Knorpel ist ein kompliziertes System aus einem kollagenen Netzwerk, gefüllt mit wasserbindenden Makromolekülen (Proteoglykanen) und darin eingebetteten Zellen. Störungen in den komplexen Wechselbeziehungen können zur Gefährdung der strukturellen Integrität des Knorpels führen. Die hochauflösende Magnetresonanztomographie (NMR-Mikroskopie) kann über die Analyse der Signalintensität interne Knorpelstrukturen darstellen (hypo- und hyperintense Zonen). Mit Hilfe ionenmikroskopischer Analysemethoden (PIXE, RBS, ERDA) wurden im Knorpel (femorale und tibiale Kondyle des Hausschweins) im Querschnitt die zweidimensionalen Verteilungen der Knorpelelemente (H, C, N, O, P, S, Cl, K und Ca) aufgenommen sowie die Konzentrationen in ausgewählten Zonen bestimmt. Ergänzend wurde mit STIM die Dichteverteilung im Knorpel untersucht. Es gelang auch mit STIM, erstmalig kollagene Fasern in ihrer, bis auf den Wasserentzug natürlichen, Umgebung im Knorpel und damit unverändert in ihrer Anordnung sichtbar zu machen (keine chemische Demaskierung nötig). Die Ergebnisse wurden mit NMR- und polarisationsmikroskopischen Untersuchungen verglichen und in ihrem Zusammenhang mit den histologischen Knorpelzonen diskutiert. In den NMR-hypointensen Zonen fanden sich eine erhöhte Chlorkonzentration und punktförmige Calciumanreicherungen. Diese Zonen waren (im gefriergetrockneten Zustand) durch eine, bis zu einem Faktor vier höhere Dichte gekennzeichnet, die im maximalen Gehalt der Matrixelemente, H, C, N, O, (höchste Kollagendichte) begründet liegt. Im tibialen Knorpel konnten in der NMR-hypointensen Zone radial verlaufende einzelne Kollagenfasern nachgewiesen werden. Im femoralen Knorpel wurden in dieser Zone keine Einzelfasern nachgewiesen. Es deutete sich eine tubuläre Anordnung der Kollagenfasern an. In der hypertrophen Zone zeigten sich hohe Konzentrationen an Phosphor (Zellorganellen), Schwefel (Proteoglykane), Kalium (alkalisches Milieu) und Calcium (Vorstufe der Kalzifizierung). Die Chlorkonzentration hatte dort ihr Minimum. In dieser Zone verlaufen die Kollagenfasern radial und münden senkrecht in den Kalkknorpel. In der Tangentialfaserschicht wurde eine erhöhte Konzentration an Calcium und Phosphor beobachtet (Einlagerung von Calciumphosphaten). In dieser Zone wurden tangential verlaufende Kollagenfasern und ihr Übergang zur stärkeren Vernetzung mit teilweise arkadenförmiger Überstruktur sichtbar gemacht. Zur genaueren Aufklärung der dreidimensionalen Anordnung der Kollagenen Strukturen wurden erste Experimente zur STIM-Tomographie durchgeführt.

