Interfacial Electron Transfer Dynamics Following Laser Flash Photolysis of [Ru(bpy)(2)((4,4 `-PO(3)H(2))(2)bpy)](2+) in TiO(2) Nanoparticle Films in Aqueous Environments

Nanosecond laser flash photolysis has been used to investigate injection and back electron transfer from the complex [(Ru-(bpy)(2)(4,4`-(PO(3)H(2))(2)bpy)](2+) surface-bound to TiO(2) (TiO(2)-Ru(II)). The measurements were conducted under conditions appropriate for water oxidation catalysis by known single-site water oxidation catalysts. Systematic variations in average lifetimes for back electron transfer, - were observed with changes in pH, surface coverage, incident excitation intensity, and applied bias. The results were qualitatively consistent with a model involving rate-limiting thermal activation of injected electrons from trap sites to the conduction band or shallow trap sites followed by site-to-site hopping and interfacial electron transfer, TiO(2)(e(-))-Ru(3+) -> TiO(2)-Ru(2+). The appearance of pH-dependent decreases in the efficiency of formation of TiO(2)-Ru(3+) and in incident-photon-to-current efficiencies with the added reductive scavenger hydroquinone point to pH-dependent back electron transfer processes on both the sub-nanosecond and millisecond-microsecond time scales, which could be significant in limiting long-term storage of multiple redox equivalents.

Lean management and innovation in operational efficiency: the EGR project implemented by Pirelli Tyre Brazil in Santo André plant

O trabalho tem como objetivo avaliar e descrever analiticamente a implementação de práticas de manufatura enxuta pela Pirelli Pneus no seu complexo industrial da América Latina. Além de uma descrição estruturada e ampla dos princípios de produção de Toyota e fundamentos teóricos do Lean thinking, uma ênfase especial será dedicada ao projeto EGR (Especialistas em Gestão da Rotina), como uma ferramenta estratégica para ser usada pela empresa multinacional italiana no futuro próximo, de modo a alcançar um resultado mais eficaz e eficiente na gestão da rotina diária. Este projeto, que representa um componente significativo do Pirelli Manufacturing System (PMS) e, principalmente, voltado para supervisores e gestores de plantas, consiste principalmente em ajudar a empresa a desenvolver a capacidade empresarial para avaliar corretamente o gap potencial existente entre os resultados atuais e os esperados, para tanto entender os desvios, bem como as causas subjacentes, e melhorar continuamente o desempenho da empresa por meio da padronização de processos e redução de desperdicios. Esses objetivos podem ser perseguidos, atuando em dois meios essenciais: habilidades técnicas e comportamentais de liderança para apoiar cada equipe de projeto; uma maior eficácia na gestão de indicadores de desempenho nas diferentes unidades de fábrica, de acordo com KPIs estabelecidos no nível central pelo Head Quarter. Além disso, a investigação será focada na experiência peculiar da planta de Santo André, onde o EGR começou como piloto, com o objetivo de captar as alterações relevantes (no lado organizacional e econômico) que este projeto trouxe para a empresa, através da realização de pesquisa de campo e entrevistas, que são orientados a recolher provas, considerações e opiniões de todos os principais atores envolvidos.

Gochnatia polymorpha (Less.) Cabrera (Asteraceae) changes in leaf structure due to differences in light and edaphic conditions

Gochnatia polymorpha (Less.) Cabrera é uma espécie de Asteraceae com ampla distribuição no bioma cerrado, sendo encontrada em diversas fisionomias florestais da região sudeste do Brasil. O presente estudo descreve alguns caracteres anatômicos foliares dessa espécie e os analisa quantitativamente em função de sua ocorrência nas formações florestais e também das diferenças de luminosidade. Foram encontradas diferenças quantitativas em todos os parâmetros anatômicos analisados. Os resultados demonstram que a alta plasticidade anatômica foliar nesta espécie pode ser considerada como uma vantagem adaptativa que a permite ocorrer em diversos ambientes do cerrado.

