Thesis advisor: James P. Morken / This dissertation describes the first enantioselective 1,2-diboration of cis-substituted 1,3-dienes. In the presence of a platinum catalyst and TADDOL-derived phosphonite ligands, both 4,4-disubstituted and mono-cis-substituted 1,3-dienes undergo regioselective 1,2-diboration to afford the corresponding 1,2-diols upon oxidation in up to 98:2 er and high yield. By achieving enantioselective 1,2-diboration of 1,3-dienes, a new synthetic route to α-chiral (Z)-allylboronate reagents has been developed. In the presence of an aldehyde, these allyl bis(boronate) esters undergo highly diastereoselective allylboration reaction to afford enantioenriched 1,5-homoallylic alcohols bearing all-carbon quaternary centers or syn-propionate motifs. In the presence of 1,4-dicarbonyl compounds, the (Z)-allylboronates undergo a double allylation reaction to afford cyclohexanols with four contiguous stereocenters in good yield and moderate to excellent diastereoselectivity. The tandem diboration/double allylation has been applied to the total synthesis of pumilaside B aglyon, and the partial synthesis 1β-hydroxy arbusculin A and bromophycolide F. / Thesis (PhD) — Boston College, 2013. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

In this paper we present a simple combinatorial approach for the derivation of zero avoiding transition probabilities in a Markovian r- node series Jackson network. The method we propose offers two advantages: first, it is conceptually simple because it is based on transition counts between the nodes and does not require a tensor representation of the network. Second, the method provides us with a very efficient technique for numerical computation of zero avoiding transition probabilities. / Series: Forschungsberichte / Institut für Statistik

This thesis describes the chemistry developed during a study of novel transition metal-catalysed reactions. Chapter 2 describes a novel procedure for the synthesis of 2,5-disubstituted furans via the isomerisation of 1,4-alkyne diols, avoiding the pitfalls of the traditional Paal-Knorr reaction. The initial ruthenium catalysed isomerisation is followed by an in situ cyclocondensation reaction using an acid co-catalyst in a one step route to furan derivatives. In addition the synthesis of the 1,4-dicarbonyl surrogates, 1,4-alkyne diols, is detailed. The methodology detailed in chapter 2 is then used in the synthesis of pyrrole derivatives in Chapter 3. Replacement of the acid co-catalyst with 2 equivalents of amine allow various pyrrole derivatives to be synthesised using the 1,4-alkynediols as starting materials. Various amines can also be used from anilines, benzylamines and aliphatic amines, allowing access to a wide range of products.

Spurious, falsely-labeled, falsified or counterfeit (SFFC) pharmaceuticals are a health concern that claims hundreds of thousands of lives annually1, a violation of intellectual property rights which cost legitimate companies billions2, and a low-risk high yield revenue stream for organized crime2. While ports of entry and border control points are the primary access control points for SFFC3,4, advances in field portable detection and equipment offers an increasingly effective method for the assessment of pharmaceuticals at regional centers and points of distribution. This is particularly important for less developed countries (LDC) who do not maintain satellite or regional testing facilities. As part of a proposed protocol to assess field portable detection equipment, an ultrafast liquid chromatography, tandem mass spectrometry (UFLC-MS/MS) method for the quantification of liquid formulation Oxytocin was developed. The six minute method was found to have a within run %bias of +/-16%, a linear dynamic range of 150-1000 nanograms/milliliter (ng/ml), and an accuracy within acceptability criteria for all tested concentrations. The effectiveness of three identified transition ions, 723.1, 86.2 and 70.1 Daltons, for the analysis of oxytocin by mass spectrometry was assessed across several figures of merit to include signal to noise ratio, %CV, calibration sensitivity, and analytical sensitivity. The 723.1 ion fragment was recommended for quantification, while the 70.1 dalton ion was recommended as a qualifier ion, although 86.2 also performed within acceptability criteria. A method for the UFLC-MS/MS assessment of degradation products for oxytocin was proposed for specificity testing. Degradation of oxytocin by exposure to highly acidic, basic, and thermal conditions for one hour was attempted. Formation of degraded products was not observed. Additionally, existing High Performance Liquid Chromatography (HPLC) methods for the simultaneous assessment of Artesunate and Amodiaquine HCl were modified to assess compatibility with UFLC. No method assessed produced sufficient quality signal to continue with method development.

