2014 UMKC Dissertations - Access Restricted to UMKC
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Item Full Employment and Development: The Case of Indian Economy(University of Missouri–Kansas City, 2014) Das, Shakuntala; Wray, L. Randall, 1953-The purpose of this study is to establish the feasibility and desirability of full employment and price stability in India via an Employer of Last resort program. After providing a brief historical background of the precolonial and colonial economy, the development of the Indian political economy since independence is analyzed in order to identify the country’s institutional characteristics and macroeconomic stability. It is shown how the traditional Indian social organization based on the self-sufficient village community system has been dismantled and all forms of social provisioning have undergone destruction in the last few decades by neoliberal policies. The current public employment program with its rights based approach can be instrumental in fostering change with social justice. The empirical content of the thesis is based on the primary field work done in one of the states in the country. Many emerging institutions are working to strengthen this program. A broader view of the public is necessary to envision ‘social security’ as an objective pursued through public action rather than a narrowly defined set of strategies relying exclusively either on market forces, or on some paternalistic initiative of the state.Item Music From the Mountain For Di and Orchestra(2014) Yun, Lu; Chen, Yi, 1953-After studying abroad, I have started my research on the comparison between the western and the traditional Chinese orchestras. The idea of forming the traditional Chinese orchestra came from the influence of the "Total Westernization" at the beginning of the 20ᵗʰ century in China. Some musicians and composers who had studied abroad tried to put Chinese instruments together to imitate the structure of western orchestra, and started to adopt its instrumental and compositional techniques in new works. The traditional Chinese orchestra has been developing for more than eighty years to become the one we can see nowadays. There are four main sections in the traditional Chinese orchestra - winds, percussion, plucked, and bowed instruments. I started composing works for the traditional Chinese orchestra since 2003 and have finished four concertos for Chinese instrument and the Chinese orcehstra. After coming to the US, I had an opportunity to learn more about western orchestra and thought about the differences between the Chinese and the western orchestras. Although the techniques of orchestration for the Chinese orchestra are adopted from the western, the component of the sonority is quite different. For example: there is only one plucked instrument - the harp in the western orchestra, but a whole section of plucked instruments in the Chinese orchestra.There is a full brass section in the western orchestra, but there is no such powerful and solid sound in the Chinese orchestra. The western string section covers almost 6 octaves, but the whole bowed-string section only covers 5 octaves. Moreover, the sonority of the string section is coherent, but the sound of the bowed instruments is relatively distinctive. Music from the Mountain was composed for Di and traditional Chinese orchestra in 2005. I attempted to preserve the original concept and structure of this piece, and re-orchestrated it for the western orchestra. Instead of making a simple arrangement, I tried to find the characters of all instruments in the western orcehstra, and use the effectively and idiomatically. The western-orchestral version of Music from the Mountain is not simply moving note-by-note from the original version, but a new hybrid between the two.Item Raman, Infrared and Microwave Spectra, Conformational Stability, R₀ Structural Parameters and Vibrational Assignments of Some Organoamines, Organophosphines, Alcohols And Substituted Four And Five Membered Rings(2014) Darkhalil, Ikhlas Daoud; Durig, James R.The infrared and Raman spectra of compounds with amino, phosphours, silane and hydroxyl functional groups, as well as some with cyclic skeletal structures have been recorded of the gas and in condensed phases. Temperature dependent infrared and Raman spectra in xenon solutions were also recorded. A complete vibrational assignment, conformational