This thesis aims to address a vital gap that has emerged in the digital identity regulatory discourse: how can the legal regulation of digital identity mirror the global nature of digital identity and be compatible with national local difference? Digital identity, or the digital representation of an individual, is a complex concept, which manifests in myriad forms (e.g. authenticators, claims, data or information, identifiers, presence, relationship representations and reputation) and natures. As such, it engages a gamut of legal domains ranging from criminal law, constitutional law, human rights law, law of identity schemes, contract law, intellectual property law, tort law and data protection law. Digital identity is global and local in its nature, influence and effects. Yet, the digital identity regulatory discourse has primarily developed in and focussed on the digitally advanced West, leaving out countries like India which are developing strong digital presences, with their own digital identity perceptions and needs. This situation is adverse to the sustained future of digital identity. Thus, the contribution of this thesis lies in filling this gap and preparing the ground for a dialogue between different countries with different national agendas through building international and local awareness of how similarities and differences operate in respect of digital identity, its regulation and providing a modest solution to help preserve the global and local dimensions of digital identity and its regulation. To this end, the thesis carried out comparative legal research on the legal regulation of digital identity using the UK and India as base jurisdictions. The original hypothesis was that that immense differences in the legal regulation of digital identity between the comparator countries would emerge. Yet, though differences were evident, considerable degrees of similarity also emerged, not just on the superficial level of mere identity of rules, but also in legal practice, in large part attributable to India’s penchant for legal transplants. While the transplantation of Western law did not result in a full-scale rejection of the transplanted laws in relation to digital identity in India, there are indications of anomalies caused by the imposition of Western cultural norms through law on an Indian society ill prepared for it. Thus there has resulted a tension between the local and the global, the indigenous and the externally imposed. The challenge is thus to resolve this, taking into account, on the one hand the need to maintain the global nature and relevance of digital identity and the other, the need to accommodate and be responsive to local differences. The thesis proposes a tentative solution called the tri-elemental framework (TeF) which draws from the Indian philosophical and legal concept of dharma (and its elements of Sad Achara, Vyavahara and Prayaschitta) and learns from the most universally relevant digital identity proposal, De Hert’s right to identity. The solution provides one way in which the law regulating digital identity, whatever its nature, can be made sense of and acquire cultural meaning appropriate to local contexts.

El objetivo de este trabajo es analizar y evaluar la contribución del modelo de gestión de la docencia “Competence Based Teaching” (CBT) en la gestión de la docencia de la educación preescolar de México. La investigación se enmarca en una metodología cualitativa con un enfoque interpretativo y un método de estudio de casos. Los resultados nos permiten analizar y evaluar los cambios en la gestión de la docencia y entre las principales conclusiones destacamos: la corroboración de que este modelo posibilita la mejora de la gestión en la educación preescolar de México; la detección de ciertas inconsistencias en la Propuesta Curricular Nacional, que han incidido en los procesos de gestión de las participantes; la importancia de seguir procesos de formación y acompañamiento adecuados, y el valor que tiene el trabajo colegiado y la práctica reflexiva para la mejora continua de la calidad educativa. / The aim of this paper is to analyze and assess the contribution that the “Competence Based Teaching” (CBT) management model of teaching has in the management of teaching preschool education of Mexico. The research is part of a qualitative methodology with an interpretive approach and a case study method. The results allow us to analyze and evaluate changes in the management of teaching, and among the key findings are: verification that this model enables improved management of preschool education in Mexico; detecting inconsistencies in the national proposal, that have influenced management processes of the participants; the importance of following proper training processes and support, and the value of collegial work and reflective practice for continuous improvement of educational quality.

A common analytical problem in applying LA sampling concerns dealing with large planar samples, e.g. gel plates, Si wafers, tissue sections or geological samples. As the current state of the art stands, there are two solutions to this problem: either sub-sample the substrate or build a custom cell. Both have their inherent drawbacks. With sub-sampling, the main issue is to ensure that a representative is sample taken to correctly determine the analytes of interest. Constructing custom cells can be time consuming, even for research groups that are experienced or skilled, as they have to be validated before data can be published. There are various published designs and ideas that attempt to deal with the issue of large samples, all of which ultimately enclose the sample in a box. The work presented in this thesis shows a viable alternative to enclosed sampling chambers. The non-contact cell is an open cell that uses novel gas dynamics to remove the necessity for an enclosed box and, therefore, enables samples of any arbitrary size to be sampled. The upper size limit of a sample is set by the travel of the XY stages on the laser ablation system, not the dimensions of the ablation cell.