Mycoplasma hyopneumoniae é uma bactéria de tamanho diminuto, caracterizada por um genoma pequeno, com baixo conteúdo GC. Está associada com doenças respiratórias de suínos, resultando em prejuízos produtivos e econômicos na indústria animal. A presença de sequências de DNA repetitivas, que ocorrem em grandes quantidades em células eucarióticas, vem sendo cada vez mais identificadas em genomas de procariotos, sendo também associadas a um potencial papel regulador. Uma vez que a regulação da transcrição nesses organismos ainda é pouco entendida, o objetivo do presente estudo foi realizar uma busca in silico por elementos repetitivos nas regiões intergênicas do genoma de M. hyopneumoniae linhagem 7448. Dois tipos de repetições foram selecionados para a busca inicial: tandem e palindromes. Regiões intergênicas de até 500 pb a montante do sítio de início da tradução de todas as CDSs do genoma de M. hyopneumoniae linhagem 7448 foram utilizadas para a predição. Para cada tipo de elemento dois programas computacionais independentes foram utilizados. As predições in silico resultaram em 144 repetições em tandem e 1.171 palindromes. O DNA repetitivo se encontra distribuído a montante de 86% das unidades transcricionais de M. hyopneumoniae linhagem 7448. Análises comparativas entre genomas de micoplasmas demonstraram diferentes níveis de conservação dos elementos repetitivos entre linhagens patogênicas e não-patogênicas. Linhagens patogênicas revelaram uma conservação de 59%, enquanto que a não patogênica, somente de 46%. Através de ensaios de amplificação quantitativa de DNA, foi observado diferentes níveis de expressão em genes codificantes para importantes proteínas, como glicina hidroximetiltransferase, lipoproteína, adesinas e proteína ligadora de GTP. Os genes codificantes para essas proteínas divergiam no número de repetições palindromes e tandens na sua respectiva região intergênica. Além disso, repetições encontradas em 206 genes já descritos como regulados em diferentes condições em M. hyopneumoniae linhagem 232 mostraram aproximadamente 80% de conservação em relação à linhagem M. hyopneumoniae linhagem 7448. Todos esses resultados sugerem um potencial papel regulador das repetições de DNA em tandem e palindromes em Mycoplasma. / Mycoplasma hyopneumoniae is a diminutive bacterium, characterized by a small genome with a low GC content. It is commonly associated with swine respiratory diseases, resulting in productivity and economic losses in the animal industry. Repetitive DNA, which occurs in large quantities in eukaryotic cells, has been increasingly identified in prokaryotic genomes, and has been associated with a potential regulatory function. Once transcription regulation in these organisms is still poorly understood, the aim of the current study was to perform an in silico search of repeat elements in the genomic intergenic regions of M. hyopneumoniae strain 7448. Two types of repeats were selected for initial search: Tandem and Palindromic. Intergenic regions up to 500 bp upstream from start codon of M. hyopneumoniae strain 7448 CDSs were used as input for the software’s prediction. For each type of repeat sequence, two independent software packages were used. Computational analysis results in 144 tandem repeats and 1,171 palindrome elements. The repeats were distributed in the upstream region of 86% of transcriptional units of M. hyopneumoniae strain 7448. Comparative analysis between distinct mycoplasmas, demonstrate different indices of repeat conservation among pathogenic and non-pathogenic strains. Pathogenic strains revealed 59% conservation, while non-pathogenic only 46%. Through assays of quantitative amplification of DNA, different levels of expression in genes coding important proteins have been demonstrated, as glycine hydroxymethyltransferase, lipoprotein, adhesins and GTP-binding protein. These protein coding genes differ in number of palindromes or tandem repeats in respective upstream regions. In addition, repeats found in 206 genes already described to be regulated in different grow conditions in M. hyopneumoniae strain 232 showed almost 80% of conservation in relation to M. hyopneumoniae strain 7448. All these findings, suggests a potential regulatory role of tandem and palindrome DNA repeats.

No description available.

