A luminescência persistente é um fenômeno em que o material emite radiação de segundos a várias horas após cessada a irradiação (luz, radiação UV, feixe de elétrons, etc.). No entanto, os mecanismos que geram o fenômeno da luminescência persistente ainda não são totalmente estabelecidos. Neste trabalho os materiais Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados pelo método de estado-sólido assistido por micro-ondas (MASS) e comparados com aqueles sintetizados pelo método cerâmico. As vantagens do método MASS incluem curto tempo de processamento, aquecimento dielétrico seletivo, baixo consumo de energia e uso de equipamentos de baixo custo (forno micro-ondas doméstico), muitas vezes produzindo produtos de alta pureza e alto rendimento. Os materiais foram caracterizados pelas técnicas de espectroscopia de absorção na região do infravermelho (IR), espectroscopia Raman, difração de raios X método do pó (DRX), microscopia eletrônica de varredura (MEV), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray Excited Optical Luminescence (XEOL), espectroscopia de fotoluminescência na região do UV-Visível, espectroscopia de fotoluminescência na região do UV-UV vácuo e termoluminescência (TL). Os fósforos Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ ou Tb,Ca2+) foram preparados em um curto período de tempo (22-26 min) pelo método MASS utilizando forno micro-ondas doméstico, carvão ativado como susceptor, fluxos (H3BO3 ou Na2CO3) e sem a aplicação de gases. Todos materiais preparados com fluxo de H3BO3 exibem impurezas de LuBO3 que foram quantificadas por refinamento Rietveld. Os fluxos e os dopantes não alteraram consideravelmente a estrutura cristalina da matriz C-Lu2O3. As micrografias MEV sugerem que o fluxo de Na2CO3 e os precursores nitratos geram partículas de Lu2O3 com tamanho menor devido a evolução de gases provenientes da decomposição destes compostos. Por outro lado, quando é usado óxidos como precursores os materiais apresentam maiores tamanhos de partícula e na presença de H3BO3 leva a maior agregação. Os dados de XANES indicam que houve completa redução do íon TbIV &#8594 Tb3+ e parcial do PrIV &#8594 Pr3+, devido ao uso de carvão ativado que gera CO(g) durante o tratamento térmico. Os espectros da luminescência persistente indicam emissões nas regiões do vermelho/NIR, vermelho alaranjado e verde atribuídas as transições 4fN &#8594 4fN características dos íons Pr3+, Eu3+ e Tb3+, respectivamente. As diferenças entre os espectros registrados sob excitação UV e após cessada a irradiação podem ser explicadas pela emissão da luminescência persistente predominante dos íons TR3+ no sítio S6 do que no C2. Além disso, a co-dopagem aliovalente com os íons HfIV e Ca2+ aumentam a intensidade e duração da luminescência persistente. Isto ocorre através da geração de armadilhas provenientes dos dois co-dopantes nos sítios de Lu3+ e por defeitos produzidos na compensação de carga. Os materiais fotônicos preparados pelo método MASS com fluxo de H3BO3 apresentam maior intensidade e duração da luminescência persistente comparados aos preparados pelo método cerâmico ou sem a presença de H3BO3. Os mecanismos da luminescência persistente foram desenvolvidos através de princípios similares baseados nos dados experimentais da energia do band gap, posição dos níveis de energia dos íons TR3+/2+ na matriz e energia das armadilhas. Isto confirma a solidez da interpretação dos dados experimentais dos materiais Lu2O3:TR3+,M exibindo luminescência persistentes e encoraja a expansão de modelos similares para outros materiais apresentando esse fenômeno. Os fósforos Lu2O3:Pr3+,HfIV,Lu2O3:Eu3+(,Ca2+) e Lu2O3:Tb3+,Ca2+) apresentaram sintonização de cores de emissão tanto para o fenômeno da fotoluminescência como da luminescência persistente, podendo atuar como bons candidatos nas aplicações de bioimageamento ou sensibilizadores de células solares. / Persistent luminescence is a phenomenon where the material emits radiation from seconds to several hours after cessation of irradiation (light, UV radiation, electron beam, etc.). The persistent luminescence mechanisms are not entirely established, however. In this work, the materials Lu2O3:TR3+,M (TR,M: PrHfIV; Eu, Ca2+ or Tb,Ca2+) were prepared by MASS method as well as compared to these materials synthetized by ceramic method. The