Negative Poisson’s ratio, or auxetic, materials present the possibility of designing structures and components with tailored or enhanced mechanical properties. This thesis explores the phenomenon of auxetic behaviour in cubic crystals using classical and quantum modelling techniques and assesses the validity of these techniques when predicting auxetic behaviour in cubic elemental metals. These techniques are then used to explore the mechanism of this behaviour. The findings of the atomistic modelling are then used as a template to create networks of bending beams with tailored Poisson’s ratio behaviour.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Doctor of Philosophy / Department of Biological & Agricultural Engineering / Zhijian Pei / Donghai Wang / Renewable fuels derived from lignocellulosic biomass could reduce our dependence on fossil fuel resources and reduce greenhouse gas emissions. Big bluestem is an ecological-dominant warm-season (C4) perennial native grass that comprises as much as 80% of the plant biomass in prairies in the Midwestern grasslands of North America. Its high cellulosic content and low agricultural input recently have made big bluestem a promising feedstock for ethanol production. The overall goals of this study are to evaluate the potential of big bluestem in terms of ethanol production comparing with other native grasses by diluted sulfuric acid pretreatment and simultaneous saccharification and fermentation and to understand the effects of ecotype and planting location on the chemical and elemental compositions and thermal properties as well as fermentable sugar yield of big bluestem along the Great Plains precipitation gradient. A total conversion efficiency of 79.2% and an ethanol concentration of 9.4 g/L were achieved after 72 h fermentation. About 0.262 kg (~0.332 Liters) ethanol could be produced from one kilogram dry mass of big bluestem under the present condition. Planting location had significant effects on chemical and elemental as well as specific heat, thermogravimetric parameters, high heating value and glucan mass yield. Ecotype had significant effects on glucan, xylan, lignin, and ash contents, and C, O, and H elemental fractions as well as specific heat, high heating value and glucan mass yield, whereas planting location significantly affected all measured variables. The ecotype-location interaction had significant effects on glucan, lignin, hydrogen contents and specific heat. Up to 97%, 88% and 80% of the variation in compositions can be explained by annual precipitation, growing degree days and potential evapotranspiration in 2010 respectively. Among all environmental factors, potential evapotranspiration had the most significant effect on thermal properties. Planting location had a stronger influence than ecotype and interaction between location and ecotype. Precipitation in 2010 possibly played a more significant role in divergence of glucan mass yield of the big bluestem.

The effective air quality management in the heavy polluted areas has to be based on high-quality monitoring with properly designed monitoring network and targeted measurements, which provided information required to source apportionment. The thesis aim was to apportion sources of atmospheric aerosol based on highly time resolved data of mass concentration of size segregated aerosol, its temporal and spatial variability, elemental composition, OC/EC and size distribution of carcinogenic polyaromatic hydrocarbons. Sampling campaigns went during winter and summer in small settlement Březno by Chomutov, residential area Ostrava - Radvanice a Bartovice and Mladá Boleslav in the years 2008 - 2010, 2012, 2013. We determined mass concentrations of PM10, PM1-10, PM1.15-10 and PM0.15-1.5 and their size fraction ratios. Based on the size ratios, the source apportionment of fine fraction (PM0.15-1.15) with focus on PM0.34-1.15 is crucial. We examined seasonal and spatial variability of PM10, PM.2.5, PM1 and PM1-10. Based on the examination, we obtained representative highly-time resolved data with regards to season and sampling locality. We analysed dynamic of size distribution of particle-bond eight carcinogenic polycyclic hydrocarbons. Based on the results the source apportionment of PM0.34-1.15 is crucial....