stability determination and adjusted r0 parameters have been obtained for each of the most stable conformers and in some cases for the less stable conformers. The vibrational assignments were supported by normal coordinate calculations with scaled force constant from MP2(full)/6-31G(d) calcualtions from which the fundamental vibrational frequencies, infrared intensities, Raman activities, depolarization ratios and infrared band contours were predicted. For ethylamine the enthalpy difference has been determined to be 62 ± 6 cm-1 (0.746 ± 0.072 kJ mol⁻¹) with the trans conformer the more stable form. For isorpropylamine, the enthalpy difference of the sample dissolved in Raman xenon has been determined to be 113 ± 11 cm⁻¹ (1.35 ± 0.13 kJ mol⁻¹) with the trans conformer the more stable form. For n-propylamine, the five possible conformers have been identified and their relative stabilities obtained with enthalpy difference relative to Tt for Tg of 79 ± 9 cm⁻¹ (0.9 ± 0.1 kJ/mol); for Gg of 91 ± 26 cm⁻¹ (1.08 ± 0.3 kJ/mol); for Gg' of 135 ± 21 cm⁻¹ (1.61 ± 0.2 kJ/mol); for Gt of 143 ± 11 cm⁻¹ (1.71 ± 0.1 kJ/mol). For 2-cyanoethylamine, the enthalpy differences between the Gg and Gt conformers was determined to be 75 cm⁻¹ and for the Gg to Tg form 333 cm⁻¹. For 2,2difluoroethylamine, the enthalpy differences have been determined among the most stable Tt conformer and the second stable conformer, Gg, to be 83 ± 8 cm⁻¹ (0.99 ± 0.10 kJ/mol), the third stable conformer, Gt, to be 235 ± 11 cm⁻¹ (2.81 ± 0.13 kJ/mol). For 2,2,2 trifluoroethylamine, the enthalpy difference has been determined to be 267 ± 27 cm⁻¹ (3.19 ± 0.32 kJ mol⁻¹) with the trans conformer the more stable form. For 2,2,3,3,3-pentafluoropropylamine, the enthalpy difference has been determined between the more stable Tt conformer and the less stable Tg form to be 280 ± 14 cm⁻¹ (3.35 ± 0.17 kJ/mol). In case of cyclopentylamine, the four possible conformers have been identified and their relative stabilities obtained with enthalpy difference relative to t-Ax of 211 ± 21 cm⁻¹ for t-Eq ≥ 227 ± 22 cm⁻¹ for g-Eq ≥ 255 ± 25 cm⁻1 for g-Ax. For cyclohexylamine, the four possible conformers have been identified as t-eq> g-eq>t-ax>g-ax. Microwave spectra for several of the molecules have been investigaged from 10,000 to 21000 MHz with transtions for the most stable conformer and in some cases for the less stable conformers. By utilizing the rotational constants reported from microwave studies combined with the structural parameters predicted from the MP2(full)/6-311+G(d,p) calcualtions, adjusted r0 strutral paramerters have been obtained for the most stable conformer(s) of the different molecules studied.Item Evaluation of therapeutic effect of PCBP2 siRNA on hepatic stellate cells and development of a streptavidin-based siRNA delivery system(2014) Shukla, Ravi Shankar; Cheng, Kun (Professor)Type I collagen accumulates during liver fibrosis primarily because α-complex protein-2 (αCP2), encoded by the poly(rC) binding protein 2 (PCBP2) gene, binds to the 3′end of the collagen mRNA and increases its half-life. Study in chapter 3 aimed to reverse the pro-fibrogenic effect of alcohol on hepatic stellate cells (HSCs) by silencing the PCBP2 gene with siRNA. The silencing effects of a series of predesigned PCBP2 siRNAs were evaluated in the rat hepatic stellate cell line, HSC-T6. The pro-fibrogenic effects of alcohol on the expression levels of PCBP2 and type-I collagen were examined by several methods. The effect of PCBP2 siRNA on the stability of type I collagen α1(I) mRNA was investigated by an in vitro mRNA decay assay. We identified one potent PCBP2 siRNA that reversed the alcohol-induced expression of PCBP2 in HSCs. The decay rate of the collagen α1(I) mRNA increased significantly in HSCs treated with the PCBP2 siRNA. This study provides the first evidence that alcohol up-regulates the expression of PCBP2, which subsequently increases the half-life of collagen α1(I) mRNA. Silencing of PCBP2 using siRNA may provide a promising strategy to reverse the alcohol-induced pro-fibrogenic effects in HSCs. Furthermore, we developed a streptavidin-based nanocomplex that can efficiently deliver the PCBP2 siRNA to HSCs. Biotin−siRNA and biotin−cholesterol were mixed with streptavidin to form the streptavidin−biotin complex, which was further condensed electrostatically with positively charged protamine