Theoretical Performance Model and Initial Experimentation of a Baffled-Tube Ram Accelerator

Thesis (Master's)--University of Washington, 2016-08

Coordination of phosphido-boratabenzene ligands to transition metals

Environ 90% des composés produits industriellement sont fabriqués à l’aide de catalyseurs. C’est pourquoi la conception de catalyseurs toujours plus performants pour améliorer les procédés industriels actuels est toujours d’intérêt. De la grande variété de complexes avec des métaux de transition rapportés jusqu’à présent, les complexes zwitterioniques attirent notre attention par leurs activités catalytiques souvent supérieures aux complexes cationiques normaux. Un complexe métallique zwitterionique est un fragment métal-ligand neutre où la charge positive est située sur le centre métallique et où la charge négative est délocalisée sur un des ligands liés au métal. Nous proposons la synthèse de ligands anioniques phosphine comportant des groupements borates et boratabenzènes. Cette dernière espèce est un cycle à 6 membres où l’un des atomes de carbone est remplacé par un atome de bore et qui est négativement chargé. La capacité de ces phosphines anioniques à se lier à un centre métallique à l’aide de la paire libre du phosphore est due à la nature du lien P-B qui défavorise l’interaction entre la paire libre du phosphore et l’orbitale p vide du bore. Les propriétés de di-tert-butylphosphido-boratabenzène (DTBB) comme ligand phosphine anionique hautement donneur et encombré ainsi que la découverte de ses modes de coordination inhabituels pour stabiliser les métaux de transition insaturés ont été étudiés au cours de ce travail. De nouvelles perspectives sur les modes de coordination de phosphido-boratabenzène et la force de l’interaction du lien P-B seront discutées ainsi que les applications catalytiques. Nous avons d’abord étudié la coordination η1 avec des complexes de fer, ce qui nous a fourni des données quantitatives précieuses sur la capacité du DTBB d’agir comme ligand très donneur par rapport aux autres ligands donneurs bien connus. La capacité du DTBB à changer de mode de coordination pour soutenir les besoins électroniques du métal a été démontrée par la découverte d’une nouvelle espèce ferrocenyl phosphido-boratabenzène et sa nucléophilie a été étudiée. Au meilleur de notre connaissance, aucun exemple d’un ligand boratabenzène coordonné aux métaux du groupe 11 n’existe dans la littérature. Voilà pourquoi nous avons décidé d’explorer les modes de coordination du ligand DTBB avec Cu(I), Ag(I) et Au(I). A notre grande surprise, le ligand DTBB est capable de stabiliser les métaux du groupe 11 aux états d’oxydation faibles par une liaison MP qui est une coordination du type η1, un mode de coordination guère observé pour les ligands boratabenzène. Pendant nos travaux, notre attention s’est tournée vers la synthèse d’un complexe de rhodium(I) afin de tester son utilité en catalyse. A notre grande satisfaction, le complexe Rh-DTBB agit comme un précatalyseur pour l’hydrogénation des alcènes et alcynes à la température ambiante et à pression atmosphérique et son activité est comparable à celle du catalyseur de Wilkinson. Dans un désir d’élargir les applications de notre recherche, notre attention se tourna vers l’utilisation des composés du bore autres que le boratabenzène. Nous avons décidé de synthétiser une nouvelle espèce phosphido-borate encombrée. Lorsqu’elle réagit avec des métaux, l’espèce phosphido-borate subit un clivage de la liaison P-B. Toutefois, cette observation met en évidence la singularité et les avantages de la stabilité de la liaison P-B lors de l’utilisation du fragment boratabenzène. Ces observations enrichissent notre compréhension des conditions dans lesquelles la liaison P-B du ligand DTBB peut être clivée. Ces travaux ont mené à la découverte d’un nouveau ligand ansa-boratabenzène avec une chimie de coordination prometteuse.

Imagens do terceiro setor: um estudo com pais e responsáveis financeiros das organizações educacionais

The present report is the result of an applied research in the educational entities of the third sector, aiming to demonstrate whether the financial influences the perception of users on the image of those entities. For both used the prospect of integrative marketing relationship adapting to and developing a set of indicators which bore the measurement of images from the model of Machado et al (2005) and Kotler and Fox (1994). The sample included a total of 187 parents and financial responsibility in 03 (three) institutions of education in Natal / RN. These data were processed by multivariate statistical analysis, factor analysis, linear regression, analysis of cluster and discriminant analysis. The factor analysis also identified 6 images perceived by users of services. Next were the relationships of cause and effect between the financial and images formed. In discriminant analysis, was identified two distinct groups of parents and guardians with financial perceptions similar and well defined. The result of the work shows that the differential level of financial participation of parents and guardians not influence the formation of the images formed from educational institutions of the third sector