Changes in abiotic characteristics of water in the Paranapanema River and three lateral lagoons at mouth zone of the Jurumirim Reservoir during the flood period, São Paulo, Brazil

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tribute to R.G. Boutilier: Skin colour and body temperature changes in basking Bokermannohyla alvarengai (Bokermann 1956)

In amphibians solar basking far from water sources is relatively uncommon since the highly permeable amphibian skin does not represent a significant barrier to the accompanying risk of losing water by evaporation. A South American frog, Bokermannohyla alvarengai (Bokermann 1956), however, spends a significant amount of the day exposed to full sun and relatively high temperatures. The means by which this frog copes with potentially high rates of evaporative water loss and high body temperatures are unknown. Thus, in this study, skin colour changes, body surface temperature, and evaporative water loss rates were examined under a mixture of field and laboratory conditions to ascertain whether changes in skin reflectivity play an important role in this animal's thermal and hydric balance. Field data demonstrated a tight correlation between the lightness of skin colour and frog temperature, with lighter frogs being captured possessing higher body temperatures. Laboratory experiments supported this relationship, revealing that frogs kept in the dark or at lower temperatures (20 degrees C) had darker skin colours, whereas frogs kept in the light or higher temperatures (30 degrees C) had skin colours of a lighter hue. Light exhibited a stronger influence on skin colour than temperature alone, suggesting that colour change is triggered by the increase in incident solar energy and in anticipation of changes in body temperature. This conclusion is corroborated by the observation that cold, darkly coloured frogs placed in the sun rapidly became lighter in colour during the initial warming up period (over the first 5 min), after which they warmed up more slowly and underwent a further, albeit slower, lightening of skin colour. Surprisingly, despite its natural disposition to bask in the sun, this species does not possess a 'waterproof' skin, since its rates of evaporative water loss were not dissimilar from many hylid species that live in arboreal or semi-aquatic environments. The natural history of B. alvarengai is largely unknown and, therefore, it is likely that the herein reported colour change and basking behaviour represent a complex interaction between thermoregulation and water balance with other ecologically relevant functions, such as crypsis.

Use of synthetic aperture radar for recognition of Coastal Geomorphological Features, land-use assessment and shoreline changes in Bragança coast, Pará, Northern Brazil

Imagens de radar de abertura sintética (SAR) vem sendo bem mais utilizadas do que antes nas aplicações de geociências em regiões tropicais úmidas. Nesta investigação, uma imagem RADARSAT-1, na banda C, polarização HH adquirida em 1998 foi usada para o mapeamento costeiro e avaliação da cobertura da terra na área de Bragança, norte do Brasil. Imagem do radar aerotransportado GEMS-1000, na banda X, polarização HH, adquirida em 1972 durante o projeto RADAM foi também utilizada para avaliar as variações costeiras ocorridas nas últimas três décadas. A pesquisa tem confirmado a utilidade da imagem RADARSAT-1 para o mapeamento geomorfológico e avaliação da cobertura da terra, particularmente em costas de manguezal de macromaré. Além disso, um novo método para estimar as variações da linha de costa baseado na superposição de vetores extraídos de diferentes imagens SAR, com alta acurácia geométrica, tem mostrado que a planície costeira de Bragança tem estado sujeita a severa erosão responsável pelo recuo de aproximadamente 32 km² e acreção de 20 km², resultando em uma perda de área de manguezal de aproximadamente 12 km². Como perspectiva de aplicação, dados SAR orbitais e aerotransportados provaram ser uma importante fonte de informação tanto para o mapeamento geomorfológico, quando para o monitoramento de modificações costeiras em ambientes tropicais úmidos.

Hematological and biochemical changes in a Phrynops geoffroanus (Schweigger, 1812) population in response to environmental stressors