advantages of MASS method include short processing time, selective dielectric heating, low energy consumption and use of inexpensive equipment (domestic microwave oven), often affording high-purity and high-yield products. The materials were characterized by Infrared absorption spectroscopy (IR), Raman spectroscopy, X-ray powder diffraction (XPD), Scanning electron microscopy (SEM), X-ray absorption near edge structure (XANES), Extended X-ray absorption fine structure (EXAFS), X-ray excited optical luminescence (XEOL), photoluminescence spectroscopy in the UV-Visible range, photoluminescence spectroscopy in the UV-UV vacuum region and thermoluminescence (TL). The phosphorsLu2O3:TR3+,M (TR,M: Pr,HfIV; Eu, Ca2+ or Tb,Ca2+) were rapidly (22-26 min) and successfully prepared by MASS method using a domestic microwave oven, carbon as susceptor, fluxes (H3BO3 or Na2CO3) and without special gases application. All materials prepared with H3BO3 flux exhibit LuBO3 impurities that were quantified by Rietveld refinement. The flux and dopants does not considerably affect the crystalline structure of the C-Lu2O3 host matrix. Scanning electron micrographs suggest that Na2CO3 flux and nitrates precursors produce Lu2O3 particles of small size due to the gases evolution from the decomposition of these compounds. On the other hand, the materials prepared from oxides precursors have particles of large size and H3BO3 flux induces particle xi aggregation. The carbon used as the susceptor generates CO gas, leading to complete reduction of TbIV to Tb3+ and partial conversion of PrIV to Pr3+ present in the Tb4O7 and Pr6O11 precursors, as indicated by XANES. Persistent luminescence spectra of the materials show emission in the red/NIR, reddish orange and green ranges assigned to the 4fN &#8594 4fN transitions characteristics of Pr3+, Eu3+ and Tb3+ ions, respectively. Differences between the spectra recorded under UV excitation and after ceased the irradiation can be explained by the predominant persistent luminescence emission of TR3+ ion in the S6 site rather than TR3+ in the C2 site. In addition, inclusion of HfIV and Ca2+ codopants in the Lu2O3 host increases the emission intensity and duration of persistent luminescence due to generation of traps caused by charge compensation in the lattice as well as these metal ions in the Lu3+ sites. The photonic materials prepared by MASS method with H3BO3 flux show higher persistent luminescence performance than those prepared by the ceramic method or MASS without flux. The persistent luminescence mechanisms were developed through similar principles based on experimental data of band gap energy, energy level positions of TR3+/2+ ions in the host and traps energy. This similarity confirms the consistency of the interpretation of experimental data for the Lu2O3:TR3+,M materials and encourages the expansion of similar models for other persistent luminescence materials. Color tuning of persistent luminescence in Lu2O3:TR3+,M (TR,M: Pr,HfIV; Eu,Ca2+ or Tb,Ca2+) provides potential applications in bioimaging as well as in solar cell sensitizers.

Evaluations of the Higher Education Sector are receiving increased attention, due to the rising expenditures and the absence of efficiency enhancing market pressure. To what extent universities are able to eliminate inefficiency is a question that has only partially been answered. This paper argues that heterogeneity among universities as well as persistent inefficiency hinder the institutions to achieve full efficiency - at least in the short run. Two standard and one novel specification of the Stochastic Frontier Analysis are applied to a new, comprehensive set of panel data to show how the standard efficiency evaluation changes when both aspects are taken into account. It is the first time that the idea of persistent inefficiency is considered in the analysis of the German Higher Education Sector. The comparison reveals that the disregard of heterogeneity distorts the estimation results towards lower efficiency values. The newly introduced specification improves the accuracy of the heterogeneity assumption and exposes that inefficiency tends to be long term and persistent rather than short term and residual. This implies that increasing efficiency requires a comprehensive change of the university structure.

