Pushing the limits of concertedness. A waltz of wandering carbocations.

Among the array of complex terpene-forming carbocation cyclization/rearrangement reactions, the so-called "triple shift" reactions are among the most unexpected. Such reactions involve the asynchronous combination of three 1,n-shifts into a concerted process, e.g., a 1,2-alkyl shift followed by a 1,3-hydride shift followed by a second 1,2-alkyl shift. This type of reaction so far has been proposed to occur during the biosynthesis of diterpenes and the sidechains of sterols. Here we describe efforts to push the limits of concertedness in this type of carbocation reaction by designing, and characterizing with quantum chemical computations, systems that could couple additional 1,n-shift events to a triple shift leading, in principle to quadruple, pentuple, etc. shifts. While our designs did not lead to clear-cut examples of quadruple, etc. shifts, they did lead to reactions with surprisingly flat energy surfaces where more than five chemical events connect reactants and plausible products. Ab initio molecular dynamics simulations demonstrate that the formal minima on these surfaces interchange on short timescales, both with each other and with additional unexpected structures, allowing us a glimpse into a very complex manifold that allows ready access to great structural diversity

GUIsurfer : a reverse engineering framework for user interface software

GUIsurfer: A Reverse Engineering Framework for User Interface Softwar

The GUISurfer tool: towards a language independent approach to reverse engineering GUI code

Graphical user interfaces (GUIs) are critical components of today's software. Developers are dedicating a larger portion of code to implementing them. Given their increased importance, correctness of GUIs code is becoming essential. This paper describes the latest results in the development of GUISurfer, a tool to reverse engineer the GUI layer of interactive computing systems. The ultimate goal of the tool is to enable analysis of interactive system from source code

Combining static and dynamic analysis for the reverse engineering of web applications

Software has become so complex that it is increasingly hard to have a complete understanding of how a particular system will behave. Web applications, their user interfaces in particular, are built with a wide variety of technologies making them particularly hard to debug and maintain. Reverse engineering techniques, either through static analysis of the code or dynamic analysis of the running application, can be used to help gain this understanding. Each type of technique has its limitations. With static analysis it is difficult to have good coverage of highly dynamic applications, while dynamic analysis faces problems with guaranteeing that generated models fully capture the behavior of the system. This paper proposes a new hybrid approach for the reverse engineering of web applications' user interfaces. The approach combines dynamic analyzes of the application at runtime, with static analyzes of the source code of the event handlers found during interaction. Information derived from the source code is both directly added to the generated models, and used to guide the dynamic analysis.This work is funded by ERDF - European Regional Development Fund through the COMPETE Programme (operational programme for competitiveness) and by National Funds through the FCT - Fundação para a Ciência e a Tecnologia (Portuguese Foundation for Science and Technology) within project FCOMP-01-0124-FEDER-015095. Carlos Eduardo Silva is further funded by the Portuguese Government through FCT, grant SFRH/BD/71136/2010

Can GUI implementation markup languages be used for modelling?

The current diversity of available devices and form factors increases the need for model-based techniques to support adapting applications from one device to another.Most work on user interface modelling is built around declarative markup languages. Markup languages play a relevant role, not only in the modelling of user interfaces, but also in their implementation. However, the languages used by each community (modellers/ developers) have, to a great extent evolved separately. This means that the step from concrete model to final interface becomes needlessly complicated, requiring either compilers or interpreters to bridge this gap. In this paper we compare a modelling language (UsiXML) with several markup implementation languages. We analyse if it is feasible to use the implementation languages as modelling languages.(undefined

Desenvolvimento e uso de um jogo didático "Corrida da Química" e sua implementação no ensino da química no 8º ano de escolaridade

A utilização de jogos didáticos no processo de ensino-aprendizagem da química é uma tendência recentemente proposta por vários autores. Esta abordagem pedagógica revela-se um útil instrumento para a promoção de aspectos relacionados com o desenvolvimento cognitivo, intelectual e criativo o que promove um acréscimo da motivação dos alunos para o processo de ensino. Consequentemente, considera-se que o uso destes instrumentos facilita a sociabilidade dos alunos, traduzindo-se num acréscimo das capacidades de interação pessoal, e contribui para promover o sucesso dos alunos na escola e na sociedade. Neste trabalho descrevem-se as etapas de construção de um jogo didático, intitulado “Corrida da Química” sendo este utilizado como suporte de aprendizagem da unidade didática “Reações Químicas". O processo de elaboração do jogo envolveu a construção dos vários componentes, nomeadamente: o tabuleiro do jogo (baseado na Tabela Periódica dos Elementos); os conjuntos de cartões; os modelos de equipamento de laboratório; modelos atómicos e peças de puzzle de modelos de iões. Serão apresentados os resultados da implementação de dois testes (teste inicial e teste final) que avaliaram o impacto do jogo no processo de aprendizagem permitindo concluir que este jogo contribuiu para uma melhoria do aproveitamento e uma participação mais ativa dos aluno