Turtles are among the most endangered vertebrate groups, and the main threats to populations are environmental pollution and habitat degradation. The species Phrynops geoffroanus, popularly known as “Geoffroy’s side-necked turtle”, has proliferated in polluted environments, where adverse conditions could influence their living habits and physiological condition. Studies that monitor the effects of environmental pollution are key to understanding the species’ biology and designing effective conservation strategies. Thus, the analysis of hematological and biochemical parameters has been shown to be important in assessing the health of wild animals and risks for the animal and ecosystem. This study aimed to assess the environmental influence on the physiology of a P. geoffroanus population through the evaluation of antioxidant status and responses to environmental stressors, compared to specimens from a place under controlled conditions. Blood samples of 60 specimens were collected, 30 from the Felicidade Stream, polluted environment, within the city of São José do Rio Preto, and 30 from the “Reginaldo Uvo Leone” breeding farm, Tabapuã, SP, a place under controlled conditions, whose samples constituted the control group. They were evaluated by hemogram and by determining thiobarbituric acid reactive species (TBARS), Trolox-equivalent antioxidant capacity (TEAC) and the activities of the antioxidant enzymes catalase and glucose-6-phosphate dehydrogenase (G6PDH). There was a wide variation in hematological parameters of P. geoffroanus from the urban environment. The red blood cell count and hemoglobin values were significantly less than those observed in animals from the breeding farm (P = 0.0004; P = 0.0371, respectively). There was a significant increase in the number of thrombocytes (P < 0.0001) and leukocytes (P < 0.0001) in the animals from Felicidade Stream. The stress indices were similar between the two groups (P = 0.4077). TBARS levels showed the cytotoxic potential of compounds in the urban environment, whose animals had elevated levels of lipid peroxidation (P < 0.0001), despite showing a response to environmental damages with increase in antioxidant capacity, as demonstrated by the TEAC assay (P = 0.0207). The lower catalase enzyme activity noted in individuals from the urban environment (P = 0.000184) could be due to the presence of inhibitory compounds. On the other hand, G6PDH activity was higher (P = 0.002962), where this enzyme acts in the generation of NADPH, which is used in several detoxification pathways. We conclude that environmental contamination can increase oxidative damages and generate physiological changes in this species. These data are very useful for the conservation of P. geoffroanus and turtles in general, and confirm that these techniques are effective in monitoring natural regions and that P. geoffroanus can serve as an environmental contamination bioindicator.

Semantic-based middleware solutions to support context-aware service provisioning in pervasive environments

The dynamicity and heterogeneity that characterize pervasive environments raise new challenges in the design of mobile middleware. Pervasive environments are characterized by a significant degree of heterogeneity, variability, and dynamicity that conventional middleware solutions are not able to adequately manage. Originally designed for use in a relatively static context, such middleware systems tend to hide low-level details to provide applications with a transparent view on the underlying execution platform. In mobile environments, however, the context is extremely dynamic and cannot be managed by a priori assumptions. Novel middleware should therefore support mobile computing applications in the task of adapting their behavior to frequent changes in the execution context, that is, it should become context-aware. In particular, this thesis has identified the following key requirements for novel context-aware middleware that existing solutions do not fulfil yet. (i) Middleware solutions should support interoperability between possibly unknown entities by providing expressive representation models that allow to describe interacting entities, their operating conditions and the surrounding world, i.e., their context, according to an unambiguous semantics. (ii) Middleware solutions should support distributed applications in the task of reconfiguring and adapting their behavior/results to ongoing context changes. (iii) Context-aware middleware support should be deployed on heterogeneous devices under variable operating conditions, such as different user needs, application requirements, available connectivity and device computational capabilities, as well as changing environmental conditions. Our main claim is that the adoption of semantic metadata to represent context information and context-dependent adaptation strategies allows to build context-aware middleware suitable for all dynamically available portable devices. Semantic metadata provide powerful knowledge representation means to model even complex context information, and allow to perform automated reasoning to infer additional and/or more complex knowledge from available context data. In addition, we suggest that, by adopting proper configuration and deployment strategies, semantic support features can be provided to differentiated users and devices according to their specific needs and current context. This thesis has investigated novel design guidelines and implementation options for semantic-based context-aware middleware solutions targeted to pervasive environments. These guidelines have been applied to different application areas within pervasive computing that would particularly benefit from the exploitation of context. Common to all applications is the key role of context in enabling mobile users to personalize applications based on their needs and current situation. The main contributions of this thesis are (i) the definition of a metadata model to represent and reason about context, (ii) the definition of a model for the design and development of context-aware middleware based on semantic metadata, (iii) the design of three novel middleware architectures and the development of a prototypal implementation for each of these architectures, and (iv) the proposal of a viable approach to portability issues raised by the adoption of semantic support services in pervasive applications.

