of carboxylic acids within soil organic matter. This dissertation utilizes electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) as well as solid-state and multi-dimensional nuclear magnetic resonance (NMR) to investigate the molecular formula composition within several organic matter sources and the primary structures that feature carboxylic acids. Soil organic matter is evaluated in two forms: as the alkali-soluble, acid-insoluble portion of organic matter (humic acids) from a collection of sources, as well as the alkali soluble soil organic material associated with high Fe and Pu metal concentrations at a contaminated munitions facility. Two predominant carboxyl-containing molecular assemblages are found to be common in a wide variety of soil humic acids. Along with lignin-like assemblages, these are carboxyl-containing aliphatic molecules (CCAM) and condensed aromatic molecules. The proportion of these groups relative to lignin-like compounds within samples and the percent of total carboxylic acid molecular formulas among samples are found to increase with increasing humification of the soil. Since CCAM and condensed aromatic molecules have previously been shown to be generated from oxidization of lignin, this represents renewed evidence for lignin as a major source of organic matter in soils. Lignin ring-opening and radical re-polymerization reactions have been proposed to form alicyclic CCAM and condensed aromatic molecules. Detailed evaluation of the aliphatic molecules using multi-dimensional NMR confirms the presence of ring structures, replete with carboxylic acids, heteroatom substitutions in the form of alcohols and ethers, as well as a variety of methyl group substituents. Additionally, condensed aromatic carboxylic acid molecular formulas, primarily those containing nitrogen, were found composed in organic matter with elevated metal ions Pu and Fe. Carboxylic acid oxygens in combination with nitrogen in aromatic structures are suspected to be partially responsible for the high metal affinity. Nitrogen-containing hydroxamate groups were also investigated for their potential to be incorporated into stable organic matter by testing the reaction between an amine-containing hydroxamate siderophore and the biopolymer cutin. While products of this reaction could not be confirmed, carboxylic acid functional groups are identified in this thesis as key molecular components contributing to Pu and Fe metal-binding attributes of organic matter, and potentially formed during the production of condensed aromatic and alicyclic compounds as a result of radical oxidation reactions of lignin

Guitar Store Inventory

This project displays my senior programming project for a made up Guitar store inventory

The Effect of rhodium reagents upon the hydroboration and thermal isomerization of quadricyclane

Simple hydroboration of a cyclopropane ring is not a reaction that is easily carried out. Attempts to hydroborate the three membered ring of quadricyciane, however are encouraged by the high strain energy (96 kcal/mol) of this tetracyclic system. Observation of nortricyclanol product would be taken as a sign of a successful oxidative hydroboration of quadricyciane. Some minor successes in earlier hydroborations of quadricyciane with a Rh (I) reagent, Wilkinson\u27s catalyst, encouraged us. Wilkinson\u27s catalyst was however better at inducing isomerization to norbornadiene than hydroboration of quadricyciane. The main focus of our research is the hydroboration of quadricyciane using RhCl3 since this rhodium reagent was very effective in promoting hydroboration of alkenes. Using RhCl3 we carried out this reaction under various conditions and we were unable to produce nortricyclanol. We have studied the ability of RhCl3 to isomerize quadricyciane to norbornadiene and as expected, the ease of this reaction suggests a the reason why nortricyclanol is not produced

Voicemail Box

A short animation using rotoscoping and stop motion. The animation depicts the simple and sometimes trivial things that keeps one from the phone, leaving the caller to speak to their voicemail. The sounds used are real voicemails left by close family members and friends. It also displays the range of emotions that can be heard through the grainy sounds

Suppression of steady-state, but not stimulus-induced NF-kappaB activity inhibits alphavirus-induced apoptosis.

Recent studies have established cell type- specific, proapoptotic, or antiapoptotic functions for the transcription factor NF-kappaB. In each of these studies, inhibitors of NF-kappaB activity have been present before the apoptotic stimulus, and so the role of stimulus- induced NF-kappaB activation in enhancing or inhibiting survival could not be directly assessed. Sindbis virus, an alphavirus, induces NF-kappaB activation and apoptosis in cultured cell lines. To address whether Sindbis virus- induced NF-kappaB activation is required for apoptosis, we used a chimeric Sindbis virus that expresses a superrepressor of NF-kappaB activity. Complete suppression of virus-induced NF-kappaB activity neither prevents nor potentiates Sindbis virus-induced apoptosis. In contrast, inhibition of NF-kappaB activity before infection inhibits Sindbis virus-induced apoptosis. Our results demonstrate that suppression of steady-state, but not stimulus-induced NF-kappaB activity, regulates expression of gene products required for Sindbis virus-induced death. Furthermore, we show that in the same cell line, NF-kappaB can be proapoptotic or antiapoptotic depending on the death stimulus. We propose that the role of NF-kappaB in regulating apoptosis is determined by the death stimulus and by the timing of modulating NF-kappaB activity relative to the death stimulus

