A unified strategy to ent-kauranoid natural products : total syntheses of (–)-maoecrystal Z, (–)-trichorabdal A, and (–)-longikaurin E

The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.

Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm^(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti^(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.

The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.

Diseño, Modelado y Análisis por Elementos Finitos de un Cuadro de Bicicleta de Carretera.

[ES]El objetivo de este proyecto es llevar a cabo el diseño conceptual, modelado y análisis estructural de un cuadro de bicicleta de geometría de carretera, empleando herramientas de Diseño Asistido por Ordenador y software de Análisis con Elementos Finitos. El modelo inicial será analizado y optimizado de cara a que cumpla los requerimientos resitentes del escenario de cargas asumido. El propósito de este proyecto es completar la primera fase de un hipotético caso de producción.

Bizikletako aurreko abatzaren mekanizaziorako cam bidezko programazioa

[EU]Lan honek bizikletako aurreko gurpileko abatz baten CAM edo CNC programazioa egitean datza, honen bidez erremintaren ibilbidea deskribatuz piezaren CAD eredutik abiatuz. Hasteko, zenbakizko kontrolak izan duen eboluzioa eta garrantzia azaltzen da. Ondoren, abatzaren funtzionamenduaren deskribapena egin da, bere osagaiak eta izan behar dituen ezaugarriak aztertuz. Gainera, fabrikazio prozesu ezberdinen analisia egin da, bakoitzaren abantaila eta desabantailak azpimarratuz. Azkenik, zenbakizko kontrolaren inguruan bereganatutako ezagutzak aplikatu dira CAM programa batean abatz baten mekanizazioa programatuz. Honez gain, erabilitako CAM programaren erabilera azaltzen da.

Coincidence and common fixed point theorems for Suzuki type hybrid contractions and applications

Coincidence and common fixed point theorems for a class of Suzuki hybrid contractions involving two pairs of single-valued and multivalued maps in a metric space are obtained. In addition, the existence of a common solution for a certain class of functional equations arising in a dynamic programming is also discussed.

Biomimetic Cloning of Quantum Observables

We propose a bio-inspired sequential quantum protocol for the cloning and preservation of the statistics associated to quantum observables of a given system. It combines the cloning of a set of commuting observables, permitted by the no-cloning and no-broadcasting theorems, with a controllable propagation of the initial state coherences to the subsequent generations. The protocol mimics the scenario in which an individual in an unknown quantum state copies and propagates its quantum information into an environment of blank qubits Finally, we propose a realistic experimental implementation of this protocol in trapped ions.

von Neumann spin measurements with Rashba fields

We show that dynamics in the spin-orbit coupling field simulate the von Neumann measurement of a particle spin. We demonstrate how the measurement influences the spin and coordinate evolution of a particle by comparing two examples of such a procedure. The first example is a simultaneous measurement of spin components, sigma(x) and sigma(y), corresponding to non-commuting operators, which cannot be accurately obtained together at a given time instant due to the Heisenberg uncertainty ratio. By mapping spin dynamics onto a spatial walk, such a procedure determines measurement-time averages of sigma(x) and sigma(y), which can already be precisely evaluated in a single short-time measurement. The other, qualitatively different, example is the spin of a one-dimensional particle in a magnetic field. Here, the measurement outcome depends on the angle between the spin-orbit coupling and magnetic fields. These results can be applied to studies of spin-orbit coupled cold atoms and electrons in solids.

A pendularidade da população em Macaé-RJ a partir do processo de periferização urbana: o exemplo da Vila de Córrego do Ouro

A pesquisa tem por objetivo investigar um dos impactos do processo de desenvolvimento da indústria do petróleo em Macaé-RJ, sobre a dinâmica urbana no município, especialmente no deslocamento pendular da população na vila serrana de Córrego do Ouro. O desenvolvimento macaense é considerado a partir da sua influência sobre a dinâmica populacional, sobretudo no que se refere à sua mobilidade espacial. A análise é sustentada por uma base teórica que articula o processo de urbanização no Brasil contemporâneo e as possibilidades de interação entre os territórios urbano e rural, às características da mobilidade pendular da população, sobretudo em espaços não-metropolitanos. A pesquisa é apresentada a partir de trabalho de campo realizado e da confrontação de seus resultados com dados do IBGE e do Programa Macaé Cidadão. Por fim, a dissertação considera a formação de vetores de expansão urbana na sede macaense, como meio de reforçar o argumento da formação de um eixo periférico nos núcleos urbanos serranos que margeiam a RJ-162, exemplificados pelo estudo da pendularidade da população na vila de Córrego do Ouro.

