Aboveground community and species-specific plant biomass from the Jena Experiment (Main Experiment, year 2009)

This data set contains aboveground community biomass in 2009 (Sown plant community, Weed plant community, Dead plant material, and Unidentified plant material; all measured in biomass as dry weight) and species-specific biomass from the sown species of the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Aboveground community biomass was harvested twice in 2009 just prior to mowing (during peak standing biomass in early June and in late August) on all experimental plots of the main experiment. This was done by clipping the vegetation at 3 cm above ground in three rectangles of 0.2 x 0.5 m per large plot. The location of these rectangles was assigned prior to each harvest by random selection of coordinates within the core area of the plots (i.e. the central 10 x 15 m). The positions of the rectangles within plots were identical for all plots. The harvested biomass was sorted into categories: individual species for the sown plant species, weed plant species (species not sown at the particular plot), detached dead plant material (i.e., dead plant material in the data file), and remaining plant material that could not be assigned to any category (i.e., unidentified plant material in the data file). All biomass was dried to constant weight (70°C, >= 48 h) and weighed. Sown plant community biomass was calculated as the sum of the biomass of the individual sown species. The data for individual samples and the mean over samples for all biomass measures are given. Overall, analyses of the community biomass data have identified species richness as well as functional group composition as important drivers of a positive biodiversity-productivity relationship.

Aboveground community and species-specific plant biomass from the Jena Experiment (Main Experiment, year 2010)

This data set contains aboveground community biomass in 2010 (Sown plant community, Weed plant community, Dead plant material, and Unidentified plant material; all measured in biomass as dry weight) and species-specific biomass from the sown species of the main experiment plots of a large grassland biodiversity experiment (the Jena Experiment; see further details below). In the main experiment, 82 grassland plots of 20 x 20 m were established from a pool of 60 species belonging to four functional groups (grasses, legumes, tall and small herbs). In May 2002, varying numbers of plant species from this species pool were sown into the plots to create a gradient of plant species richness (1, 2, 4, 8, 16 and 60 species) and functional richness (1, 2, 3, 4 functional groups). Plots were maintained by bi-annual weeding and mowing. Aboveground community biomass was harvested twice in 2010 just prior to mowing (during peak standing biomass in early June and in late August) on all experimental plots of the main experiment. This was done by clipping the vegetation at 3 cm above ground in two rectangles of 0.2 x 0.5 m per large plot. The location of these rectangles was assigned prior to each harvest by random selection of coordinates within the core area of the plots (i.e. the central 10 x 15 m). The positions of the rectangles within plots were identical for all plots. The harvested biomass was sorted into categories: individual species for the sown plant species, weed plant species (species not sown at the particular plot), detached dead plant material (i.e., dead plant material in the data file), and remaining plant material that could not be assigned to any category (i.e., unidentified plant material in the data file). All biomass was dried to constant weight (70°C, >= 48 h) and weighed. Sown plant community biomass was calculated as the sum of the biomass of the individual sown species. The data for individual samples and the mean over samples for all biomass measures are given. Overall, analyses of the community biomass data have identified species richness as well as functional group composition as important drivers of a positive biodiversity-productivity relationship.

Biomass, quality traits and methane production of extensive grassland: biodiversity effects and sensor approaches

Energy policies around the world are mandating for a progressive increase in renewable energy production. Extensive grassland areas with low productivity and land use limitations have become target areas for sustainable energy production to avoid competition with food production on the limited available arable land resources and minimize further conversion of grassland into intensively managed energy cropping systems or abandonment. However, the high spatio-temporal variability in botanical composition and biochemical parameters is detrimental to reliable assessment of biomass yield and quality regarding anaerobic digestion. In an approach to assess the performance for predicting biomass using a multi-sensor combination including NIRS, ultra-sonic distance measurements and LAI-2000, biweekly sensor measurements were taken on a pure stand of reed canary grass (Phalaris aruninacea), a legume grass mixture and a diversity mixture with thirty-six species in an experimental extensive two cut management system. Different combinations of the sensor response values were used in multiple regression analysis to improve biomass predictions compared to exclusive sensors. Wavelength bands for sensor specific NDVI-type vegetation indices were selected from the hyperspectral data and evaluated for the biomass prediction as exclusive indices and in combination with LAI and ultra-sonic distance measurements. Ultrasonic sward height was the best to predict biomass in single sensor approaches (R² 0.73 – 0.76). The addition of LAI-2000 improved the prediction performance by up to 30% while NIRS barely improved the prediction performance. In an approach to evaluate broad based prediction of biochemical parameters relevant for anaerobic digestion using hyperspectral NIRS, spectroscopic measurements were taken on biomass from the Jena-Experiment plots in 2008 and 2009. Measurements were conducted on different conditions of the biomass including standing sward, hay and silage and different spectroscopic devices to simulate different preparation and measurement conditions along the process chain for biogas production. Best prediction results were acquired for all constituents at laboratory measurement conditions with dried and ground samples on a bench-top NIRS system (RPD > 3) with a coefficient of determination R2 < 0.9. The same biomass was further used in batch fermentation to analyse the impact of species richness and functional group composition on methane yields using whole crop digestion and pressfluid derived by the Integrated generation of solid Fuel and Biogas from Biomass (IFBB) procedure. Although species richness and functional group composition were largely insignificant, the presence of grasses and legumes in the mixtures were most determining factors influencing methane yields in whole crop digestion. High lignocellulose content and a high C/N ratio in grasses may have reduced the digestibility in the first cut material, excess nitrogen may have inhibited methane production in second cut legumes, while batch experiments proved superior specific methane yields of IFBB press fluids and showed that detrimental effects of the parent material were reduced by the technical treatment