Despite measures on the European level to increase the compatibility between the HE sectors of the member states, the recent literature exposes variations in their efficiencies. To gain insights into these differences we split the efficiency term according to the two management levels each university is confronted with. Utilizing a recent advancement in the method to measure efficiency, we separate short-term (transient) and long-term (persistent) efficiency, while controlling for unobserved institution specific heterogeneity. While the first term reflects the efficiency of the individual universities working within the country, the second term echoes the influence of the country specific overall HE structure. The cross-country comparison displays if the overall efficiency difference between countries is related to individual performance of their universities or their HE structure. This allows more purposeful policy recommendation and expands the literature regarding the efficiency of universities in a fundamental way. Choosing Italy and Germany as two important illustrative examples we can take advantage of a novel dataset including characteristics of institutions in both countries for an exceptional long period of time from 2001 to 2011. We show that the Italian universities exhibit a higher overall efficiency value than their German counterparts. With the individual universities working at the upper bound of efficiency in both countries, the overall inefficiency as well as the gap between the countries is caused by persistent, structural inefficiency. To expedite a true European Area of Higher Education future measures should hence aim at the country specific structure, not solely at affecting the activities of single universities.

Qu’est-ce qui détermine la survie et le succès des organisations à travers les différents régimes institutionnels? La présente étude tente à répondre à la question en analysant l’évolution d'une institution médicale publique russe, c. à. d. l'Institution de l'Etat Fédéral « Le Complexe Intersectoriel de Recherche et Technologie « Microchirurgie de l'Œil » de Rosmedtechnologie. L’étude s’étend sur quatre périodes bien définies: 1960-1985 (la Russie Soviétique, la période de pré-perestroïka), 1986-1991 (la perestroïka de Gorbatchev), 1992-2000 (la transition), et 2001-2009 (la Russie actuelle, la période post-Fyodorov). L’analyse se centre sur une coévolution des institutions externes et de la structure organisationnelle de l'entreprise, le système de droits de propriété, les tendances d'innovation et les canaux de diffusion technologique. Les conclusions suggèrent que l'environnement institutionnel général exerce une influence sur la performance de l'entreprise en déterminant « les règles du jeu » pour les transactions économiques et en établissant un ensemble de possibilités de développement. C'est alors les processus internes à l'entreprise, ses compétences dynamiques et sa capacité à innover qui déterminent si l'organisation peut s'adapter aux changements externes, reconnaître les possibilités de développement et en profiter. Par ailleurs, la direction (le leadership), le type de technologie et le niveau de sa diffusion, l’initial soutien de l'Etat, de même que la demande jouent un rôle apparent pour soutenir la performance réussie. Une structure multi-niveaux des récompenses de performance en combinaison avec les méthodes de traitement innovatrices (c. à. d. l’usage d’un conveyor chirurgical et la production en brigades) ont amené à des volumes de procédures cliniques performées plus élevées, de même que la qualité, la complexité et la diversité de traitement plus élevées. D’autant plus, pendant les étapes plus anciennes du développement de l’entreprise, la présence des inventeurs prolifiques et la structure organisationnelle qui soutenait l’apprentissage, la production et l’accumulation des connaissances (le cycle « clinique – ingénierie – approbation – production – clinique ») étaient cruciaux pour la création d’une base d’innovation persistante. Pendant les périodes plus récentes, la combinaison d’accès aux ressources (matérielles, financières, capital humain), les collaborations externes, les méthodes innovatrices d’organisation de traitement, la diffusion extensive des technologies inter- et intra-firme ont aussi contribué à des hauts niveaux d’innovation. Au total, le travail soutient une approche interdisciplinaire à l’étude des organisations, c. à. d. une combinaison de l'analyse institutionnelle, l’économie évolutionnaire et l’économie dynamique d’organisations, le management stratégique, l’économie d'innovation, l’analyse des droits de propriété et le rôle de leadership. / What determines organizational survival and success across different institutional regimes? The present historical case study attempts to answer the question by analyzing the evolution of a Russian state medical institution, i.e. the S.N. Fyodorov “Inter-Sectoral Research and Technology Complex “Eye Microsurgery””. The study spans over four clearly defined regimes: 1960 – 1985 (Soviet Russia, pre-perestroika period), 1986 – 1991 (Gorbachev’s perestroika), 1992 – 2000 (the transition years), and 2001 – 2009 (current Russia, post-Fyodorov period). The analysis focuses on the co-evolution of the external institutions and the firm’s organizational structure, the system of property rights, innovation patterns and the channels of technological diffusion. The findings suggest that the general institutional environment exerts influence on the firm’s performance through determining the “rules of the game” for economic