Adaptações e improvisações: repercussões para o processo de trabalho hospitalar da enfermagem

O estudo do fenômeno das adaptações e improvisações de materiais e equipamentos elaboradas no ambiente hospitalar é relativamente recente nas ciências da saúde. Pode-se inferir que esses artefatos decorrem predominantemente devido à adoção de políticas de recorte neoliberal, que gera carência qualitativa e quantitativa de recursos, material e humano, refletindo no gerenciamento administrativo e assistencial do cuidado. Objeto de estudo: as repercussões da prática de improvisar e de adaptar recursos materiais no processo de trabalho da enfermagem em ambiente hospitalar. Os objetivos foram: I) descrever as adaptações e improvisações de materiais e equipamentos no ambiente hospitalar; II) analisar as consequências das adaptações e improvisações de materiais e equipamentos para o processo de trabalho em enfermagem; III) discutir as concepções da prática das adaptações e improvisações para a qualidade do trabalho da enfermagem e para a saúde do cliente, na visão dos trabalhadores de enfermagem. Pesquisa qualitativa e descritiva, desenvolvida em um hospital geral situado no Rio de Janeiro. Os sujeitos foram vinte trabalhadores de enfermagem. A coleta de dados se deu por meio de entrevista semiestruturada e observação sistemática. O método de análise utilizado foi a análise de conteúdo. A partir da apropriação da técnica, emergiram três categorias empíricas: categoria 1: o contexto de criação das adaptações/improvisações no ambiente hospitalar; categoria 2: as adaptações e improvisações de recursos materiais presentes na organização e no processo de trabalho da enfermagem; categoria 3: A dialética da prática das adaptações e improvisações para a qualidade do trabalho da enfermagem e saúde do paciente. Os resultados consolidaram o entendimento de que as adaptações e improvisações surgem predominantemente devido a um contexto de precarização, que impelem os trabalhadores a elaborarem estas criações, a fim de assegurar que o processo de trabalho da enfermagem aconteça. Constatou-se que as adaptações e improvisações interferem no processo de trabalho, no sentido de aumentar o volume de trabalho, o modo operatório da enfermagem, o tempo gasto no processo de criação, os deslocamentos do profissional, a dificuldade do seguimento aos princípios científicos em situações emergenciais. No entanto, depreendeu-se que a enfermagem faz uma multiplicidade de adaptações e improvisações em prol da assistência, porém há concepções dialéticas, as quais simbolizam aspectos positivos e negativos para o trabalho de enfermagem e para a saúde do paciente. Conclui-se que o processo de trabalho na instituição não está em consonância com as necessidades práticas do trabalho da enfermagem, acarretando em sobrecargas, adaptações e improvisações, e em última instância, em transgressões do trabalho prescrito.

A Insustentabilidade do transporte em automóveis

A mobilidade urbana é um problema em diversos centros urbanos e é agravada pelo número crescente de automóveis e seu uso indiscriminado. Este estudo exploratório-descritivo abordará revisões conceituais e levantamento extenso de dados sobre a função de transporte; o automóvel, quanto a sua origem e simbolismos; o contexto do Brasil e da cidade do Rio de Janeiro; a dependência dos veículos e os impactos do trânsito na sociedade, a fim de explicar a insustentabilidade desse meio de transporte, da forma como tem sido utilizado nas cidades. Dentre os principais impactos causados pela dependência do automóvel, destacam-se os relativos a saúde, com problemas que vão desde complicações no sistema respiratório e circulatório até o comprometimento da saúde mental; qualidade de vida e a relação entre tempo e custos de locomoção; segurança e todo aparato tecnológico de automóveis que protege o usuário em detrimento do público mais vulnerável, como pedestres e ciclistas; morfologia da cidade, que acaba por privilegiar um modal individual e cria novas formas urbanas que demandam mais espaços para automóveis; mudanças climáticas devido à poluição desproporcional, que influencia os padrões bioquímicos de vários ecossistemas, gerando mudanças climáticas; e prejuízos econômicos, estimados por três diferentes metodologias de estudo, que procuraram monetizar o custo dos congestionamentos. A pesquisa propõe diversas atitudes para reverter ou mitigar o uso excessivo do Transporte em Automóveis. Esta contribuição para os estudos da geografia de transportes vislumbra deixar subsídios para que se avance no debate sobre a dependência do automóvel, especialmente em grandes cidades