Functional Genomics and Cell Biology of the Dolphin (Tursiops runcatus): Establishment of Novel Molecular Tools to Study Marine Mammals in Changing Environments

The dolphin (Tursiops truncatus) is a mammal that is adapted to life in a totally aquatic environment. Despite the popularity and even iconic status of the dolphin, our knowledge of its physiology, its unique adaptations and the effects on it of environmental stressors are limited. One approach to improve this limited understanding is the implementation of established cellular and molecular methods to provide sensitive and insightful information for dolphin biology. We initiated our studies with the analysis of wild dolphin peripheral blood leukocytes, which have the potential to be informative of the animal’s global immune status. Transcriptomic profiles from almost 200 individual samples were analyzed using a newly developed species-specific microarray to assess its value as a prognostic and diagnostic tool. Functional genomics analyses were informative of stress-induced gene expression profiles and also of geographical location specific transcriptomic signatures, determined by the interaction of genetic, disease and environmental factors. We have developed quantitative metrics to unambiguously characterize the phenotypic properties of dolphin cells in culture. These quantitative metrics can provide identifiable characteristics and baseline data which will enable identification of changes in the cells due to time in culture. We have also developed a novel protocol to isolate primary cultures from cryopreserved tissue of stranded marine mammals, establishing a tissue (and cell) biorepository, a new approach that can provide a solution to the limited availability of samples. The work presented represents the development and application of tools for the study of the biology, health and physiology of the dolphin, and establishes their relevance for future studies of the impact on the dolphin of environmental infection and stress.

DEVELOPMENT OF A HUMANOID ROBOT ARM FOR USE IN URBAN ENVIRONMENTS

The Bucknell Humanoid Robot Arm project was developed in order toprovide a lightweight robotic arm for the IHMC / Bucknell University bipedal robot that will provide a means of manipulation and facilitate operations in urban environments. The resulting fabricated arm described in this thesis weighs only 13 pounds, and is capable of holding 11 pounds fully outstretched, lifting objects such as tools, and it can open doors. It is also capable of being easily integrated with the IHMC / Bucknell University biped. This thesis provides an introduction to robots themselves, discusses the goals of the Bucknell Humanoid Robot Arm project, provides a background on some of the existing robots, and shows how the Bucknell Humanoid Robot Arm fits in with the studies that have been completed. After reading these studies, important items such as design trees and operational scenarios were completed. The completion of these items led to measurable specifications and later the design requirements and specifications. A significant contribution of this thesis to the robotics discipline involves the design of the actuator itself. The arm uses of individual, lightweight, compactly designed actuators to achieve desired capabilities and performance requirements. Many iterations were completed to get to the final design of each actuator. After completing the actuators, the design of the intermediate links and brackets was finalized. Completion of the design led to the development of a complex controls system which used a combination of Clanguage and Java.

Extending lifetime of plastic changes in the human brain

The ability of the brain to adjust to changing environments and to recover from damage rests on its remarkable capacity to adapt through plastic changes of underlying neural networks. We show here with an eye movement paradigm that a lifetime of plastic changes can be extended to several hours by repeated applications of theta burst transcranial magnetic stimulation to the frontal eye field of the human cortex. The results suggest that repeated application of the same stimulation protocol consolidates short-lived plasticity into long-lasting changes.

GLORIA Slope Approach - Monitoring Plant Community Changes in Mountain Ecosystems

The research described in this presentation is part of the Global Observation Research Initiative in Alpine Environments (GLORIA) whose purpose is to establish and maintain a global, long-term observation network in alpine environments. Despite changes in mountaintop-vegetation due to recent climate change being observed throughout the world, trends are not consistent. Moreover, as plant communities can be impacted by several different factors, it is important to be able to separate what is due to climate change and what is due to e.g. changes in grazing pressure (see additional file below).

The stable isotopic composition of Daphnia ephippia reflects changes in δ13C and δ18O values of food and water

