Synthesis of chiral bicyclo[2.2.2]oct-5-en-2-ones via an intramolecular alkylation reaction

Generation of the thermodynamic dienolate of 9-bromocarvone derivatives 5, 7 and 11 furnished the chiral bicycle[2.2.2] octenones 6, 8 and 9 and 12 and 13 containing a bridgehead methyl group via an intramolecular alkylation reaction. In an analogous manner intramolecular alkylation reaction of the bromo enones 15a-e, obtained from carvone 2 by 1,3-alkylative enone transposition (-->14) followed by a regiospecific bromoetherification reaction, furnished the bicyclo[2.2.2]oct-5-en-2-ones 16a-e and 17a-e.

An Effective Seamless Connectivity Scheme for Ubiquitous Applications

The idea of ubiquity and seamless connectivity in networks is gaining more importance in recent times because of the emergence of mobile devices with added capabilities like multiple interfaces and more processing abilities. The success of ubiquitous applications depends on how effectively the user is provided with seamless connectivity. In a ubiquitous application, seamless connectivity encompasses the smooth migration of a user between networks and providing him/her with context based information automatically at all times. In this work, we propose a seamless connectivity scheme in the true sense of ubiquitous networks by providing smooth migration to a user along with providing information based on his/her contexts automatically without re-registration with the foreign network. The scheme uses Ubi-SubSystems(USS) and Soft-Switches(SS) for maintaining the ubiquitous application resources and the users. The scheme has been tested by considering the ubiquitous touring system with several sets of tourist spots and users.

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.

Formação de Formadores e Educação Superior na cibercultura: itinerâncias de Grupos de Pesquisa no Facebook

Esta tese origina-se da pesquisa de doutoramento na Universidade do Estado do Rio de Janeiro UERJ - Proped e tem como objetivo compreender a formação do formador no contexto da cibercultura e como este vem estruturando sua atuação na docência universitária. Este trabalho faz parte do eixo 2 da Pesquisa Institucional A cibercultura na era das redes sociais e da mobilidade: novas potencialidades para a formação de professores. O campo da pesquisa foi a rede social Facebook. Constituíram-se praticantes da pesquisa seis professores-formadores do ProPEd e seus orientandos. A pertinência desta pesquisa inscreveu-se num amplo movimento da perspectiva epistemológica da multirreferencialidade com os cotidianos e pelo método atualizado da pesquisa-formação. A intenção primeira deste trabalho consistiu em mapear as experiências e itinerâncias do formador em suas práticas cotidianas nos espaçostempos da cibercultura. Tencionamos que a sistematização de ambiências formativas articulando o espaço da universidade e das redes sociais criou redes de docência e aprendizagem. Como dispositivos de pesquisa, lançamos mão de oficinas, interações nas redes sociais, conversas, participação nos grupos de pesquisa. A tese revela que a formação do formador na cibercultura forja outros espaçostempos de pesquisa acadêmica e de criação de dispositivos online. Revela também que os usos do digital em rede pelos praticantes da pesquisa fizeram emergir processos de orientação coletiva, de experiências formadoras e de articulação da interface cidadeuniversidade, estabelecendo outros sentidos para a prática pedagógica e para a pesquisa acadêmica

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.

一种自主越障巡检机器人行走夹持机构

在机器人越障过程中,由于重力的影响使得机器人车体水平姿态发生变化,从而机器人自主越障变得十分困难。分析了超高压输电线路障碍物的类型,提出了一种新的双臂自主越障巡检机器人构型,该构型能够跨越输电线路上的障碍物。针对这种新构型,阐述了机器人行走夹持机构的工作原理和实现形式,着重分析研究了偏心夹持机构对保持车体水平姿态的机理。最后,通过越障实验验证了行走夹持机构的可行性。

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.

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.

Charabanc, cultural capital and the men of recognised credit

This paper compares the cultural legacy of the all-female Charabanc with that of Field Day, its fellow counterpart in the Irish Theatre touring movement in the 1980s. It suggests that a conscious awareness amongst the all-male Field Day board of successful writers and directors of what Bourdieu has called 'cultural capital' is implicated in the enduring authority of the work of that company within the history of Irish theatre. Conversely the paper considers if the populist Charabanc, in its steadfast refusal to engage with the hierarchies of academia and publishing, was too neglectful of the cultural capital which it accrued in its heyday and has thus been party to its own occlusion from that same history.

Designing Bare Essentials: Aldi, Lidle and the architectures of cheapness

They’re cheap. They’re in every settlement of significance in Britain, Ireland and elsewhere. We all use them but perhaps do not always admit to it. Especially, if we are architects.
Over the past decades Aldi/Lidl low cost supermarkets have escaped from middle Europe to take over large tracts of the English speaking world remaking them according to a formula of mass-produced sheds, buff-coloured cobble-lock car parks, logos in primary colours, bare-shelves and eclectic special offers. Response within architectural discourse to this phenomenon has been largely one of indifference and such places remain, perhaps reiterating Pevsner’s controversial insights into the bicycle shed, on the peripheries of what we might term architecture. This paper seeks to explore the spatial complexities of the discount supermarket and in doing so open up a discussion on the architecture of cheapness. As a road-map, it takes former managing director Dieter Brandes’ treatise on the Aldi formula, Bare Essentials: the Aldi Way to Retailing, and investigates the strategies through which economic exigencies manifest themselves in a series of spatial tactics which involve building. Central to this is the idea of architecture as system rather than form and, in Aldi/Lidl’s case, the result of a spatial network of flows. To understand the architecture of the supermarket, then, it is necessary to measure the times and spaces of supply across the scales of intersection between global and local.
Evaluating the energy, economy and precision of such systems challenges the liminal position of the commercial, the placeless and especially the cheap within architectural discourse. As is well known, architectures of mass-production and prefabrication and their origins exercised modernist thinkers such as Sigfried Giedion and Walter Gropius in the early twentieth century and has undergone a resurgence in recent times. Meanwhile, the mapping of the hitherto overlooked forms and iconography of commerce in Learning from Las Vegas (1971) was extended by Rem Koolhaas et al into an investigation of the technologies, systems and precedents of retail in the Harvard Design School Guide to Shopping, thirty years later in 2001. While obviously always a criteria for building, to find writings on architecture which explicitly celebrate cheapness as a design virtue or, indeed, even iterate the word cheap is more difficult. Walter Gropius’ essay ‘How can we build cheaper, better, more attractive houses?’ (1927), however, situates the cheap within the discussions – articulated, amongst others, by Karl Teige and Bruno Taut – surrounding the minimal dwelling and the moral benefits of absence of the 1920s and 30s.
In our contemporary age of heightened consumption, it is perhaps fitting that an architecture of bare essentials is defined in retail rather than in housing, a commercial existenzminimum where the Miesian paradox of ‘less is more’ is resold as a paradigm of ‘more for less’ in the ubiquitous yet overlooked architectures of the discount supermarket.

The Virgin Father (Revival of 2009 production):The Virgin Father: A Stage Play (Revival of 2009 production)

A stage play touring Cushendall, Down Arts Centre, The Playhouse Derry/Londonderry, with a further one-week run at the Lyric Theatre, Belfast.

Boronic acids as partners in multicomponent reactions

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014