Besides collagen, elastin is the most common connective tissue structural protein in vertebrates and similar to collagen relatively resistant to non-specific degradation. Typical elastolytic proteases are the serine-dependent pancreatic and leukocyte elastases, the Zn-dependent matrix metalloproteinase 12, and several lysosomal cysteine proteases. Among the cysteine cathepsins, cathepsins S, K and V are highly potent elastases with cathepsin V displaying the highest activity among all known mammalian elastases. Despite a shared amino acid sequence identity of over 80% between cathepsins V and L and very similar subsite specificities, only cathepsin V has a potent elastase activity whereas cathepsin L lacks it. A series of chimera mutants containing various proportions of cathepsin V and cathepsin L were constructed in an attempt to define a specific region needed for elastin degradation. It was found that retaining the peptide sequence region from amino acids 89 to 119 of cathepsin V preserves the mutant’s elastolytic activity against elastin-Rhodamine conjugates whereas the region FTVVAPGK (amino acids 112-119) contributes approximately 60% of activity retention. Several additional mutant proteins involving mutual swapping of residues VDIPK (amino acids 113-117) of cathepsin L with residues TVVAPGK (amino acids 113-119) of cathepsin V, deletion of Glyl 18 from cathepsin V, and insertion of Gly between Prol 16 and Lysi 17 in cathepsin L were constructed and evaluated for their elastolytic activities. The results obtained with those mutant cathepsin proteins support the importance of the amino acid region spanning the residues from 112 to 119 in cathepsin V. Based on the 3-D structure of cathepsin V, this peptide region is located below subsite binding pocket S2 and forms a wall-like barrier which may act as an exosite for the productive binding of cross-linked elastin. / Medicine, Faculty of / Biochemistry and Molecular Biology, Department of / Graduate

Que ce soit pour la fabrication de transistors ultimes fonctionnant à haute fréquence et faible consommation d’énergie ou pour celle de composants quantiques exploitant le transport balistique d’électrons, l’élaboration de nanostructures de semiconducteurs III-V à faible masse effective électronique est aujourd’hui un enjeu majeur. Différentes approches existent pour atteindre des dimensions caractéristiques largement sub-100nm. Les nanostructures peuvent être définies par une approche descendante en combinant gravure sèche anisotrope et amincissement chimique digital d’une couche semiconductrice ou par une approche ascendante en élaborant directement les nanostructures désirées. Dans le deuxième cas, la croissance de nanofils catalysée par une bille métallique nanométrique a connu un engouement important ces quinze dernières années. La fabrication de composants utilisant ce procédé reste cependant très compliquée et nécessite souvent le report des nanofils sur un substrat hôte rendant extrêmement difficile la réalisation de circuits complexes. L’approche par croissance sélective dans les ouvertures d’un masque diélectrique offre au contraire des perspectives plus intéressantes. Si l’épitaxie à base d’organométalliques en phase vapeur a démontré son efficacité pour ce type de croissance, l’épitaxie par jets moléculaires peut permettre d’améliorer encore la pureté des nanostructures. C’est dans ce contexte que nous avons étudié les propriétés électriques de nanostructures III-V épitaxiées sélectivement sur substrat InP. L’utilisation d’un flux d’hydrogène atomique pendant la croissance permet d’obtenir une bonne sélectivité de croissance. Son impact sur les propriétés optiques et électriques du semiconducteur a d’abord été étudié puis l’utilisation de procédés de nanofabrication a permis l’élaboration et la caractérisation électrique de nanostructures. Des composants en InGaAs de type TLM, multi-branches ou MOSFET ont démontré la qualité des matériaux épitaxiés puisque des mobilités effectives à l’état de l’art pour ce type de matériau ont été obtenues. Grâce à l’utilisation de croissances sélectives multiples, nous avons pu élaborer des hétérostructures originales telles que des nanofils planaires à cœur InGaAs et coquille InP ou des hétérojonctions InGaAs/GaSb radiales ou axiales. Pour ces dernières, l’obtention de caractéristiques courant-tension présentant une résistance différentielle négative montre une bonne qualité d’interface, offrant des perspectives intéressantes pour la fabrication de nano-hétérojonctions tunnel. / The fabrication of nanoscale devices such as high frequency and low energy consumption transistors or quantum devices exploiting ballistic electrons transport requires the development of nanostructures with