Nucleophilic addition of Nitrones to Electron deficient acetylenes and related studies

Nitrones or azomethine-N-oxides are important precursors for the synthesis of several heterocyclic systems. They belong to the allyl anion type 1,3-dipoles and possess unique structural features which make them extraordinarily useful synthons. They behave as 1,3-dipoles in 1,3-dipolar cycloaddition reactions and as electrophiles in reactions with organometallic reagents. These are the two basic reactions given by nitrones. Nitrones also act as ‘spin traps’ in which they react with short-lived radicals to furnish stable nitroxide radicals which can be detected and identified by electron paramagnetic resonance (EPR) spectroscopy. Recently SmI2 catalysed reductive cross-coupling reactions of nitrones have gained significant interest in which the reactions are initiated by single electron transfer (SET) to nitrones. Apart from these reactions, nitrones are also known to participate in reactions which are initiated by the nucleophilic attack of nitrone-oxygen. In our group, we have also explored the nucleophilic character of nitrones through various reactions. The results obtained enabled us to develop a novel two-step one-pot strategy for quinolines and indoles - the heterocycles renowned for their pharmacological applications, from nitrones and electron deficient acetylenes. Using dibenzoylacetylene and phenylbenzoylacetylene as dipolarophiles, we could introduce a desired functional group at a predetermined position of the quinolines or indoles to be synthesised. In this context, the thesis entitled “NUCLEOPHILIC ADDITION OF NITRONES TO ELECTRON DEFICIENT ACETYLENES AND RELATED STUDIES” portrays our attempt to expand the scope of our x novel synthetic protocol using ester functionalised acetylenes: dimethyl acetylenedicarboxylate (DMAD) and methyl propiolate. The thesis is organised in to five chapters. The first chapter briefly describes the different classes of reactions that nitrone functionality can tolerate. The research problem is defined at the end of this chapter. The second chapter describes the synthesis of different nitrones used for the present study. The optimisation and expansion of scope of the novel strategy towards quinoline synthesis is discussed in the third chapter. The fourth chapter portrays the synthesis of indole-3-carboxylates using the novel strategy. In the fifth chapter, the reaction of N-(2,6-dimethylphenyl) and N-(2,4,6-trimethylphenyl)nitrones are discussed. Here we also discuss the mechanistic reinvestigation of Baldwin’s proposal in the isoxazoline-oxazoline rearrangement. The major outcome of the work is given at the end of the thesis. The structural formulae, schemes, tables and figures are numbered chapter-wise since each chapter of the thesis is organized as an independent unit. All new compounds (except two compounds reported in fourth chapter) are fully characterised on the basis of spectral and analytical data and single crystal X-ray analysis on representative examples. Relevant references are included at the end of individual chapters.