The stable isotopic composition of fossil resting eggs (ephippia) of Daphnia spp. is being used to reconstruct past environmental conditions in lake ecosystems. However, the underlying assumption that the stable isotopic composition of the ephippia reflects the stable isotopic composition of the parent Daphnia, of their diet and of the environmental water have yet to be confirmed in a controlled experimental setting. We performed experiments with Daphnia pulicaria cultures, which included a control treatment conducted at 12 °C in filtered lake water and with a diet of fresh algae and three treatments in which we manipulated the stable carbon isotopic composition (δ13C value) of the algae, stable oxygen isotopic composition (δ18O value) of the water and the water temperature, respectively. The stable nitrogen isotopic composition (δ15N value) of the algae was similar for all treatments. At 12 °C, differences in algal δ13C values and in δ18O values of water were reflected in those of Daphnia. The differences between ephippia and Daphnia stable isotope ratios were similar in the different treatments (δ13C: +0.2 ± 0.4 ‰ (standard deviation); δ15N: −1.6 ± 0.4 ‰; δ18O: −0.9 ± 0.4 ‰), indicating that changes in dietary δ13C values and in δ18O values of water are passed on to these fossilizing structures. A higher water temperature (20 °C) resulted in lower δ13C values in Daphnia and ephippia than in the other treatments with the same food source and in a minor change in the difference between δ13C values of ephippia and Daphnia (to −1.3 ± 0.3 ‰). This may have been due to microbial processes or increased algal respiration rates in the experimental containers, which may not affect Daphnia in natural environments. There was no significant difference in the offset between δ18O and δ15N values of ephippia and Daphnia between the 12 and 20 °C treatments, but the δ18O values of Daphnia and ephippia were on average 1.2 ‰ lower at 20 °C than at 12 °C. We conclude that the stable isotopic composition of Daphnia ephippia provides information on that of the parent Daphnia and of the food and water they were exposed to, with small offsets between Daphnia and ephippia relative to variations in Daphnia stable isotopic composition reported from downcore studies. However, our experiments also indicate that temperature may have a minor influence on the δ13C, δ15N and δ18O values of Daphnia body tissue and ephippia. This aspect deserves attention in further controlled experiments.

Climatic and anthropogenic changes in Western Switzerland: Impacts on water stress

Recent observed hydro-climatic changes in mountainous areas are of concern as they may directly affect capacity to fulfill water needs. The canton of Vaud in Western Switzerland is an example of such a region as it has experienced water shortage episodes during the past decade. Based on an integrated modeling framework, this study explores how hydro-climatic conditions and water needs could evolve in mountain environments and assesses their potential impacts on water stress by the 2060 horizon. Flows were simulated based on a daily semi-distributed hydrological model. Future changes were derived from Swiss climate scenarios based on two regional climate models. Regarding water needs, the authorities of the canton of Vaud provided a population growth scenario while irrigation and livestock trends followed a business-as-usual scenario. Currently, the canton of Vaud experiences moderate water stress from June to August, except in its Alpine area where no stress is noted. In the 2060 horizon, water needs could exceed 80% of the rivers' available resources in low- to mid-altitude environments in mid-summer. This arises from the combination of drier and warmer climate that leads to longer and more severe low flows, and increasing urban (+ 40%) and irrigation (+ 25%) water needs. Highlighting regional differences supports the development of sustainable development pathways to reduce water tensions. Based on a quantitative assessment, this study also calls for broader impact studies including water quality issues.

Photochemical responses of the diatom Skeletonema costatum grown under elevated CO2 concentrations to short-term changes in pH

Variability in pH is a common occurrence in many aquatic environments, due to physical, chemical and biological processes. In coastal waters, lagoons, estuaries and inland waters, pH can change very rapidly (within seconds or hours) in addition to daily and seasonal changes. At the same time, progressive ocean acidification caused by anthropogenic CO2 emissions is superimposed on these spatial and temporal pH changes. Photosynthetic organisms are therefore unavoidably subject to significant pH variations at the cell surface. Whether this will affect their response to long-term ocean acidification is still unknown, nor is it known whether the short-term sensitivity to pH change is affected by the pCO2 to which the cells are acclimated. We posed the latter open question as our experimental hypothesis: Does acclimation to seawater acidification affect the response of phytoplankton to acute pH variations? The diatom Skeletonema costatum, commonly found in coastal and estuarine waters where short-term acute changes in pH frequently occur, was selected to test the hypothesis. Diatoms were grown at both 390 (pH 8.2, low CO2; LC) and 1000 (pH 7.9, high CO2; HC) µatm CO2 for at least 20 generations, and photosynthetic responses to short-term and acute changes in pH (between 8.2 and 7.6) were investigated. The effective quantum yield of LC-grown cells decreased by ca. 70% only when exposed to pH 7.6; this was not observed when exposed to pH 7.9 or 8.2. HC-grown cells did not show significant responses in any pH treatment. Non-photochemical quenching showed opposite trends. In general, our results indicate that while LC-grown cells are rather sensitive to acidification, HC-grown cells are relatively unresponsive in terms of photochemical performance.