Poverty in the fisheries, inductors, causes and intervention

The study is prompted by the poverty that persisted among the fishing communities of lake victoria at time of considerable cash inflow into the fisheries development of fish processing industry. There has been need for understanding of the poverty and what strategies would be most appreciate for it's reduction.This study has attempted to respond to the needby identifying the nature and distribution of the poverty within the fisheries lake victoria,Uganda, the factor responsible for itand the options for poverty reduction intervention. The study examined the global and regional perspectives of poverty and wealth distribution, noting that wide disparities existed between the developed and the developing world and also between the developing countries themselves. A historical review of development policies and strategies revealed that while successive strategies were able to contribute to growth, their achievement towards poverty alleviation were less than satisfactory, hence the need for continually developing new strategies. A background to Uganda’s society and economy is provided, examining the demographic, political, environmental and economic conditions of the country. Uganda’s development strategies are reviewed, highlighting the role of the Poverty Eradication Action Plan, Uganda’s main strategy for implementing the policy of poverty reduction and wealth distribution. At the agricultural sector level, the Plan for the Modernisation of Agriculture has been formulated, followed by the National Fisheries Policy, aimed at providing a policy framework for the management and development of the fisheries. An appropriate definition of poverty was formulated, considered relevant to the situation of Lake Victoria. The dimensions of poverty included inadequate basic necessities, low education and health achievements, a sense of insecurity and exposure to risk. The research methodology was enhanced by the examination of the Lélé Model of the Poverty–Environmental Degradation problem, the World Bank Model of Poverty Causation and the subsequent Lake Victoria Model developed in this study. It has provided a plan for the research, the consideration of criteria and a data collection plan. The data collection instruments included secondary data search, key informant interviews and a sample survey based on a structured questionnaire. The study identified all the four dimensions of poverty in the fisheries, provided poverty profiles with respect to the different activities, groups of people and regions in the fisheries, based on consumption poverty. Among the people identified to be in poverty were the fishing labourers, fishers of Oreochromis niloticus and those operating with non-powered boats. In the post-harvest fisheries, large proportions of processors involved in salting and sun-drying, market stall and bicycle traders were in the poverty category. The ethnic groups most affected included the Samia, Basoga and Bakenye while the Districts of Jinja, Bugiri and Busia had the highest proportions of fishers in the poverty category. With respect to the other dimensions of poverty, the study showed that educational achievement was low within the fishing communities. The health status was poor, due mainly to the prevalence of malaria, diarrhoea, bilharzia and HIV/AIDS. There was a sense of insecurity within certain sections of the fishing community, due to leadership weaknesses within the local as well as the Government institutions. Some community members operated in a state of risk because they were vulnerable to episodes of income, health and education. The causes of poverty in fisheries included weaknesses within the institutional and social environment, limitations in the technology available to the poor, resource degradation and unfavourable economic factors. The recommendations of the study for poverty reduction included strengthening of policies, developing links, improving capacities and increasing resources, to be applied at the levels of Central Government, Local Government and of the community. In view of the achievements of the methodology used on this study, involving reference to the models, it is recommended that future research should build upon this model approach, as it will continue to produce results, especially when attempting to forecast changes relating to interventions.

The Essential Dynamics Algorithm: Essential Results

This paper presents a novel algorithm for learning in a class of stochastic Markov decision processes (MDPs) with continuous state and action spaces that trades speed for accuracy. A transform of the stochastic MDP into a deterministic one is presented which captures the essence of the original dynamics, in a sense made precise. In this transformed MDP, the calculation of values is greatly simplified. The online algorithm estimates the model of the transformed MDP and simultaneously does policy search against it. Bounds on the error of this approximation are proven, and experimental results in a bicycle riding domain are presented. The algorithm learns near optimal policies in orders of magnitude fewer interactions with the stochastic MDP, using less domain knowledge. All code used in the experiments is available on the project's web site.

Associations between BMI and home, school and route environmental exposures estimated using GPS and GIS: do we see evidence of selective daily mobility bias in children?

