999 resultados para Soft nucleophiles


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In this paper, the chemical reactivity of C3 of phosphoenolpyruvate (PEP) has been analyzed in terms of density functional theory quantified through quantum chemistry calculations. PEP is involved in a number of important enzymatic reactions, in which its C3 atom behaves like a base. In three different enzymatic reactions analyzed here, C3 sometimes behaves like a soft base and sometimes behaves like a hard base in terms of the hard-soft acid-base principle. This dual nature of C3 of PEP was found to be related to the conformational change of the molecule. This leads to a testable hypothesis: that PEP adopts particular conformations in the enzyme-substrate complexes of different PEP-using enzymes, and that the enzymes control the reactivity through controlling the dihedral angle between the carboxylate and the C==C double bond of PEP.

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The phase diagram of soft spheres with size dispersion is studied by means of an optimized Monte Carlo algorithm which allows us to equilibrate below the kinetic glass transition for all size distributions. The system ubiquitously undergoes a first-order freezing transition. While for a small size dispersion the frozen phase has a crystalline structure, large density inhomogeneities appear in the highly disperse systems. Studying the interplay between the equilibrium phase diagram and the kinetic glass transition, we argue that the experimentally found terminal polydispersity of colloids is a purely kinetic phenomenon.

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Several recent works deal with 3D data in mobile robotic problems, e.g., mapping. Data comes from any kind of sensor (time of flight, Kinect or 3D lasers) that provide a huge amount of unorganized 3D data. In this paper we detail an efficient approach to build complete 3D models using a soft computing method, the Growing Neural Gas (GNG). As neural models deal easily with noise, imprecision, uncertainty or partial data, GNG provides better results than other approaches. The GNG obtained is then applied to a sequence. We present a comprehensive study on GNG parameters to ensure the best result at the lowest time cost. From this GNG structure, we propose to calculate planar patches and thus obtaining a fast method to compute the movement performed by a mobile robot by means of a 3D models registration algorithm. Final results of 3D mapping are also shown.

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Commercial off-the-shelf microprocessors are the core of low-cost embedded systems due to their programmability and cost-effectiveness. Recent advances in electronic technologies have allowed remarkable improvements in their performance. However, they have also made microprocessors more susceptible to transient faults induced by radiation. These non-destructive events (soft errors), may cause a microprocessor to produce a wrong computation result or lose control of a system with catastrophic consequences. Therefore, soft error mitigation has become a compulsory requirement for an increasing number of applications, which operate from the space to the ground level. In this context, this paper uses the concept of selective hardening, which is aimed to design reduced-overhead and flexible mitigation techniques. Following this concept, a novel flexible version of the software-based fault recovery technique known as SWIFT-R is proposed. Our approach makes possible to select different registers subsets from the microprocessor register file to be protected on software. Thus, design space is enriched with a wide spectrum of new partially protected versions, which offer more flexibility to designers. This permits to find the best trade-offs between performance, code size, and fault coverage. Three case studies have been developed to show the applicability and flexibility of the proposal.

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Integrity assurance of configuration data has a significant impact on microcontroller-based systems reliability. This is especially true when running applications driven by events which behavior is tightly coupled to this kind of data. This work proposes a new hybrid technique that combines hardware and software resources for detecting and recovering soft-errors in system configuration data. Our approach is based on the utilization of a common built-in microcontroller resource (timer) that works jointly with a software-based technique, which is responsible to periodically refresh the configuration data. The experiments demonstrate that non-destructive single event effects can be effectively mitigated with reduced overheads. Results show an important increase in fault coverage for SEUs and SETs, about one order of magnitude.

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The diseases that affect the oral cavity are wide and diverse, comprising a broad spectrum of either benign or malignant lesions. However, few histological-based studies were performed for the evaluation of oral cavity lesions, and very few directed to oral soft tissue pathology. The aim of this study was to carry out pioneering research, within a Portuguese population, to determine the frequency and characteristics of oral malignancies, potential malignant disorders, and soft benign tissues pathologies submitted for biopsy in a north Portugal (Oporto) hospital population.