Pediatric Oncology Palliative Care: Experiences of General Practitioners and Bereaved Parents

Objective: This qualitative study set in the West Midlands region of the United Kingdom, aimed to examine the role of the general practitioner (GP) in children's oncology palliative care from the perspective of GPs who had cared for a child with cancer receiving palliative care at home and bereaved parents. Methods: One-to-one semi-structured interviews were undertaken with 18 GPs and 11 bereaved parents following the death. A grounded theory data analysis was undertaken; identifying generated themes through chronological comparative data analysis. Results: Similarity in GP and parent viewpoints was found, the GPs role seen as one of providing medication and support. Time pressures GPs faced influenced their level of engagement with the family during palliative and bereavement care and their ability to address their identified learning deficits. Lack of familiarity with the family, coupled with an acknowledgment that it was a rare and could be a frightening experience, also influenced their level of interaction. There was no consistency in GP practice nor evidence of practice being guided by local or national policies. Parents lack of clarity of their GPs role resulted in missed opportunities for support. Conclusions: Time pressures influence GP working practices. Enhanced communication and collaboration between the GP and regional childhood cancer centre may help address identified GP challenges, such as learning deficits, and promote more time-efficient working practices through role clarity. Parents need greater awareness of their GP's wide-ranging role; one that transcends palliative care incorporating bereavement support and on-going medical care for family members

Royal Artillery Centre for Personal Development case study

Case study on online delivery and support for functional skills in Mathematics, English and ICT

An electrochemical process for the production of synthetic fuels at low temperatures [Resumo]

Following work exploring the low temperature electrolysis in alkaline media, using graphite consumable anodes, from which syngas was obtained1, laboratory studies have been conducted in acid media pursuing higher efficiency in the production of hydrogen and synthetic fuels. Experiments were conducted in an own designed undivided planar cell with 25 cm2 geometrical area electrodes using a 0.5 M H2SO4 solution with and without Fe(II) additions. Fe2+ oxidizes to Fe3+ at the anode surface. The redox couple Fe3+/ Fe2+ acts as an oxidation mediator not only oxidizing the bulk and detached graphite but also the surface functional groups. The practical experimental potential for graphite oxidation is within the range for the electroxidation of the Fe redox couple giving as a result a 4-fold increase in the amount of produced CO2 at near room temperature, when using 0.025 M FeSO4.