to form the final multicomponent siRNA nanocomplex in the size range of 150−250 nm. The siRNA nanocomplex does not induce cytotoxicity in rat HSCs as compared to commercially available transfection agents. The cellular uptake efficiency of the siRNA nanocomplex is higher in rat HSCs than other cell lines, such as Caco-2 and PC-3, indicating that receptor-mediated endocytosis mainly contributes to the cellular uptake of the siRNA nanocomplex. The siRNA nanocomplex exhibits more than 85% silencing effect on the PCBP2 mRNA in HSCs. Stability study indicates that the nanocomplex can efficiently protect siRNA from degradation in the serum. The streptavidin-based multicomponent siRNA nanocomplex provides a promising strategy to deliver the PCBP2 siRNA to HSCs. Moreover, the nanocomplex can be used as a platform for other diseases by changing the siRNA sequence and targeting ligand. Understanding of the subcellular distribution of a small interfering RNA (siRNA) formulation is essential for improving the silencing activity of the siRNA. Previously, we have developed a multicomponent streptavidin-based nanocomplex to deliver the PCBP2 siRNA to rat hepatic stellate cells (HSCs) to inhibit the expression of αCP2, a critical protein in alcoholic liver fibrogenesis. This study at chapter 5 aims to evaluate the cellular uptake, subcellular trafficking and intracellular fate of the siRNA and other components, such as protamine and streptavidin, of the nanocomplex. Cellular uptake and silencing activity of the siRNA nanocomplex was compared with commercially available Lipofectamine-2000. siRNA nanocomplexes containing fluorescently labeled siRNA, streptavidin and protamine were used for thealuation of subcellular trafficking of each of the components. The results showed that the silencing activity of the siRNA nanocomplex decreases with incubation time, indicating that part of the siRNA is either entrapped in the endosomes or associated with streptavidin. The intracellular trafficking of the siRNA nanocomplex exhibits divergent cellular distribution of siRNA, protamine and streptavidin. These findings can facilitate the rational design of streptavidin based siRNA delivery systems.Item Development of polymeric nanoparticulate formulation encapsulating protein molecules following hydrophobic ion pairing complexation(2014) Patel, Ashaben; Mitra, Ashim K., 1954-Several formulation strategies have been employed to enable sustained delivery of antibody therapeutics by nanoparticulate based dosage forms. However, development of sustained release nanoparticulate based dosage form for protein therapeutics represents a real challenge to scientists. These protein molecules are prone to denaturation under stress conditions such as sonication and presence of organic solvents. Another limiting factor in developing nanoparticulate formulation of protein therapeutics is their hydrophilic nature. Because of hydrophilic nature, these molecules partition poorly into polymer matrix leading to very low encapsulation efficiency. Hydrophobic ion pairing (HIP) complexation represents a novel approach to enhance protein encapsulation into nanoparticles. It also stabilizes protein molecules during nanoparticle preparation. We have chosen two model antibody proteins: Human IgG-Fab fragment and Human IgG, and prepared their HIP complexes. Different ion pairing agents and HIP complexation parameters were optimized. Consequently, optimized HIP complexes were loaded in polymeric nanoparticles. As a result, significant augmentation in encapsulation efficiency of these protein molecules was observed in the nanoparticles. Based on optimized parameters with IgG-Fab fragment, ranibizumab (Lucentis®), an anti-VEGF antibody fragment used for the treatment of age-related macular degeneration, loaded nanoparticulate formulation was also successfully developed. Developed nanoparticles formulations were characterized with respect to particle size, surface morphology and stability of entrapped protein. Further, nanoparticles were suspended in thermosensitive gel to achieve sustained release. HIP complexation has provided sustained release of protein from nanoparticles suspended in thermosensitive gel. Released protein maintained their physical stability and biological activity. No deleterious effects of HIP complexation and method of nanoparticles preparation on protein stability were observed.