Neue Erkenntnisse zum geologischen Bau des “Kleinen Berges” zwischen Bad Laer und Bad Rothenfelde (südwestliches Niedersachsen) aufgrund der Ergebnisse der Tiefbohrung ‘Bad Laer Z 1’

The 2108,0 m deep exploration well "Bad Laer Z 1" (1993) has been carried down in order to investigate the deeper ground lying beneath the "Kleiner Berg" anticline, concerning the existence of reservoir beds which was postulated according to preceeding seismic investigations. This aim of the borehole was not attained, because no formations have been drilled suitable for the construction of an artificial gas reservoir. On the other hand the bore hole revealed a great amount of new regional geologic, stratigraphic, mining, coalification and coal bed gas data. Therefore, from a scientific point of view the exploration well must be considered successful. After the drilling of a stratigraphic succession, mainly consisting of cretaceous "Pläner" limestones (from Albian to Turonian), surprisingly in a depth of only 439 m productive Upper Carboniferous rocks formed by the Lembeck beds of uppermost Westfalian C have been found. In addition to this discovery, nearly the whole Westfalian C and B reaching down to the coal bed "Katharina" at the Westfalian A boundary were drilled through revealing over 66 partly minable coal beds. Investigations of the coalification pattern showed a more or less continuous increase of the rank gradient with depth reaching from the step of gas flame coal down to 700 m over that of gas coal down to 1600 m to that of fat coal down to the bottom of the borehole. An additional surprising result of the exploration well was the observation, that immediately below the base of the Cretaceous the coal beds revealed a high gas content without the presence of a desorption zone. This result must also be considered as success of the drilling with respect to the strong interest in a potential utilization of coal bed methane nowadays.

Postharvest handling practices and irradiation increase lenticel discolouration in ‘B74’ mango fruit

ABSTRACT 'B74' mango is a recently commercialised cultivar in Australia, with an appealing skin colour and firm fibreless flesh. However, fruit can develop lenticel discolouration (LD) after harvest, with loss of commercial value, especially after γ-irradiation as a disinfestation treatment. We hypothesised that postharvest practices could increase fruit sensitivity to LD and tested that by sequentially sampling fruit between the orchard and the end of the packing line over two seasons, followed by ripening without and with irradiation treatment. Exposure of 441-610 Gy γ-irradiation significantly increased the severity of LD by 6.8-fold in commercially picked and packed ripe fruit, reducing the proportion of marketable fruit from 98% to 2%, compared to irradiated fruit harvested directly from the trees and not exposed to de-sapping solution and packing operations. Also, LD increased progressively as the fruit passed through the harvesting and packing processes, and exposure to only bore water increased LD severity compared with no water contact. Results suggest that the typical de-sapping process used during harvesting is a major contributor to skin sensitivity to LD in 'B74' mango fruit, and that other packing operations involving wetting of the fruit have an additive effect on it. These effects are exacerbated if fruit is irradiated.