low effective mass III-V materials. Several technologies exist to reach typical dimensions well below the 100-nm range. The nanostructures can be defined by a top-down approach through a combination of anisotropic dry etching and digital chemical thinning of a semiconductor layer, or by a bottom-up approach with a direct elaboration of the nanostructures. In the second case, metal-catalyst-assisted nanowire growth has been widespread since the last fifteen years. However, the fabrication of devices based on this process is still tricky and often requires the transfer of the nanowires to a host substrate for device processing, preventing any complex circuit production. The approach by selective area growth inside dielectric mask openings exhibits a better scalability. If the organometallic vapor phase epitaxy (MOVPE) has proved its efficiency for this type of growth, molecular beam epitaxy (MBE) may further improve the nanostructure purity. Within this context, we study the electrical properties of selectively grown III-V materials on InP substrate by MBE. We demonstrate that the use of an atomic hydrogen flux during the growth ensures a good selectivity with respect to the dielectric mask and has a positive impact on the optical and electrical properties of the grown semiconductor. The electrical characterization of InGaAs nanostructures is performed thanks to the development of dedicated process such as TLM, branched nanowires or MOSFET devices. It reveals good transport properties with the state-of-the-art effective mobility for this kind of alloy. We then show that selective area epitaxy is also a valuable tool to develop original heterostructures such as in-plane InGaAs/InP core-shell nanowires with raised contacts and radial or axial InGaAs/GaSb heterojunctions. For these latter, the negative differential resistances observed on the current-voltage characteristics demonstrate a good interface quality, offering interesting possibilities for tunnel nano-heterojunction development.

<p> Acceptor compounds of C60 and hexafluoride ions of group V elements (P, As, Sb) were studied by infrared spectroscopy, x-ray diffraction and resistivity measurements. C60(AsF 6)1.9 was formed by reacting C60 powder with AsF5 gas dissolved in liquid S02. The AsF 6 ion was identified by a broad v3 absorption at 703 cm^-1, a shoulder at 681 cm^-1 and evidence of the sharp v4 absorption just below 400 cm^-1 in the infrared spectrum. The low frequency modes ofC60 at 527 and 576 cm^-1 were unshifted in the reacted powder. The T1u(3) mode of C60 , at 1183 cm^-1 was accompanied by neighbouring absorptions at 1194 and 1206 cm^-1, which were assigned tentatively to splitting of the triply degenerate mode. Three strong peaks at 1549, 1406 and 1322 cm^-1 observed in the spectra were assigned to splitting of the threefold degenerate T1u(4) mode of pristine C60 at 1428 cm^-1. Heat treatments ofthe sample, with temperatures ranging up to 350°C, were performed to thermally deintercalate the sample and to aid in identifying the infrared modes. The decrease in intensity ofthe AsF6 absorptions and the return ofthe four strong absorption lines ofundoped C60 indicated the successful deintercalation of the sample. X-ray diffraction indicated that the C60 lattice, which had expanded to body centered tetragonal to accommodate the AsF 6 ion, returned to the face centered cubic arrangement of pristine C60 following heat treatments at 350 degrees Celcuis. The C60(AsF6)1.9 compound exhibited semiconductor characteristics with an activation energy of 0.12 ± 0.05 eV. Possible interstitial sites for the AsF6- ion in the body-centered-tetragonal lattice of C60(AsF 6)1.9 have also been calculated. </p> <p> The PF6 ion, in the sample of C60 reacted with N02PF6 in S02, was observed in the IR spectra by the broad v3 absorption at 830 cm^-1 and the sharp v4 absorption at 558 cm^-1 No strong absorption of NO2+ at 2360 cm^-1 was observed indicating that the sample was not a simple mixture of the two powders. The C60 absorption lines, at 527, 576, I I 83 and 1428 cm^-1 were unshifted. However, the T1u(4) mode at 1428 cm^-1 showed asymmetric broadening on the low frequency side and small absorptions flanking the T 10( 4) mode. These features, although much less pronounced, may correspond to the shifting and splitting observed in the T1u(4) mode ofthe C6o{AsF6)1.9 compound. The octahedral SbF6- ion was identified in the sample of C60 powder reacted with N02SbF6 by the strong v3 absorption at 660 cm^-1. The C60 lines were unshifted, but small absorptions flanking the T1u(4) mode, are again similar to the absorptions assigned to splitting in the C60(AsF6)1.9 compound. </p> / Thesis / Master of Science (MSc)

No description available.