Submitted by DIOGO MILANI null (azafta@gmail.com) on 2017-03-14T19:28:19Z No. of bitstreams: 1 Dissertação_Final_Milani.pdf: 20096682 bytes, checksum: c3ba1f1d35902ae0f6c7c33176ff9274 (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2017-03-20T22:53:25Z (GMT) No. of bitstreams: 1 milani_d_me_rcla.pdf: 20096682 bytes, checksum: c3ba1f1d35902ae0f6c7c33176ff9274 (MD5) / Made available in DSpace on 2017-03-20T22:53:25Z (GMT). No. of bitstreams: 1 milani_d_me_rcla.pdf: 20096682 bytes, checksum: c3ba1f1d35902ae0f6c7c33176ff9274 (MD5) Previous issue date: 2017-03-02 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / DNAs satélites (DNAsat) são sequências usualmente repetidas centenas a milhares de vezes arranjadas consecutivamente uma à outra, enriquecidas geralmente na heterocromatina em regiões específicas ou cromossomos, tais como os cromossomos B. Neste trabalho, isolamos o primeiro DNAsat no gafanhoto Abracris flavolineata, nomeado AflaSAT-1. A sequência foi caracterizada integrando abordagem molecular, genômica e citogenética objetivando compreender a organização estrutural, evolução nos cromossomos A e B e possível atividade transcricional. O AflaSAT-1 é compartilhado entre espécies de gafanhotos, mas revelou uma evidente amplificação em A. flavolineata formando arranjos detectáveis. A sequência apresentou baixa variabilidade em nível interpopulacional; no entanto monômeros do cromossomo B (μB-DNA) da população de Rio Claro/SP exibiram maior variabilidade e quatro mutações exclusivas, refletindo a comum taxa mutacional mais elevada dos cromossomos B. A análise genômica estrutural revelou organizações distintas para o DNAsat, apresentando uma associação alternativa com outro DNAsat, nomeado AflaSAT-2. A análise cromossômica revelou que ambos os DNAsat estão interligados um ao outro formando grandes blocos nos centrômeros de quase todos os cromossomos (exceto para o menor par), e para o cromossomo B apenas um pequeno sinal centromérico foi notado em indivíduos da população de Rio Claro/SP. Nas distintas populações a distribuição cromossômica do AflaSAT-1 revelou variabilidade, como ausência de algumas marcas, blocos adicionais e também heteromorfismo, a qual se correlacionou com a estimativa de número de cópias, sugerindo uma dinâmica de expansão ou eliminação de repetições. Finalmente, a constitutiva atividade transcricional de AflaSAT-1 foi observada nos distintos tecidos de adultos, e em distintas fases de desenvolvimento, tanto em indivíduos portadores e não portadores de cromossomo B. / Satellite DNAs (satDNA) are sequences usually repeated hundred to thousand times tandemly arrayed, enriched in heterochromatin from specific region or chromosomes, including B chromosomes. Here, we isolated the first satDNA in the grasshopper Abracris flavolineata, named AflaSAT-1. The sequence was characterized by integration of cytogenetic, molecular and genomics approaches, aiming to understand the structural organization, evolution in A and B chromosomes and possible transcriptional activity. The AflaSAT-1 is shared with other grasshopper species, but it was evidently amplified in A. flavolineata forming detectable clustered arrays. AflaSAT-1 presented low variability at interpopulational level; but monomers from B chromosome observed in individuals from Rio Claro/SP were more variable presenting four exclusive mutations, reflecting the common higher mutational rate in this chromosome. Genomic structural analysis revealed distinct organization for the satDNA, with its alternative association with other satDNA, named AflaSAT-2. The chromosomal analysis showed that both satDNAs were also interglimed to each other, forming large blocks in centromeres of almost all chromosomes (except the smallest pair), but in the B chromosome only a small centromeric signal was noticed in individuals from Rio Claro/SP. Chromosomal distribution for AflaSAT-1 revealed variability, at populational level, with absence of marks, additional clusters and heteromorphism. This variation was coincidentally followed by variability in copy number, suggesting dynamic expansion or elimination of repeats. Finally, AflaSAT-1 was constitutively transcriptionally active in five tissues of adults, in distinct life cycle phases, and both in carrier and non-B chromosome carriers. / FAPESP: 2015/05246-3

High performance multijunction solar cells based on polycrystalline thin films will require a wide bandgap top cell with at least 15% efficiency. With the bottom cell being CIGS which have already demonstrated the required efficiencies, this work aims to study the complete fabrication and performance of Cd1-xZnxTe solar cells with a bandgap of 1.7eV on glass and flexible polyimide substrates. Cd1-xZnxTe films were deposited by RF magnetron co-sputtering with CdTe and ZnTe sources. By varying the composition of Cd1-xZnxTe being deposited the required bandgap of 1.7eV was achieved. The optical and structural properties of the films were studied with optical transmission, SEM and XRD measurements. The films exhibited high optical transmission and pinhole free grain structure. CZT solar cells were fabricated on glass and flexible polyimide substrate and were analyzed by J-V and spectral response measurements. The effect of post deposition treatments and the effect of N2 during sputtering on CZT device performance were studied.