O objetivo desse trabalho foi demonstrar a viabilidade do acoplamento entre as técnicas de cromatografia líquida de alta eficiência com a espectrometria de emissão óptica com plasma indutivamente acoplado (HPLC - ICP OES) em um equipamento da Thermo Fisher Scientific, visando análise de especiação elementar de espécies com maiores concentrações na amostra. A identificação de espécies moleculares associadas aos elementos Cu, Fe, Mg, e Zn em amostras de castanha de caju foi adotada como modelo para comprovar tal acoplamento. Para que o ICP OES pudesse adquirir sinais de emissão ao longo de um tempo determinado, ou seja, para que o equipamento pudesse coletar um sinal transiente, fundamental para o acoplamento HPLC - ICP OES, foi necessário executar algumas modificações. Para isso, foram feitas alterações na placa eletrônica principal do equipamento, e trocada sua caixa controladora de gases. Os parâmetros instrumentais do ICP OES foram otimizados em uma série de ensaios com o intuito de estabelecer e avaliar desempenho do instrumento e a robustez do método empregado nas análises de castanha de caju. Determinações das concentrações totais de Ca, Cu, Fe, Mg, Mn, Ni, e Zn foram feitas em amostras de castanha de caju e nos materiais de referência NIST 1515 e NIST 1547, apresentando uma exatidão do método aceitável, levando-se em consideração o preparo de amostra e a medida no ICP OES. As determinações totais elementares nas amostras de castanha de caju indicaram que os teores de Ca foram de (0,04 ± 0,01) % ; Cu (26,3 ± 5,0) mg kg-1; Fe (47,9 ± 8,8) mg kg-1; Mg (0,31 ± 0,04) %; Mn (25,6 ± 3,9) mg kg-1; Ni (24,8 ± 1,9) mg kg-1; Zn (66,3 ± 2,4) mg kg-1. Para identificação de espécies moleculares associadas aos elementos Cu, Fe, Mg, e Zn, foi feita nas amostras de castanha de caju uma extração de metais e proteínas utilizando-se de uma solução extrato de NaOH 1 mol L-1. O extrato ainda foi submetido à uma etapa de clean-up, com precipitação das proteínas com acetona e ressupenção das mesmas com tampão Tris-HCl, pH 7,4. As proteínas e metais ressupensos em tampão foram analisados no sistema HPLC ICP OES, em que a separação cromatográfica ocorreu através de uma coluna de exclusão por tamanho (SEC), a detecção molecular através do detector UV-Vis do HPLC, e a detecção elementar através do ICP OES. As espécies moleculares identificadas estão no intervalo de massa molecular compreendido entre 2 e 177 kDa, sendo que Cu, Fe e Zn apresentam associação com essas espécies moleculares. Foram monitorados ainda, no ICP OES, os sinais de intensidade de emissão de P e S. Esses elementos também apresentaram associação com espécies moleculares com peso molecular entre 2 e 177 kDa, sugerindo que essas espécies se tratam de metaloproteínas. / The aim of this study was to demonstrate the capability of coupling between liquid chromatography techniques of high efficiency with the optical emission spectrometry with inductively coupled plasma (HPLC - ICP OES) in an equipment of Thermo Fisher Scientific, aiming elemental speciation analysis of species with higher concentrations in the sample. The identification of molecular species associated with elements Cu, Fe, Mg and Zn in cashew nuts samples was adopted as a model to prove such coupling. For ICP OES could get emission signal through a certain time, so that the equipment could collect a transient signal, critical to the HPLC coupling - ICP OES, it was necessary to perform some modifications in the instrument. For this, changes were made to the main electronic board of the equipment and also changed their gas controller box. The instrumental parameters of the ICP OES were optimized in a series of tests in order to establish and evaluate performance of the instrument and the robustness of the method employed in cashew nut analysis. Determination of the total concentration of Ca, Cu, Fe, Mg, Mn, Ni and Zn were made in cashew sample and reference materials NIST 1515 and NIST in 1547, with an accuracy acceptable method, taking into account the sample preparation and measurement by ICP OES. The elemental total determinations in cashew nut samples indicated that Ca were (0.04 ± 0.01)%; Cu (26.3 ± 5.0) mg kg-1; Fe (47.9 ± 8.8) mg kg-1; Mg (0.31 ± 0.04)%; Mn (25.6 ± 3.9) mg kg-1; Ni (24.8 ± 1.9) mg kg-1; Zn (66.3 ± 2.4) mg kg-1. For the identification of molecular species associated with the elements Cu, Fe, Mg, and Zn was performed on samples of cashew nuts an extract of metals and proteins using an extract solution of NaOH 1 mol L-1. The extract was further subjected to one-step of clean-up with protein precipitation with acetone following by a resuspension with Tris-HCl buffer, pH 7.4. Proteins and metals resuspended in buffer, were analyzed in the HPLC - ICP OES system, wherein the chromatographic separation took place by a size exclusion column (SEC), the molecular detection by UV-Vis detector of HPLC, and elemental detection by ICP OES. The molecular species were identified in the molecular weight range between 2 and 177 kDa, and Cu, Fe and Zn are associated with these molecular species. Were also monitored in the ICP OES, P and S emission intensity signals. These elements also associated with molecular species having a molecular weight between 2 and 177 kDa, suggesting that this species are metalloproteins.

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