Made available in DSpace on 2016-12-08T16:44:49Z (GMT). No. of bitstreams: 1 PGPV14MA154.pdf: 838575 bytes, checksum: 1ddc3528cf3bc228191e87bd98d4719f (MD5) Previous issue date: 2014-08-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The use of rootstocks in viticulture emerged in Europe in the late nineteenth century, in order to protect European grapevines (Vitis vinifera L.)from phylloxera. As a consequence, the study of the influence of rootstocks on wine and oenological characteristics of the scion has become increasingly important, since there is no other way to avoid the attack of phylloxera. Viticulture in the South Highlands of Santa Catarina State is a recent activity when compared to the main wine regions, technical and scientific information about combinations of rootstocks and canopy varieties best suited to the conditions environment of the region. This purpose of this thesis was to evaluate de performance of Merlot variety grafted onto three rootstocks, and grown in three different altitudes of highlands of Santa Catarina State. The study was conducted in two commercial vineyards located in the counties of São Joaquim (1.300 m) and Urubici (1.150 m). The vineyard was established in 2004, spacing 1,5 x 3,0 m, with vines trained to one trunk and bilateral cordons and winter-pruned to two bud spurs per vine. Shoots were positioned in a Y-shaped trellis system. Merlot grapevines grafted onto 1103P, 3309C and 101-14 were evaluated during 2012/2013 and 2013/2014 cycles, according to the following variables: phenology, production, vigor, technological and phenolic ripening. Besides that, the phenolic and chromatic compositions of the wines were evaluated by spectrophotometer. The results reveal that Merlot vines grafted onto 101-14 and 3309C showed an anticipation of 5 days in São Joaquim and 3 days in Urubici, in the occurrence of véraison compared to vines combined with 1103P. This anticipation conferred a greater GDD accumulation until harvest. The Merlot variety grafted onto 3309C and 101-14 produced the lowest number of canes per meter of canopy, and 3309C produced the largest number of cluster per shoot. When grafted on 1103P, Merlot produced the lowest number of cluster per shoot the larger leaf area and higher chlorophyll content per area unit of leaf. In Urubici, Merlot had yielded the highest fruit load in plants grafted on 101-14. The increase in production was associated with increased physical characteristics of clusters. Rootstocks that induced low vigor as 3309 and 101-14, advanced the technology maturation. The rootstock 101-14 was related to higher accumulation of anthocyanins in grapes and wines. Chromatic characteristics related to the color of anthocyanins was also higher in wines from Merlot grafted onto 101-14 / O uso de portaenxertos na viticultura surgiu na Europa, no final do século XIX, com a finalidade de controlar a filoxera, principal praga que ataca a videira européia (Vitis vinifera L.). Como consequência, o estudo da influência dos portaenxertos sobre as características vitícolas e enológicas das variedades copa tem se tornado cada vez mais importante. A vitivinicultura do Planalto Sul de Santa Catarina é uma atividade recente, quando comparada às regiões tradicionais de produção de uvas destinadas à elaboração de vinhos finos, carecendo de informações técnico-científicas a respeito de combinações entre portaenxertos e variedades copa que melhor se adaptem às condições ambientais da região. Este trabalho teve por objetivo avaliar o desempenho viti-enológico da variedade Merlot produzida sobre três portaenxertos e em dois municípios de elevadas altitudes de Santa Catarina. O estudo foi realizado em vinhedos comerciais localizados nos municípios de São Joaquim (1.300 m) e em Urubici (1.150 m). O plantio foi realizado em 2004, com espaçamento 1,5 x 3,0 m, e as plantas foram conduzidas