TRIB2 in human AML: a biological and clinical investigation

Acute myeloid leukemia (AML) involves the proliferation, abnormal survival and arrest of cells at a very early stage of myeloid cell differentiation. The biological and clinical heterogeneity of this disease complicates treatment and highlights the significance of understanding the underlying causes of AML, which may constitute potential therapeutic targets, as well as offer prognostic information. Tribbles homolog 2 (Trib2) is a potent murine oncogene capable of inducing transplantable AML with complete penetrance. The pathogenicity of Trib2 is attributed to its ability to induce proteasomal degradation of the full length isoform of the transcription factor CCAAT/enhancer-binding protein alpha (C/EBPα p42). The role of TRIB2 in human AML cells, however, has not been systematically investigated or targeted. Across human cancers, TRIB2 oncogenic activity was found to be associated with its elevated expression. In the context of AML, TRIB2 overexpression was suggested to be associated with the large and heterogeneous subset of cytogenetically normal AML patients. Based upon the observation that overexpression of TRIB2 has a role in cellular transformation, the effect of modulating its expression in human AML was examined in a human AML cell line that expresses high levels of TRIB2, U937 cells. Specific suppression of TRIB2 led to impaired cell growth, as a consequence of both an increase in apoptosis and a decrease in cell proliferation. Consistent with these in vitro results, TRIB2 silencing strongly reduced progression of the U937 in vivo xenografts, accompanied by detection of a lower spleen weight when compared with mice transplanted with TRIB2- expressing control cells. Gene expression analysis suggested that TRIB2 modulates apoptosis and cell-cycle sensitivity by influencing the expression of a subset of genes known to have implications on these phenotypes. Furthermore, TRIB2 was found to be expressed in a significant subset of AML patient samples analysed. To investigate whether increased expression of this gene could be afforded prognostic significance, primary AML cells with dichotomized levels of TRIB2 transcripts were evaluated in terms of their xenoengraftment potential, an assay reported to correlate with disease aggressiveness observed in humans. A small cohort of analysed samples with higher TRIB2 expression did not associate with preferential leukaemic cell engraftment in highly immune-deficient mice, hence, not predicting for an adverse prognosis. However, further experiments including a larger cohort of well characterized AML patients would be needed to clarify TRIB2 significance in the diagnostic setting. Collectively, these data support a functional role for TRIB2 in the maintenance of the oncogenic properties of human AML cells and suggest TRIB2 can be considered a rational therapeutic target. Proteasome inhibition has emerged as an attractive target for the development of novel anti-cancer therapies and results from translational research and clinical trials support the idea that proteasome inhibitors should be considered in the treatment of AML. The present study argued that proteasome inhibition would effectively inhibit the function of TRIB2 by abrogating C/EBPα p42 protein degradation and that it would be an effective pharmacological targeting strategy in TRIB2-positive AMLs. Here, a number of cell models expressing high levels of TRIB2 were successfully targeted by treatment with proteasome inhibitors, as demonstrated by multiple measurements that included increased cytotoxicity, inhibition of clonogenic growth and anti-AML activity in vivo. Mechanistically, it was shown that block of the TRIB2 degradative function led to an increase of C/EBPα p42 and that response was specific to the TRIB2-C/EBPα axis. Specificity was addressed by a panel of experiments showing that U937 cells (express detectable levels of endogenous TRIB2 and C/EBPα) treated with the proteasome inhibitor bortezomib (Brtz) displayed a higher cytotoxic response upon TRIB2 overexpression and that ectopic expression of C/EBPα rescued cell death. Additionally, in C/EBPα-negative leukaemia cells, K562 and Kasumi 1, Brtz-induced toxicity was not increased following TRIB2 overexpression supporting the specificity of the compound on the TRIB2-C/EBPα axis. Together these findings provide pre-clinical evidence that TRIB2- expressing AML cells can be pharmacologically targeted with proteasome inhibition due, in part, to blockage of the TRIB2 proteolytic function on C/EBPα p42. A large body of evidence indicates that AML arises through the stepwise acquisition of genetic and epigenetic changes. Mass spectrometry data has identified an interaction between TRIB2 and the epigenetic regulator Protein Arginine Methyltransferase 5 (PRMT5). Following assessment of TRIB2‟s role in AML cell survival and effective targeting of the TRIB2-C/EBPα degradation pathway, a putative TRIB2/PRMT5 cooperation was investigated in order to gain a deeper understanding of the molecular network in which TRIB2 acts as a potent myeloid oncogene. First, a microarray data set was interrogated for PRMT5 expression levels and the primary enzyme responsible for symmetric dimethylation was found to be transcribed at significantly higher levels in AML patients when compared to healthy controls. Next, depletion of PRMT5 in the U937 cell line was shown to reduce the transformative phenotype in the high expressing TRIB2 AML cells, which suggests that PRMT5 and TRIB2 may cooperate to maintain the leukaemogenic potential. Importantly, PRMT5 was identified as a TRIB2-interacting protein by means of a protein tagging approach to purify TRIB2 complexes from 293T cells. These findings trigger further research aimed at understanding the underlying mechanism and the functional significance of this interplay. In summary, the present study provides experimental evidence that TRIB2 has an important oncogenic role in human AML maintenance and, importantly in such a molecularly heterogeneous disease, provides the rational basis to consider proteasome inhibition as an effective targeting strategy for AML patients with high TRIB2 expression. Finally, the identification of PRMT5 as a TRIB2-interacting protein opens a new level of regulation to consider in AML. This work may contribute to our further understanding and therapeutic strategies in acute leukaemias.

Multi-Agent Simulation and Management Practices

Intelligent agents offer a new and exciting way of understanding the world of work. Agent-Based Simulation (ABS), one way of using intelligent agents, carries great potential for progressing our understanding of management practices and how they link to retail performance. We have developed simulation models based on research by a multi-disciplinary team of economists, work psychologists and computer scientists. We will discuss our experiences of implementing these concepts working with a well-known retail department store. There is no doubt that management practices are linked to the performance of an organisation (Reynolds et al., 2005; Wall & Wood, 2005). Best practices have been developed, but when it comes down to the actual application of these guidelines considerable ambiguity remains regarding their effectiveness within particular contexts (Siebers et al., forthcoming a). Most Operational Research (OR) methods can only be used as analysis tools once management practices have been implemented. Often they are not very useful for giving answers to speculative ‘what-if’ questions, particularly when one is interested in the development of the system over time rather than just the state of the system at a certain point in time. Simulation can be used to analyse the operation of dynamic and stochastic systems. ABS is particularly useful when complex interactions between system entities exist, such as autonomous decision making or negotiation. In an ABS model the researcher explicitly describes the decision process of simulated actors at the micro level. Structures emerge at the macro level as a result of the actions of the agents and their interactions with other agents and the environment. We will show how ABS experiments can deal with testing and optimising management practices such as training, empowerment or teamwork. Hence, questions such as “will staff setting their own break times improve performance?” can be investigated.