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Do realizacji niemieckich interesów w polityce zagranicznej, bezpieczeństwa i gospodarczej RFN wykorzystuje instrumenty soft power z obszaru dyplomacji publicznej, polityki rozwojowej, kulturalnej i naukowej. Budowanie sieci kontaktów i lobbing polityczny, programy współpracy rozwojowej oraz zagranicznej polityki kulturalnej i naukowej, mają służyć wspieraniu niemieckiej gospodarki uzależnionej od eksportu, uzyskaniu statusu europejskiego ośrodka technologii i innowacji oraz zwiększeniu wpływu RFN na działania zewnętrzne UE. Jednym z priorytetowych obszarów stosowania tych instrumentów są dla Niemiec państwa Europy Wschodniej, Kaukazu Południowego i Azji Centralnej. Decydują o tym bliskość geograficzna i otwierające się rynki zbytu, konieczność modernizacji gospodarek tych krajów, zagrożenia dla „miękkiego” bezpieczeństwa RFN oraz rozwój relacji UE z tymi państwami. Niemiecka aktywność jest w tych krajach niezależna od sytuacji politycznej i stanowi długofalową strategię ugruntowującą pozycję RFN jako ich najważniejszego europejskiego partnera gospodarczego i politycznego.

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Russian President Vladimir Putin’s visit to Serbia on 16 October has demonstrated Moscow’s willingness to secure its interests in the Balkans and use Belgrade in its confrontation with the West. It seems, however, that Russia does not have much to offer to Serbia’s authorities, which are reluctant to make more concessions towards Russia. However, Moscow has already gained a strong position in Serbia, which is due to the country’s dependence on Russian natural resources and, in particular, strong support for Russian policy on the part of Serbian elites and society. The traditional pro-Russian attitudes have been strengthened as a result of a series of Russia-inspired, wide-ranging soft power initiatives which have proved so successful that a large part of society has begun to believe that Russia’s interests are consistent with Serbia’s. Russia’s increasingly active policy towards Serbia and the Serbian minorities in the neighbouring countries – Bosnia and Herzegovina, Montenegro and Kosovo – has been part of a larger plan aimed at hampering the integration of the Balkan states with the Euro-Atlantic structures and maintaining an area of instability and frozen conflicts in the EU’s near neighbourhood. Russia’s policy is also becoming increasingly effective due to the EU states’ diminishing support for Balkan countries’ European integration.

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The European Union and Singapore are vastly different entities, each with its own regional and global priorities and policies. Both actors employ a range of tools and instruments to aid in their foreign policy objectives, including in the projection of their soft power. It is worth analysing and comparing the specific instruments of these two actors’ soft power strategies, including but not limited to their stated objectives and perceived effectiveness. This paper will compare the role of higher education and scholarships in diffusing soft power through a comparative case study of the Erasmus Mundus scholarship program and the Singapore Scholarship administered by the Ministry of Foreign Affairs. It will look at the ways in which these programs have shaped the standing of the actors in diffusing their norms and objectives in the regional and international arena. A comparative analysis of these programs will hopefully provide some insight into the proximity between foreign policy-making and higher education internationalisation. This paper will begin with an overview of the aforementioned programs and related schemes, before dissecting and comparing the intent and the policy-making processes behind these, and concludes with a discussion on the present and future role of higher education as a strategic soft power tool.

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The EU is in uncharted waters when it comes to negotiating the UK’s exit from the Union. Creative and flexible thinking will be required from all parties if an orderly departure is to be managed. The alternative is a fractious, mutually damaging and disorderly Brexit. This commentary argues for a short-term, time-limited agreement to stabilise the EU-UK relationship and to allow breathing space to develop the terms of a long-term strategic partnership.