em cordão duplo, com poda em esporões de duas gemas. Os ramos do ano foram conduzidos no sistema de sustentação em Y . As plantas da variedade Merlot em combinação com os portaenxertos 1103P, 3309C e 101-14, foram avaliadas durante os ciclos 2012/2013 e 2013/2014, quanto às seguintes variáveis: ciclo fenológico, produtividade, vigor, maturação tecnológica e fenólica. Além disso, a composição fenólica e cromática dos vinhos, provenientes de cada combinação, foram avaliadas por métodos de espectrofotometria. Os resultados revelaram que as plantas Merlot enxertada sobre 101-14 e 3309C apresentaram uma antecipação média de 5 dias em São Joaquim e 3 dias em Urubici, na ocorrência da mudança de cor das bagas, quando comparadas às plantas combinadas com 1103P. Esta antecipação possibilitou um maior acúmulo de soma térmica (GDD) até a data da colheita. Quando enxertada em 3309C e 101-14, a variedade Merlot produziu os menores números de ramos por metro linear de dossel, e em 3309C produziu o maior número de cachos por ramo. Quando enxertada sobre 1103P, produziu o menor número de cachos por ramo, a maior área foliar e o maior teor de clorofila nas folhas. Em Urubici, obteve-se maior produção de carga de frutos em plantas enxertadas sobre 101-14. O aumento da produção esteve relacionado com o aumento das características físicas do cacho. Portaenxertos que induziram baixo vigor, como 3309C e 101-14, adiantaram a maturação tecnológica. O portaenxerto 101-14 esteve relacionado ao maior acúmulo de antocianinas nas uvas e nos vinhos. As características cromáticas relacionadas à cor das antocianinas também foi maior nos vinhos da combinação de Merlot com 101-14

Etwa 15% aller Paare bleiben ungewollt kinderlos. Männliche Faktoren sind in circa einem Drittel der Fälle als ursächlich anzusehen. Jedoch sind die Erfolgsraten der Therapie männlicher Infertilität durch assistierte Reproduktion auch nach über 30 Jahren seit deren Einführung unbefriedigend. Bestehende Spermienaufbereitungsmethoden wie einfaches Waschen, swim up oder die Dichtegradientenzentrifugation basieren auf makroskopisch-funktionellen Parametern wie Motilität und Morphologie. Spezifische Eigenschaften wie etwa eine aktivierte Apoptosesignalkaskade der Spermien werden dabei nicht berücksichtigt. Die wesentlichen Elemente verschiedener Signalwege der aus somatischen Zellen bekannten Apoptose konnten auch am humanen ejakulierten Spermatozoon nachgewiesen werden. Über die (negativen) Auswirkungen der Apoptose auf die männliche Fruchtbarkeit gibt es einen Konsens. Ziel der vorliegenden Arbeit war es, Selektionsmethoden zu entwickeln, welche auf subzellulärer Ebene intakte Spermien mit dem größtmöglichen Fertilisationspotential aus dem Ejakulat extrahieren. In einem ersten Versuchskomplex konnte gezeigt werden, dass durch die Kombination von Dichtegradientenzentrifugation und swim-up (Standardmethoden in Reproduktionskliniken und andrologischen Laboren) zur Aufbereitung der Spermien von subfertilen Patienten eine akzeptable Reduktion der Spermien mit aktivierter Apoptosesignalkaskade erreicht werden kann. Jedoch gaben die großen interindividuellen Unterschiede im Separationseffekt Anlass zur Entwicklung innovativer Untersuchungs- und Separationsmethoden. So wurden unter anderem fluoreszenzbasierte Tests zur Evaluation von Spermiendefekten, wie beispielsweise einer gestörten Integrität des mitochondrialen Membranpotentials, eingeführt. In den Untersuchungen wurde die Praktikabilität dieser neuen Analyseverfahren im Routineeinsatz unter Standardbedingungen getestet und bestätigt. Die innovative Selektionsmethode der Annexin V-MACS Separation basiert auf der Bindung von Annexin V-MicroBeads an apoptotische Spermien, womit eine Subpopulation reifer, motiler und vitaler Spermien mit inaktivierter Apoptosesignalkaskade gezielt angereichert wird. Das Konzept wurde zudem erfolgreich auf ein (Glaswoll-) Festphasen-Filtersystem ohne frei schwimmende Microbeads übertragen. Dadurch gelang die Minimierung eines potentiellen Transmissionsrisikos der Microbeads bei der Anwendung im Rahmen der künstlichen Befruchtung. Den hohen Stellenwert dieser Verfahren belegen die Ergebnisse zweier in-vitro Modelle, an denen erstmalig gezeigt werden konnte, dass durch die Selektion von Spermien mit inaktivierter Apoptose-Signalkaskade höhere Fertilisationsraten erreichbar sind.