Characterizing the control logic of web applications’ user interfaces

In order to develop an hybrid approach to the Reverse Engineer of Web applications, we need first to understand how much of the control logic of the user interface can be obtained from the analysis of event listeners. To that end, we have developed a tool that enables us to perform such analysis, and applied it to the implementation of the one thousand most widely used Websites (according to Alexa Top Sites). This paper describes our approach for analyzing the user interface layer of those Websites, and the results we got from the analysis. The conclusions drawn from the exercise will be used to guide the development of the proposed hybrid reverse engineering tool.This work was partly funded by project LATiCES (Ref. NORTE-07-0124-FEDER-000062) financed by the North Portugal Regional Operational Programme (ON.2 – O Novo Norte), under the National Strategic Reference Framework (NSRF), through the European Regional Development Fund (ERDF), and by national funds, through the Portuguese funding agency, Fundação para a Ciência e a Tecnologia (FCT). Carlos Eduardo Silva is further funded by the Portuguese Government through FCT, grant SFRH/BD/71136/2010

The role of intermolecular coupling in the photophysics of disordered organic semiconductors: Aggregate emission in regioregular polythiophene

We address the role of excitonic coulping on the nature of photoexcitations in the conjugated polymer regioregular poly(3-hexylthiophene). By means of temperature-dependent absorption and photoluminescence spectroscopy, we show that optical emission is overwhelmingly dominated by weakly coupled H-aggregates. The relative absorbance of the 0-0 and 0-1 vibronic peaks provides a powerfully simple means to extract the magnitude of the intermolecular coupling energy, approximately 5 and 30 meV for films spun from isodurene and chloroform solutions respectively.Comment: 10 pages, 4 figures, published in Phys. Rev. Let

Ingestion of small-sized and irregularly shaped polyethylene microplastics affect Chironomus riparius life-history traits

Microplastics (MPs) are emerging contaminants of freshwater ecosystems. Once in aquatic systems, most of these plastic particles undergo processes of fragmentation, biofouling, and sedimentation, resulting in increased concentrations of smaller sized and irregularly-shaped particles in the sediment. High levels of MPs in freshwater sediments can denote a potential threat to benthic and sediment-dwelling organisms such as dipteran larvae. This study evaluates the ecotoxicological effect of three pools of irregularly-shaped polyethylene (PE) microplastics (pools containing 90% of the particles within 32–63 μm (size-class A), 63–250 μm (size-class B) and 125–500 μm (size-class C)), with concentrations ranging from 1.25 to 20 g Kg−1 sediment, on the dipteran Chironomus riparius life-history traits. After ten days of exposure, larvae ingested PE particles typically in the 32–63 μm range, even when 90% of the particles possessed higher size (i.e., in size-classes B and C) and the larvae mandible allowed the ingestion of such bigger-sized particles. Thus, the number of ingested particles was higher in size-class A, followed by B and C, and led to a significant reduction with similar magnitude on larval growth (Lowest Observed Effect Concentrations (LOEC) = 2.5 g Kg−1 sediment DW) and a significant delay on imagoes emergence (e.g., LOEC = 1.5 g Kg−1 sediment DW for females). The results from this study show that the ingestion and persistence of small-sized polyethylene microplastics caused significant impairments on life-history traits of C. riparius. Considering their role on freshwater food-webs and the potential persistence of small-sized PE particles in their larval gut, these results also point for the potential adverse effects of small-sized microplastics at the community and ecosystem level.This study was supported by FCT through national funds (PIDDAC), and the cofunding by the FEDER, within the PT2020 Partnership Agreement and Compete 2020 within the research project ComPET (POCI-01-0145-FEDER-030361) and CESAM (UID/AMB/50017). Also, by FCT and FSE/POCH, via a Post-Doc grant to A.L. Patricio Silva (SFRH/BPD/114870/2016), a Ph.D. grant to Carlos Silva (SFRH/BD/128134/2016) and a research contract under the program “Investigador FCT2015” to João L.T. Pestana (IF/01420/2015).publishe