Sex segregation and young adults\u27 gender-typed attitudes about occupations

The present study examined the relation between the prevalence of sex segregation, or the division of men and women within social interactions, and young adults\u27 gender-typed attitudes. Specifically, gender-typed attitudes about the occupations that are preferred for the self and viewed as appropriate for others were investigated. The objectives of the current study were partially based on the suggestion that gender-typed attitudes may be a consequence, as well as a cause, of sex segregation (McHale, Kim, Whiteman, & Crouter, 2004). The gender-typed personality traits of expressivity (i.e., traits typically associated with femininity; e.g., being emotional) and instrumentality (i.e., traits typically associated with masculinity; e.g., being assertive) were examined as mediators of the relation between sex segregation and gender-typed attitudes about occupations. Activity preferences, or the activities that individuals choose to engage in, was also investigated as a mediator of the relation between sex segregation and gender-typed attitudes about occupations. Participants were 284 young adult college students between 18 to 23 years who completed questionnaires for the study online. The results indicated that men and women have more same-sex friends than other-sex friends. The frequency of sex segregation was found to be partially dependent on factors such as sex and context of the interaction (i.e., school vs. hanging out ). Furthermore, men and women were found to have gender-typed attitudes about occupations viewed as appropriate for the self and for others. Overall, sex segregation was not found to be related to gender-typed attitudes about occupations. Reasons for these findings are discussed. Additionally, the potential consequences of the findings are discussed in relation to the continuing sex segregation that is observed within many occupations

Causes and causation in Pseudo-Dionysius the Areopagite and modern natural sciences

This project traces shifts in understandings of causation from the premodern to the early modern period, focusing on one premodern interpretation of causation as representative of the Neoplatonic period, that of Pseudo-Dionysius the Areopagite, and comparing this perspective to several early modern thinkers, especially, Isaac Newton, Rene Descartes, John Locke, Thomas Hobbes, and Francis Bacon. For Dionysius, formal and final causation have metaphysical superiority over efficient and material causation. By contrast, beginning in the early modern period, efficient causation, the sense that describes how an object acquires a particular shape, begins to be seen as metaphysically supreme. The main historical and philosophical reasons for this shift in perceived supremacy are the affirmation of the primary-secondary quality distinction, and the rejection of Forms and teleology. The primary-secondary quality distinction allows for reality to be completely quantified, and thereby renders superfluous qualitative approaches to reality, such as formal causation. Similarly, the rejection of Forms and teleology leaves formal causation meaningless. After this historical overview, the philosophical hypothesis that Dionysius's premodern understanding of causation is more amenable to those who want to avoid nihilism is defended: purely scientific notions of causation have no means for providing whatness, intelligibility, or determinacy to the world in a rationally defensible manner, and thus, when pressed, a purely scientific view of the world is without whatness, intelligibility, and determinacy, which, by definition, leads to nihilism. By contrast, a world with causes other than solely scientific causes, specifically, a world with formal (and final) causation such as Dionysius's, allows for whatness, intelligibility, and determinacy, and thereby escapes nihilism because whatness requires Form, intelligibility requires Form and teleology, and determinacy requires teleology (which, in turn, is a supplement to Form). As argued, science studies the world of becoming, and therefore cannot provide the grounds for the world of being (which belongs to metaphysics); to live in a world of pure becoming without being is to have a nihilistic worldview. The epilogue draws a significant implication from this conclusion: the premodern approach invites a necessary revival of natural philosophy because the world of becoming is wider than modern science acknowledges

Building the meat packing industry in South Omaha, 1883-1898

An article by Gregory R. Zieren was brought to my attention as I was completing this study. I Dealing with recently published works on the packing industry, it critiques books that have been my constant companions over the last two years. Zieren writes, Despite the local focus [Chicago], none of the works is parochial in its scholarly concerns, and all of them broaden our understanding of the urban and social history of one the nation\u27s quintessential working-class districts. Chicago was the environment for the development of the modern industry and, for almost a century, was the world\u27s leading packing center. But other locales such as South Omaha were part of the industry as well. As the refrigerated dressed meat trade gained in importance, this new livestock and packing center on the Missouri River emerged as a major participant in the building of the packers\u27 powerful business empire. While South Omaha\u27s emergence provided a rich and colorful story of local development, it also demonstrated the big packers\u27 all-encompassing presence in the industry. But little attention has been paid to the packers\u27 role in the early years of this community. Local histories record the activities of Omaha entrepreneurs in establishing South Omaha and bringing the packers here. Most rely heavily on the pioneer works of Counsul Butterfield and Alfred Sorenson, while Minnie Ferguson\u27s 1934 thesis, South Omaha Packing Industry, 11 offered an overview of the local topic. But no through study of the packers\u27 role in this community has been undertaken, and as a result, South Omaha has been neglected by historians of the packing industry. Yet all the big packers were there in some capacity in the late nineteenth and early twentieth centuries. Each carved their piece out of Nebraska, where they had come to dominate both the local industry and much of the local economy. In the pages that follow, I examine the emergence of South Omaha as a major packing center in the late nineteenth century

Small places, big outcomes: An ethnographic case study on social emotional learning skills and development, organizational culture, and place-making in small, rural schools in southern New Jersey

The purpose of this qualitative, ethnographic case study was to describe the ways in which three school leaders from small, rural PreK-8 districts (less than 1,000 students) in Southern New Jersey used similar methods for fostering partnerships with families and bonds between individuals, families and schools to address social emotional learning skills and development in the early childhood setting (grades pre-kindergarten through third grade). In addition, this study examined how the organizational culture of the educational organizations reinforced or undermined the relationship between school and family partnerships and bonds. This study investigated the linkage between school leaders\u27 experiences and social development theory and theory of family-school connections and how the norms, values and beliefs held by the schools and families created or maintained the organizational culture for partnership. This study encompassed research that suggested educational organizations, facilitated by school leaders, have their own culture and serve as a place where families become attached to, involve themselves, and construct partnerships