The aim of this thesis is to explore how does the marketing management of major Czech drama scenes reflect strategies and concepts described in the theoretical approaches to marketing, particularly in the specialized foreign literature. The goal is the marketing analysis of the most significant theaters in the Czech Republic, research the functionality and importance of marketing plans, strategies and tools, analysis of marketing management, awareness of audience and customer care. The methods used are literature search, description of known marketing concepts (marketing mix, segmentation, positioning, audience building, and audience development), and comparison of different approaches to marketing management, qualitative research, analysis of data obtained through research and expert interviews.

The speed and complexity of globalisation and reduction of natural resources on the one hand, and interests of large multinational corporations on the other, necessitates proper management of mineral resources and consumption. The need for scientific research and application of new methodologies and approaches to maximise Net Present Value (NPV) within mining operations is essential. In some cases, drill core logging in the field may result in an inadequate level of information and subsequent poor diagnosis of geological phenomenon which may undermine the delineation or separation of mineralised zones. This is because the interpretation of individual loggers is subjective. However, modelling based on logging data is absolutely essential to determine the architecture of an orebody including ore distribution and geomechanical features. For instance, ore grades, density and RQD values are not included in conventional geological models whilst variations in a mineral deposit are an obvious and salient feature. Given the problems mentioned above, a series of new mathematical methods have been developed, based on fractal modelling, which provide a more objective approach. These have been established and tested in a case study of the Kahang Cu-Mo porphyry deposit, central Iran. Recognition of different types of mineralised zone in an ore deposit is important for mine planning. As a result, it is felt that the most important outcome of this thesis is the development of an innovative approach to the delineation of major mineralised (supergene and hypogene) zones from ‘barren’ host rock. This is based on subsurface data and the utilisation of the Concentration-Volume (C-V) fractal model, proposed by Afzal et al. (2011), to optimise a Cu-Mo block model for better determination of an ultimate pit limit. Drawing on this, new approaches, referred to Density–Volume (D–V) and RQD-Volume (RQD-V) fractal modelling, have been developed and used to delineate rock characteristics in terms of density and RQD within the Kahang deposit (Yasrebi et al., 2013b; Yasrebi et al., 2014). From the results of this modelling, the density and RQD populations of rock types from the studied deposit showed a relationship between density and rock quality based on RQD values, which can be used to predict final pit slope. Finally, the study introduces a Present Value-Volume (PV-V) fractal model in order to identify an accurate excavation orientation with respect to economic principals and ore grades of all determined voxels within the obtained ultimate pit limit in order to achieve an earlier pay-back period.