The relationship between distinctive characteristic fluid-flow regimes and the sound radiation generated by them has been investigated, over a range of Reynolds numbers, for various single plates and two-plate arrays in nominally two-dimensional flows. In preliminary experiments, the characteristics of flow over single plates with rectangular cross-section and faired leading edges and over tandem arrays of an upstream plate with rectangular cross-section and faired leading edges and a downstream plate of rectangular cross-section were investigated, together with the sound radiation produced. However, the main investigation has been concentrated on single plates of rectangular cross-section with various chord-to-thickness ratios C and on arrays of two plates of rectangular cross-section in tandem having various chord-to-thickness ratios C₁ and C₂ and a range of gaps (with gap-to-thickness ratios G) between them. The range of Reynolds number based on plate thickness t and free-stream velocity U, Re[subscript]t = Ut/ν (where ν is the kinematic viscosity of fluid) covered in the measurements is 3.2 x 10[superscript]3 ≤ Re[subscript]t 53 x 10[superscript]3. Spectra of velocity fluctuations in the flow and radiated sound have been measured and their characteristic frequencies related. An attempt has been made to measure force fluctuations on surfaces of the plates in order to relate them to flow characteristics and radiated sound power. Mean and fluctuating pressures associated with the force fluctuations on the plates have also been obtained. The lengths of separation bubbles on long rectangular plates have also been determined. In most cases, the measurements have been complemented by flow-visualisation in a water tunnel to provide additional detailed insight into the flow patterns. Three flow regimes have been identified for single plates of rectangular cross-section. In the first regime (1 ≤ C ≤ 3.13), shear layers separated from the leading edges form a vortex street downstream of the plate without reattachment to it. Associated force fluctuations on the plate are the main source of acoustic radiation. In the second regime (3.05 ≤ C ≤ 9.65), the separated shear layers reattach intermittently to the streamwise plate surfaces. Vortex formation in the shear layer is the dominant cause of sound radiation but the effect becomes weaker as C increases. In the third regime (6.52 ≤ C ≤ 68), the separated shear layers form closed leading-edge separation bubbles. Weak vortex shedding, with only a small contribution to the sound radiation, occurs only at the trailing edges of the plate. Bistable behaviour of the flow over a plate, with random switching between the regimes, occurs for C ≈ 3 and 6.52 ≤ C ≤ 9.65. A proposed classification of possible flow regimes for the flow around two plates of rectangular cross-section in tandem has been confirmed experimentally. For small G, the flow in the gap between the plates is isolated from the external flow. When the gap G between the plates is increased to or beyond a critical value (between 2 and 3.5), the shear layers separated from the upstream plate form a von Karman vortex street in the gap before interacting with the downstream plate. Flow and acoustic measurements indicate that this transition is associated with dramatic changes in the flow character. / http://proxy.library.adelaide.edu.au/login?url= http://library.adelaide.edu.au/cgi-bin/Pwebrecon.cgi?BBID=1320474 / Thesis (Ph.D.) -- University of Adelaide, School of Mechanical Engineering, 2008

This thesis describes the application of mass spectrometry (MS) to glycoprotein and oligosaccharide analysis. Glycosylated proteins are involved in cell-cell and cell-matrix recognition. Applications of trypsin and proteinase K to hydrolyze glycoproteins into glycopeptides that are compatible with MS and MS/MS analysis are investigated. For successful site-specific analysis of glycans, glycopeptides with short peptide (3-8 residues) are needed. Although trypsin is an important enzyme for protein identification, proteinase K is superior for site-specific glycan analysis due to its potential to hydrolyze every glycoprotein to short glycopeptides. The gas-phase dissociation pathways, kinetics and energetics of protonated oligosaccharides are described. The oligosaccharides dissociate via cleavage at the glycosidic linkages during thermal activation. Using double resonance experiments, it was established that oligosaccharides undergo sequential and parallel fragmentation reactions. Furthermore, dissociation of product ions to secondary ions was confirmed. Arrhenius activation parameters, Ea and A for protonated alpha- and beta-linked D-glucopyranose oligosaccharides are reported.