Développement et caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque

Ce projet de recherche mené en collaboration industrielle avec St-Jean Photochimie Inc. / PCAS Canada vise le développement et la caractérisation de dérivés dipyrrométhène pour des applications dans le domaine du photovoltaïque. La quête du récoltage des photons se situant dans le proche-infrarouge a été au centre des modifications structurales explorées afin d’augmenter l’efficacité de conversion des cellules solaires de type organique et à pigments photosensibles. Trois familles de composés intégrant le motif dipyrrométhène ont été synthétisées et caractérisées du point de vue spectroscopique, électrochimique, structural ainsi que par modélisation moléculaire afin d’établir des relations structures-propriétés. La première famille comporte six azadipyrrométhènes au potentiel de coordination tétradentate sur des centres métalliques. Le développement d’une nouvelle voie synthétique asymétrique combinée à l’utilisation d’une voie symétrique classique ont permis d’obtenir l’ensemble des combinaisons de substituants possibles sur les aryles proximaux incluant les noyaux 2-hydroxyphényle, 2-méthoxyphényle et 2- pyridyle. La modulation du maximum d’absorption dans le rouge a pu être faite entre 598 et 619 nm. De même, la présence de groupements méthoxyle ou hydroxyle augmente l’absorption dans le violet (~410 nm) tel que démontré par modélisation. La caractérisation électrochimique a montré que les dérivés tétradentates étaient en général moins stables aux processus redox que leur contre-parti bidentate. La deuxième famille comporte dix dérivés BODIPY fusionnés de façon asymétrique en position [b]. L’aryle proximal a été modifié de façon systématique afin de mieux comprendre l’impact des substituents riches en électron et de la fusion de cycles aromatiques. De plus, ces dérivés ont été mis en relation avec une vaste série de composés analogues. Les résultats empiriques ont montré que les propriétés optoélectroniques de la plateforme sont régies par le degré de communication électronique entre l’aryle proximal, le pyrrole sur lequel il est attaché et le noyau indolique adjacent à ce dernier. Les maximums d’absorption dans le rouge sont modulables entre 547 et 628 nm et la fluorescence des composés se situe dans le proche- infrarouge. L’un des composé s’est révélé souhaitable pour une utilisation en photovoltaïque ainsi qu’à titre de sonde à pH. La troisième famille comporte cinq complexes neutres de RuII basés sur des polypyridines et portant un ligand azadipyrrométhène cyclométalé. Les composés ont montré une forte absorption de photons dans la région de 600 à 800 nm (rouge à proche- infrarouge) et qui a pu être étendue au-delà de 1100 nm dans le cas des dérivés portant un ligand terpyridine. L’analyse des propriétés optoélectroniques de façon empirique et théorique a montré un impact significatif de la cyclométalation et ouvert la voie pour leur étude en tant que photosensibilisateurs en OPV et en DSSC. La capacité d’un des complexes à photo-injecter un électron dans la bande de conduction du semi-conducteur TiO2 a été démontré en collaboration avec le groupe du Pr Gerald J. Meyer à University of North Carolina at Chapel Hill, premier pas vers une utilisation dans les cellules solaires à pigments photosensibles. La stabilité des complexes en solution s’est toutefois avérée problématique et des pistes de solutions sont suggérées basées sur les connaissances acquises dans le cadre de cette thèse.

Project work in a Basque L2 classroom: students’ perceptions

[EN] Project Work has been acknowledged as an efficient medium for language learning for more than two decades (Stoller, 2006) according to the numerous successful applications of project-based programmes that have been reported. In spite of the lack of sufficient controlled studies to assess the benefits of project work, and the existence of some studies giving evidence of students discontent with project work, the reports given by second language (SL) and foreign language students (FL) who have experienced project based instruction give support to the success attributed to project-based learning, as they recognised having improved language skills, learnt content, developed real life skills, as well as gained in self-confidence and motivation (Sierra, 2008 and 2011; Stoller, 2006). The aim of the present study is to explore some key issues involved in implementing a project-based programme focusing on the students’ perceptions of learning gains, their views on the collaborative assessment scheme used in the programme, and the students’ overall evaluations of the implementation of project work in a post-compulsory secondary education context in Navarre, Spain, with students learning Basque as a second language. A group of 12 students enrolled in a project work based programme participated in the study. Results showed that the students’ perceptions were very positive concerning doing projects, learning gains and group work, although more grammar instruction and teacher-fronted activities were requested by the students. However, the collaborative assessment process and the use of a Notebook/Diary as a reflection tool bore mixed evaluations.

Imagens do terceiro setor: um estudo com pais e responsáveis financeiros das organizações educacionais

The present report is the result of an applied research in the educational entities of the third sector, aiming to demonstrate whether the financial influences the perception of users on the image of those entities. For both used the prospect of integrative marketing relationship adapting to and developing a set of indicators which bore the measurement of images from the model of Machado et al (2005) and Kotler and Fox (1994). The sample included a total of 187 parents and financial responsibility in 03 (three) institutions of education in Natal / RN. These data were processed by multivariate statistical analysis, factor analysis, linear regression, analysis of cluster and discriminant analysis. The factor analysis also identified 6 images perceived by users of services. Next were the relationships of cause and effect between the financial and images formed. In discriminant analysis, was identified two distinct groups of parents and guardians with financial perceptions similar and well defined. The result of the work shows that the differential level of financial participation of parents and guardians not influence the formation of the images formed from educational institutions of the third sector

Factors influencing compliance to universal precautions in healthcare workers: a systematic literature review