In this thesis I propose an improved theory of ontological commitment, one which is neutral on epistemology. Although Quine's quantificational criterion of ontological commitment has many advantages over its competitors, like its univocal treatment of being and existence, its clear account of ontological reduction and its capacity to accommodate implicit commitments, I argue that it has a fatal flaw: the inability to account for ontological commitment to individuals. Quine's choice of a first-order language of regimentation without constants is so entwined with his holist epistemology that imputations of existence cannot be made except to objects-qua-F, qua some wholly third-personal description. Commitments of those who believe that minds reach out directly to objects by means of acquaintance or introspection, encoded in language by constants, are ungrammatical in Quine's language. This breakdown of grammaticality, on my view, is an avoidable result of Quine's behaviourism and holist epistemology filtering into his choice of canonical language. I opt for a broader conception of ontological commitments as incurred by formalised theories with one or more semantic categories of categorematic objectual expressions, whose function is to stand for objects. I expand the language of regimentation at least to first-order logic with constants and identity. This preserves the attractive features of Quine's position. It retains its elegant treatment of reduction and implicit ontological commitments, and its capacity to explain away Meinongian confusions, without being beholden to global holism. My canonical language makes room for acquaintance and first-personal methods as sources of ontological commitment. It has the advantage of allowing theories like Quine's, which confine themselves to objects-qua-F, to be regimented as well as non-holist theories whose criteria of ontological commitment are 'to be is to be the referent of a name' or 'to be is to be the value of a constant or variable'.

Depuis quelques années, le protactinium suscite un regain d'intérêt en raison de l'implication de cet élément dans les réacteurs à combustible thorium, qui font partie des scénarios envisagés pour répondre aux besoins énergétiques du futur. Dans ce travail, le comportement du protactinium(V) en solution aqueuse acide a été étudié en présence de deux ligands organiques : l'acide oxalique et le DTPA. L'étude a été conduite selon une double approche : structurale, à l'aide des techniques de Spectroscopie d'Absorption des rayons X (SAX) et d'Electrophorèse Capillaire (EC-ICP-MS), complétée par des calculs de type DFT, et thermodynamique par la technique d'extraction par solvant. Le protactinium forme avec l'acide oxalique un complexe limite d'ordre 3 dans lequel la présence de la liaison courte mono-oxo a été mise en évidence grâce à l'analyse des spectres XANES et EXAFS. La charge (–3) de ce complexe a pu être déduite de mesures d'électrophorèse capillaire couplée ICP-MS. La structure optimisée de l'entité [PaO(C2O4)3] se caractérise par une coordination bidentate des trois oxalates, dont deux se situent dans le plan “équatorial” de la liaison Pa=O. Les constantes de formation des différents complexes successifs conduisant à PaO(C2O4)33– ont été déterminées à partir de l'analyse des variations du coefficient de partage D de Pa(V) en fonction de la concentration de ligand, dans le système TTA/toluène/H2O/NaClO4/HClO4/H2C2O4 à différentes températures pour une force ionique de 3 M. L'influence de la température a révélé une forte contribution entropique (excepté lors de la formation de PaO(C2O4)2–). La variation enthalpique relative aux équilibres successifs, accompagnant la formation des complexes est favorable pour les deux premiers complexes mais légèrement défavorable pour la formation du complexe limite. Avec le DTPA, les expériences d'électrophorèse capillaire ont clairement montré la formation d'un complexe neutre ; d'après les expériences d'extraction par solvant, il s'agit d'un complexe (1:1), pouvant donc correspondre à la formulation Pa(DTPA). L'arrangement le plus stable, issu de calculs de type DFT, montre que la coordination du protactinium est assurée par l'ensemble des atomes donneurs de la molécule de DTPA : les 3 atomes d'azote et les 5 atomes d'oxygène de chacune des fonctions carboxyliques. La constante de stabilité βapp de ce complexe a été déterminée pour différentes valeurs de force ionique et de température. La température s'est révélée sans influence sur les constantes de complexation entrainant l'hypothèse d'une variation enthalpique nulle et donc de la formation de Pa(DTPA) gouvernée par l'entropie.