Introduction to Multi-Agent Simulation

When designing systems that are complex, dynamic and stochastic in nature, simulation is generally recognised as one of the best design support technologies, and a valuable aid in the strategic and tactical decision making process. A simulation model consists of a set of rules that define how a system changes over time, given its current state. Unlike analytical models, a simulation model is not solved but is run and the changes of system states can be observed at any point in time. This provides an insight into system dynamics rather than just predicting the output of a system based on specific inputs. Simulation is not a decision making tool but a decision support tool, allowing better informed decisions to be made. Due to the complexity of the real world, a simulation model can only be an approximation of the target system. The essence of the art of simulation modelling is abstraction and simplification. Only those characteristics that are important for the study and analysis of the target system should be included in the simulation model. The purpose of simulation is either to better understand the operation of a target system, or to make predictions about a target system’s performance. It can be viewed as an artificial white-room which allows one to gain insight but also to test new theories and practices without disrupting the daily routine of the focal organisation. What you can expect to gain from a simulation study is very well summarised by FIRMA (2000). His idea is that if the theory that has been framed about the target system holds, and if this theory has been adequately translated into a computer model this would allow you to answer some of the following questions: · Which kind of behaviour can be expected under arbitrarily given parameter combinations and initial conditions? · Which kind of behaviour will a given target system display in the future? · Which state will the target system reach in the future? The required accuracy of the simulation model very much depends on the type of question one is trying to answer. In order to be able to respond to the first question the simulation model needs to be an explanatory model. This requires less data accuracy. In comparison, the simulation model required to answer the latter two questions has to be predictive in nature and therefore needs highly accurate input data to achieve credible outputs. These predictions involve showing trends, rather than giving precise and absolute predictions of the target system performance. The numerical results of a simulation experiment on their own are most often not very useful and need to be rigorously analysed with statistical methods. These results then need to be considered in the context of the real system and interpreted in a qualitative way to make meaningful recommendations or compile best practice guidelines. One needs a good working knowledge about the behaviour of the real system to be able to fully exploit the understanding gained from simulation experiments. The goal of this chapter is to brace the newcomer to the topic of what we think is a valuable asset to the toolset of analysts and decision makers. We will give you a summary of information we have gathered from the literature and of the experiences that we have made first hand during the last five years, whilst obtaining a better understanding of this exciting technology. We hope that this will help you to avoid some pitfalls that we have unwittingly encountered. Section 2 is an introduction to the different types of simulation used in Operational Research and Management Science with a clear focus on agent-based simulation. In Section 3 we outline the theoretical background of multi-agent systems and their elements to prepare you for Section 4 where we discuss how to develop a multi-agent simulation model. Section 5 outlines a simple example of a multi-agent system. Section 6 provides a collection of resources for further studies and finally in Section 7 we will conclude the chapter with a short summary.

Estudo da adesão de pinos endodônticos modificados superficialmente por plasma de oxigênio

The work presents the effect of plasma treatment when applied in fibers or carbon/glass posts in the adhesion fiber/resin and posts/cement. This has for objective the modification of the surface of the fibers, as well as the wettability of the posts, seeking the improvement of the adhesion and of the connection fiber/resin in the processing of polymeric composites reinforced with the same ones. 120 posts (Reforpost) were used and 30 meters of fibers of carbon and of glass (Fibrex), of the company Angelus. The samples were divided in three groups of 40 specimens: GROUP I - 20 posts of glass fiber and 20 of carbon without treatment to it shapes, GROUP II -20 posts of glass fiber and 20 of carbon treated to it shapes in the surface and GROUP III - 20 posts of glass fiber and 20 of carbon make with fibers in natura after plasma treatment. The plasma treatment was accomplished with oxygen and with temperature in the camera fixed at 200°C, for one hour of exhibition. The posts and the fibers were characterized before and after the treatment. The wettability was measure by pendent drop method, and interface fiber/resin and posts/cement were observed by optical and electronic microscopy. It was observed that both wettability and texture were increased with plasma treatment