Background: Occupational exposure to blood borne viruses involving hollow bore needles is one of the most commonly reported adverse events affecting staff in the National Health Service in the UK. Universal Precautions Guidelines were originally developed in 1987 in order to minimise the risk of contact with body fluid. Universal precautions not only protect staff against blood borne pathogens but are also considered as an efficient mean to reduce the spread of pathogens from patients to patients via healthcare workers.Aim of the study: The aim of this study was to identify and evaluate the objective evidence on factors influencing healthcare workers compliance to universal precautions through a systematic literature review.Methodology: This systematic review was conducted in 2009 and studies were retrieved through electronic databases, manual journal searches and communications with experts in the field. Studies of cross sectional survey design and observational design were included in the review as they constituted the most commonly used research design evaluating compliance to universal precautions.A quality checklist was developed based on existing assessment criteria.Findings: Studies conducted to ascertain compliance to universal precautions are plentiful but remain of low quality. Sixty studies were retrieved and evaluated for potential inclusion in this study. Four studies met the inclusion criteria. Three were of cross-sectional survey design and one of direct observational design.Conclusions: Uptake of universal precautions remains low despite known benefits. Lack of time, resources and lack of knowledge have been shown as being factors negatively influencing healthcare workers compliance with universal precautions.This paper also highlights the issues surrounding the inclusion of low grade evidence in systematic literature reviews and the implications of reviews including low grade evidence on practice.Type of article: Research paperKeywords: systematic review, universal precautions, standard precautions, compliance, healthcare worker.

Coexistence of mcr-1 and blaNDM-1 in Escherichia coli from Venezuela

We studied the presence of the mobile colistin resistance gene mcr-1 in human, animal, and environmental Enterobacteriaceae samples from Cumana, Venezuela, that were collected in 2015. The mcr-1 gene was detected in 2/93 Escherichia coli isolates from swine (novel ST452) and human (ST19) samples that were resistant to colistin. Whole-genome sequencing and transformation experiments identified mcr-1 on an IncI2 plasmid. One of the isolates also bore the widely spread carbapenemase NDM-1. A One Health approach is necessary to further elucidate the flux of these high-risk genes.

Multiresistance in Pasteurella multocida is mediated by coexistence of small plasmids

In most gram-negative bacteria, acquired multiresistance is conferred by large plasmids compiling numerous antimicrobial resistance genes. Here, we show an evolutionary alternative strategy used by Pasteurella multocida to become resistant to multiple clinically relevant antibiotics. Thirteen beta-lactam-resistant clinical isolates, concomitantly resistant to tetracyclines and/or streptomycin as well as to sulfonamides, were studied. Pulsed-field gel electrophoresis analysis revealed different profiles among the isolates, showing that clonal dissemination was not the sole event responsible for the spread of multiresistance. Each P. multocida strain carried two or three small plasmids between 4 and 6 kb in size. A direct association between resistance profile and plasmid content was found. Complete nucleotide sequencing of all plasmids revealed seven different replicons, six of them belonging to the ColE1 superfamily. All plasmids carried one, or a maximum of two, antimicrobial resistance determinants. Plasmids pB1000 and pB1002 bore bla(ROB-1), pB1001 carried tet(B), pB1003 and pB1005 carried sul2 and strA, pB1006 harbored tet(O), and p9956 bore the tet(H) gene. All plasmids except pB1002 and pB1006 were successfully transformed into Escherichia coli. pB1000, also involved in beta-lactam resistance in Haemophilus parasuis (A. San Millan et al., Antimicrob. Agents Chemother. 51:2260-2264, 2007), was mobilized in E. coli using the conjugation machinery of an IncP plasmid. Stability experiments proved that pB1000 was stable in P. multocida but highly unstable in E. coli. In conclusion, bla(ROB-1) is responsible for beta-lactam resistance in P. multocida in Spain. Coexistence and the spread of small plasmids are used by P. multocida to become multiresistant.

Playing with tension; national charisma at Euro 2012

European National football came together in the summer of 2012 for the 14th occasion. This book sets out to examine the enduring social tensions between supporters and authorities, as well as those between local, national and European identities, which formed the backdrop to the 14th staging of the European National football tournament, Euro2012. The context of the tournament was somewhat unique from those staged in previous years, being jointly hosted for the first time by two post-Communist nations still in the process of social and economic transition. In this respect, the decision to stage Euro 2012 in Poland and Ukraine bore its own material and symbolic legacies shaping the tournament: the unsettling of neo-liberal imaginings and emergent ‘East-West’ fears about poor infrastructure, inefficiencies and corruption jostled with moral panics about racism and fears surrounding the potentially unfulfilled consumerist expectations of west European supporters. The book seeks to explore the ideologies and practices invoked by competing national sentiments and examine the social tensions, ambiguities and social capital generating potentials surrounding national, ethnic, European identity, with respect to national football teams, supporters and supporter movements.