transactions and through establishing a set of development possibilities. It is then the firm’s internal processes, dynamic competences and the ability to innovate that determine whether the organization can adapt to external changes, recognize the development possibilities and take advantage of them. In addition, the roles of leadership, the type of technology and its diffusion scope, initial State support, as well as the extent of demand are apparent in sustaining successful performance. Multi-level high performance rewards structure in combination with novel industrialized treatment methods (e.g. the use of a surgical conveyer and team production) resulted in greater volumes of clinical procedures performed, as well as higher quality, complexity and diversity of treatment. In addition, at the earlier stages of the firm’s development, the presence of prolific innovators and the organizational structure that supported learning, knowledge production and accumulation (the “clinic – engineering – approbation – production – clinic” cycle) were crucial for creating a basis for persistent innovation. In later periods, the combination of resource availability (material, financial, human capital), external collaborations, novel ways of organizing treatment, extensive inter and intra-firm diffusion of technologies also contributed to high levels of innovation. Overall, the work provides support for an interdisciplinary approach to the study of organizations, i.e. combining institutional analysis, evolutionary and dynamic organizational economics, strategic management, the economics of innovation, the analysis of property rights and the role of leadership.

As aves marinhas são sensíveis às alterações em todos os níveis tróficos, decorrentes de variações na disponibilidade de presas e contaminação por alguns compostos, capazes de se acumular nos tecidos dos organismos e magnificar-se através da cadeia trófica. As ilhas oceânicas brasileiras abrigam importantes colônias reprodutivas de aves marinhas e, apesar de serem consideradas locais remotos, estão sujeitas à contaminação decorrente de atividades humanas. Este trabalho avaliou a presença de poluentes orgânicos persistentes (POPs) em sangue, uma matriz não-destrutiva, de seis espécies de aves marinhas no Arquipélago de São Pedro e São Paulo e na Ilha da Trindade, que possibilita o monitoramento destes indivíduos ao longo dos anos. Os resultados indicaram que os principais POPs detectados no sangue (em ng g-1 de massa úmida) foram PCBs (0,05 a 55,09), DDTs (0,01 a 17,36) e Mirex (0,01 a 5,53). A migração influenciou nos altos níveis de POPs encontrados em Pterodroma arminjoniana e a massa (g) média dos indivíduos apresentou uma forte correlação negativa com as concentrações dos compostos predominantes no sangue. O sexo das aves não contribuiu significativamente nas concentrações de POPs em espécies monotípicas, exceto para a espécie Sula leucogaster que apresenta dimorfismo sexual acentuado. O comportamento alimentar, avaliado através da análise de isótopos estáveis de carbono e de nitrogênio (δ13C e δ15N), bem como as condições biológicas de cada animal contribuíram para explicar as variações nos perfis de contaminação entre as diferentes espécies. No geral, observou-se que as concentrações de POPS nos dois locais apresentaram valores baixos e similares sugerindo a via atmosférica como principal mecanismo de entrada desses contaminantes para estas regiões. Os resultados inéditos de POPs em sangue das aves marinhas nas duas mais recentes unidades de conservação marinhas criadas no Brasil, podem contribuir como referência para o monitoramento desses compostos em longo-prazo nessas regiões. / Seabirds are sensitive to changes at all trophic levels, due to variations in prey availability and contamination by some compounds, which can be accumulated in the tissues of organisms and to be magnified through the trophic chain. The Brazilian oceanic islands harbor important seabird breeding colonies and, although they are considered remote sites, they are subject to contamination from human activities. This work evaluated the presence of Persistent Organic Pollutants (POPs) in blood, a non-destructive matrix, of six species of seabirds in the São Pedro and São Paulo Archipelago (SPSPA) and Trindade Island (TI), that allows the monitoring of these individuals over the years. The results indicated that the major POPs detected in blood (ng g-1 in wet weight) were PCBs (0.05 to 55.09), DDTs (0.01 to 17.36) and Mirex (0.01 to 5,53). Migration influenced the high levels of POPs found in Pterodroma arminjoniana and the mean mass (g) of the individuals drove a strong negative correlation with the concentrations of the predominant compounds in the blood. The gender of the individuals did not contribute significantly to the concentrations of POPs in monotypic species, except for the species Sula leucogaster that presents marked sexual dimorphism. The feeding behavior was evaluated through the analysis of stable isotopes of carbon and nitrogen (δ13C and δ15N) as well as the biological conditions of each animal contributed to explain the variations in the contamination profiles between the different species. In general, we observed that POPS concentrations at both sites presented low and similar values suggesting the atmospheric transport as the main input mechanism of these compounds for these regions. The unpublished results of POPs, in blood of seabirds from the two most recent marine conservation units created in Brazil, can contribute as reference values for their long-term monitoring in those regions.