Air Entrainment in the Turbulent Ship Hull Boundary Layer

Turbulent fluctuations in the vicinity of the water free surface along a flat, vertically oriented surface-piercing plate are studied experimentally using a laboratory-scale experiment. In this experiment, a meter-wide stainless steel belt travels horizontally in a loop around two rollers with vertically oriented axes, which are separated by 7.5 meters. This belt device is mounted inside a large water tank with the water level set just below the top edge of the belt. The belt, rollers, and supporting frame are contained within a sheet metal box to keep the device dry except for one 6-meter-long straight test section between rollers. The belt is launched from rest with an acceleration of up to 3-g in order to quickly reach steady state velocity. This creates a temporally evolving boundary layer analogous to the spatially evolving boundary layer created along a flat-sided ship moving at the same velocity, with a length equivalent to the length of belt that has passed the measurement region since the belt motion began. Surface profile measurements in planes normal to the belt surface are conducted using cinematic Laser Induced Fluorescence and quantitative surface profiles are extracted at each instant in time. Using these measurements, free surface fluctuations are examined and the propagation behavior of these free surface ripples is studied. It is found that free surface fluctuations are generated in a region close to the belt surface, where sub-surface velocity fluctuations influence the behavior of these free surface features. These rapidly-changing surface features close to the belt appear to lead to the generation of freely-propagating waves far from the belt, outside the influence of the boundary layer. Sub-surface PIV measurements are performed in order to study the modification of the boundary layer flow field due to the effects of the water free surface. Cinematic planar PIV measurements are performed in horizontal planes parallel to the free surface by imaging the flow from underneath the tank, providing streamwise and wall-normal velocity fields. Additional planar PIV experiments are performed in vertical planes parallel to the belt surface in order to study the bahvior of streamwise and vertical velocity fields. It is found that the boundary layer grows rapidly near the free surface, leading to an overall thicker boundary layer close to the surface. This rapid boundary layer growth appears to be linked to a process of free surface bursting, the sudden onset of free surface fluctuations. Cinematic white light movies are recorded from beneath the water surface in order to determine the onset location of air entrainment. In addition, qualitative observations of these processes are made in order to determine the mechanisms leading to air entrainment present in this flow.

Diversity in Catalytic Reactions of Propargylic Diazoesters

Abstract Title of Document: Diversity in Catalytic Reactions of Propargylic Diazoesters Huang Qiu, Doctor of Philosophy, 2016 Directed By: Professor Michael P. Doyle, Department of Chemistry and Biochemistry Propargylic aryldiazoesters, which possess multiple reactive functional groups in a single molecule, were expected to undergo divergent reaction pathways as a function of catalysts. A variety of transition metal complexes including rhodium(II), palladium(II), silver(I), mercury(II), copper(I and II), and cationic gold (I) complexes have been examined to be effective in the catalytic domino reactions of propargylic aryldiazoesters. An unexpected Lewis acid catalyzed pathway was also discovered by using FeCl3 as the catalyst. Under the catalysis of selected gold catalysts, propargylic aryldiazoesters exist in equilibrium with 1-aryl-1,2-dien-1-yl diazoacetate allenes that are rapidly formed at room temperature through 1,3-acyloxy migration. The newly formed allenes further undergo a metal-free rearrangement in which the terminal nitrogen of the diazo functional group adds to the central carbon of the allene initiating a sequence of bond forming reactions resulting in the production of 1,5-dihydro-4H-pyrazol-4-ones in good yields. These 1,5-dihydro-4H-pyrazol-4-ones undergo intramolecular 1,3-acyl migration to form an equilibrium mixture or quantitatively transfer the acyl group to an external nucleophile with formation of 4-hydroxypyrazoles. In the presence of a pyridine-N-oxide, both E- and Z-1,3-dienyl aryldiazoacetates are formed in high combined yields by Au(I)-catalyzed rearrangement of propargyl arylyldiazoacetates at short reaction times. Under thermal reactions the E-isomers form the products from intramolecular [4+2]-cycloaddition with H‡298 = 15.6 kcal/mol and S‡298= -27.3 cal/ (mol•degree). The Z-isomer is inert to [4+2]-cycloaddition under these conditions. The Hammett relationships from aryl-substituted diazo esters ( = +0.89) and aryl-substituted dienes ( = -1.65) are consistent with the dipolar nature of this transformation. An unexpected reaction for the synthesis of seven-membered conjugated 1,4-diketones from propargylic diazoesters with unsaturated imines was disclosed. To undergo this process vinyl gold carbene intermediates generated by 1,2-acyloxy migration of propargylic aryldiazoesters undergo a formal [4+3]-cycloaddition, and the resulting aryldiazoesters tethered dihydroazepines undergo an intricate metal-free process to form observed seven-membered conjugated 1,4-diketones with moderate to high yields.

O contributo da animação na qualidade de vida dos idosos do serviço de apoio domiciliário do centro comunitário de Estoi

Dissertação de Mestrado, Educação Social, Escola Superior de Educação e Comunicação, Universidade do Algarve, 2016

Avaliação da atividade muscular do vasto medial oblíquo em diferentes exercícios

Projeto de Graduação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Licenciado em Fisioterapia