BACKGROUND: This study examined whether objective measures of food, physical activity and built environment exposures, in home and non-home settings, contribute to children's body weight. Further, comparing GPS and GIS measures of environmental exposures along routes to and from school, we tested for evidence of selective daily mobility bias when using GPS data. METHODS: This study is a cross-sectional analysis, using objective assessments of body weight in relation to multiple environmental exposures. Data presented are from a sample of 94 school-aged children, aged 5-11 years. Children's heights and weights were measured by trained researchers, and used to calculate BMI z-scores. Participants wore a GPS device for one full week. Environmental exposures were estimated within home and school neighbourhoods, and along GIS (modelled) and GPS (actual) routes from home to school. We directly compared associations between BMI and GIS-modelled versus GPS-derived environmental exposures. The study was conducted in Mebane and Mount Airy, North Carolina, USA, in 2011. RESULTS: In adjusted regression models, greater school walkability was associated with significantly lower mean BMI. Greater home walkability was associated with increased BMI, as was greater school access to green space. Adjusted associations between BMI and route exposure characteristics were null. The use of GPS-actual route exposures did not appear to confound associations between environmental exposures and BMI in this sample. CONCLUSIONS: This study found few associations between environmental exposures in home, school and commuting domains and body weight in children. However, walkability of the school neighbourhood may be important. Of the other significant associations observed, some were in unexpected directions. Importantly, we found no evidence of selective daily mobility bias in this sample, although our study design is in need of replication in a free-living adult sample.

De la cooperativa agroalimentaria a la "learning netchain". Hacia un planteamiento teorico interorganizativo e interpersonal

Se propone un planteamiento teórico/conceptual para determinar si las relaciones interorganizativas e interpersonales de la netchain de las cooperativas agroalimentarias evolucionan hacia una learning netchain. Las propuestas del trabajo muestran que el mayor grado de asociacionismo y la mayor cooperación/colaboración vertical a lo largo de la cadena están positivamente relacionados con la posición horizontal de la empresa focal más cercana del consumidor final. Esto requiere una planificación y una resolución de problemas de manera conjunta, lo que está positivamente relacionado con el mayor flujo y diversidad de la información/conocimiento obtenido y diseminado a lo largo de la netchain. Al mismo tiempo se necesita desarrollar un contexto social en el que fluya la información/conocimiento y las nuevas ideas de manera informal y esto se logra con redes personales y, principalmente, profesionales y con redes internas y, principalmente, externas. Todo esto permitirá una mayor satisfacción de los socios de la cooperativa agroalimentaria y de sus distribuidores y una mayor intensidad en I+D, convirtiéndose la netchain de la cooperativa agroalimentaria, así, en una learning netchain.

Reliability of blood pressure determination with the Finapres with altered physiological states or pharmacodynamic conditions

The blood pressure waveform is modified on distal propagation by phenomena such as dispersion, reflection and the state of the arterial compliance. The consequent effects are amplification and narrowing of the wave, with an increased systolic, reduced diastolic and essentially unaltered mean blood pressure. The Finapres measures the peripheral pressure using the volume clamp principle; it has not been validated under altered physiological conditions and during pharmacodynamic interventions. We studied simultaneous Finapres and brachial blood pressures (using a conventional oscillometric sphygmomanometer—Vitalmap) in ten normal volunteers at rest, and during dynamic exercise and a cold pressor test. The effects of pharmacodynamic intervention were examined following beta-adrenoceptor blockade with propranolol (160 mg) or beta-adrenoceptor modulation with the beta-adrenoceptor partial agonist celiprolol (400 mg). The Finapres systolic pressure was significantly higher than the brachial value during all three test states. The difference between the systolic pressures measured by the two devices was shown to increase significantly during the cold pressor test, but not during dynamic (supine bicycle) exercise. The Finapres diastolic pressure was significantly higher than the Vitalmap value during exercise and the cold pressor test. The differences between the two methods increased significantly over time. Beta-adrenergic blockade with propranolol or modulation with celiprolol had no significant interaction with the pressure differences between the Finapres and Vitalmap techniques. The results would support the view that the Finapres can provide blood pressure information which is robust under most circumstances. Although this pharmacodynamic intervention did not alter the relationship between the peripheral and central blood pressure, it is important to note that this dynamic relationship is sensitive to circulatory loading conditions and wave transmission characteristics; it is possible that the Finapres could be less reliable in clinical settings where potent vasoactive agents were being administered.

Tensor products of operator systems

The purpose of the present paper is to lay the foundations for a systematic study of tensor products of operator systems. After giving an axiomatic definition of tensor products in this category, we examine in detail several particular examples of tensor products, including a minimal, maximal, maximal commuting, maximal injective and some asymmetric tensor products. We characterize these tensor products in terms of their universal properties and give descriptions of their positive cones. We also characterize the corresponding tensor products of operator spaces induced by a certain canonical inclusion of an operator space into an operator system. We examine notions of nuclearity for our tensor products which, on the category of C*-algebras, reduce to the classical notion. We exhibit an operator system S which is not completely order isomorphic to a C*-algebra yet has the property that for every C*-algebra A, the minimal and maximal tensor product of S and A are equal.