Gestillte Kinder sind über die Muttermilch mit persistenten organischen Schadstoffen (POPs) belastet. Tierexperimentelle Studien deuten auf eine besondere Empfindlichkeit des sich entwickelnden Immunsystems für POPs hin. Mögliche Effekte dieser Verbindungen auf den kindlichen Organismus sind bisher kaum untersucht. Es wurden potenzielle Einflüsse verschiedener POPs (PCDDs, PCDFs, PCBs, beta-HCH, HCB und pp-DDE) auf natürliche Killerzellen (NK-Zellen) und NK-Aktivität bei gestillten im Vergleich zu nicht gestillten Kindern untersucht. NK-Zellen sind eine Lymphozytensubpopulation (CD3-CD56/16+), die über ihre zytotoxische Aktivität allogene, virusinfizierte und maligne Zellen ohne vorherige Sensibilisierung töten kann. Es wurden 66 gesunde Kinder im Alter von 11-12 Monaten untersucht, davon waren 50 Kinder mindestens 4 Monate lang voll gestillt und 16 Kinder nicht gestillt. Aus einer Region mit bekannter erhöhter PCDD/PCDF-Belastung stammten 13 gestillte Kinder. Die NK-Zellzahlen wurden mittels Immunphänotypisierung am Durchflusszytometer bestimmt. Die Aktivität der NK-Zellen wurde mit einem nicht-radioaktiven, durchflusszytometrischen Zytotoxizitäts-Assay gemessen. Die POP-Konzentrationen im Blutfett der Probanden wurden kommerziell bestimmt. Weder bei den NK-Zellzahlen, noch bei der NK-Aktivität konnten zwischen den gestillten und nicht-gestillten Kindern signifikante Unterschiede im t-Test nachgewiesen werden. In Korrelationsanalysen zeigten sich keine signifikanten Einflüsse der POP-Konzentrationen auf NK-Zellzahlen und NK-Aktivität. Im Laufe der Untersuchung zeigte sich, dass der eingesetzte Zytotoxizitäts-Assay nur semiquantitative Daten lieferte. Die vorliegenden Ergebnisse und weitere Befunde bezüglich des Immunsystems der Probanden weisen darauf hin, dass die relativ hohe Belastung lange gestillter Säuglinge mit POPs nicht zu einer biologischen Wirkung im kindlichen Organismus führt. Angesichts der nachgewiesenen positiven Effekte des Stillens, kann diesbezüglich die bestehende Stillempfehlung bekräftigt werden. / Breast-fed infants are exposed to persistent organic pollutants (POPs) via breast milk. Animal studies indicate a special sensitivity of the maturing immune system to POPs. Possible effects of these compounds on the infantile organism are so far barely examined. Potential influences of several POPs (PCDDs, PCDFs, PCBs, beta-HCH, HCB and pp-DDE) on natural killer (NK) cells and NK activity of breast-fed infants in comparison to formula-fed infants were investigated. NK cells are a subset of lymphocytes (CD3-CD56/16+) that can kill allogeneic, virus-infected and malignant cells via their cytotoxic activity without prior sensitization. The study group consisted of 66 healthy infants examined at age 11 to 12 months, of which 50 infants were breast-fed and 16 infants were formula-fed. 13 breast-fed infants came from a region with known increased PCDD/PCDF-burden. Numbers of NK cells were measured by flow cytometric immunophenotyping. NK activity was analysed by a non-radioactive flow cytometric cytotoxicity assay. POP concentrations in the blood fat of the probands were calculated commercially. There were no significant differences between breast-fed and formula-fed infants concerning number and activity of NK cells in the t-test. Analysis of correlation showed no significant influences of POP concentrations on the number and activity of NK cells. In the course of the study the data obtained by the employed cytotoxicity assay proved to be only semiquantitative. The presented findings and further results concerning the immune system of the study subjects suggest that the relatively high burden of long-term breast-fed infants with POPs does not lead to a biological effect in the infantile organism. Regarding the proven positive effects of breast-feeding the existing recommendation to breastfeed can be encouraged.

No description available.

Die elektrische Signalverarbeitung in Nervenzellen basiert auf deren erregbarer Zellmembran. Üblicherweise wird angenommen, dass die in der Membran eingebetteten leitfähigen Ionenkanäle nicht auf direkte Art gekoppelt sind und dass die Kapazität des von der Membran gebildeten Kondensators konstant ist. Allerdings scheinen diese Annahmen nicht für alle Nervenzellen zu gelten. Im Gegenteil, verschiedene Ionenkanäle “kooperieren” und auch die Vorstellung von einer konstanten spezifischen Membrankapazität wurde kürzlich in Frage gestellt. Die Auswirkungen dieser Abweichungen auf die elektrischen Eigenschaften von Nervenzellen ist das Thema der folgenden kumulativen Dissertationsschrift. Im ersten Projekt wird gezeigt, auf welche Weise stark kooperative spannungsabhängige Ionenkanäle eine Form von zellulärem Kurzzeitspeicher für elektrische Aktivität bilden könnten. Solche kooperativen Kanäle treten in der Membran häufig in kleinen räumlich getrennte Clustern auf. Basierend auf einem mathematischen Modell wird nachgewiesen, dass solche Kanalcluster als eine bistabile Leitfähigkeit agieren. Die dadurch entstehende große Speicherkapazität eines Ensembles dieser Kanalcluster könnte von Nervenzellen für stufenloses persistentes Feuern genutzt werden -- ein Feuerverhalten von Nutzen für das Kurzzeichgedächtnis. Im zweiten Projekt wird ein neues Dynamic Clamp Protokoll entwickelt, der Capacitance Clamp, das erlaubt, Änderungen der Membrankapazität in biologischen Nervenzellen zu emulieren. Eine solche experimentelle Möglichkeit, um systematisch die Rolle der Kapazität zu untersuchen, gab es bisher nicht. Nach einer Reihe von Tests in Simulationen und Experimenten wurde die Technik mit Körnerzellen des *Gyrus dentatus* genutzt, um den Einfluss von Kapazität auf deren Feuerverhalten zu studieren. Die Kombination beider Projekte zeigt die Relevanz dieser oft vernachlässigten Facetten von neuronalen Membranen für die Signalverarbeitung in Nervenzellen. / Electrical signaling in neurons is shaped by their specialized excitable cell membranes. Commonly, it is assumed that the ion channels embedded in the membrane gate independently and that the electrical capacitance of neurons is constant. However, not all excitable membranes appear to adhere to these assumptions. On the contrary, ion channels are observed to gate cooperatively in several circumstances and also the notion of one fixed value for the specific membrane capacitance (per unit area) across neuronal membranes has been challenged recently. How these deviations from the original form of conductance-based neuron models affect their electrical properties has not been extensively explored and is the focus of this cumulative thesis. In the first project, strongly cooperative voltage-gated ion channels are proposed to provide a membrane potential-based mechanism for cellular short-term memory. Based on a mathematical model of cooperative gating, it is shown that coupled channels assembled into small clusters act as an ensemble of bistable conductances. The correspondingly large memory capacity of such an ensemble yields an alternative explanation for graded forms of cell-autonomous persistent firing – an observed firing mode implicated in working memory. In the second project, a novel dynamic clamp protocol -- the capacitance clamp -- is developed to artificially modify capacitance in biological neurons. Experimental means to systematically investigate capacitance, a basic parameter shared by all excitable cells, had previously been missing. The technique, thoroughly tested in simulations and experiments, is used to monitor how capacitance affects temporal integration and energetic costs of spiking in dentate gyrus granule cells. Combined, the projects identify computationally relevant consequences of these often neglected facets of neuronal membranes and extend the modeling and experimental techniques to further study them.