130 research outputs found

    Event Detection in Wikipedia Edit History Improved by Documents Web Based Automatic Assessment

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    A majority of current work in events extraction assumes the static nature of relationships in constant expertise knowledge bases. However, in collaborative environments, such as Wikipedia, information and systems are extraordinarily dynamic over time. In this work, we introduce a new approach for extracting complex structures of events from Wikipedia. We advocate a new model to represent events by engaging more than one entities that are generalizable to an arbitrary language. The evolution of an event is captured successfully primarily based on analyzing the user edits records in Wikipedia. Our work presents a basis for a singular class of evolution-aware entity-primarily based enrichment algorithms and will extensively increase the quality of entity accessibility and temporal retrieval for Wikipedia. We formalize this problem case and conduct comprehensive experiments on a real dataset of 1.8 million Wikipedia articles in order to show the effectiveness of our proposed answer. Furthermore, we suggest a new event validation automatic method relying on a supervised model to predict the presence of events in a non-annotated corpus. As the extra document source for event validation, we chose the Web due to its ease of accessibility and wide event coverage. Our outcomes display that we are capable of acquiring 70% precision evaluated on a manually annotated corpus. Ultimately, we conduct a comparison of our strategy versus the Current Event Portal of Wikipedia and discover that our proposed WikipEvent along with the usage of Co-References technique may be utilized to provide new and more data on events

    DISULFIND: a disulfide bonding state and cysteine connectivity prediction server

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    DISULFIND is a server for predicting the disulfide bonding state of cysteines and their disulfide connectivity starting from sequence alone. Optionally, disulfide connectivity can be predicted from sequence and a bonding state assignment given as input. The output is a simple visualization of the assigned bonding state (with confidence degrees) and the most likely connectivity patterns. The server is available at

    RC deck - stiffened arch existing bridges: simulated design and structural analysis

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    The 20th century is known as the age that gave birth to the largest reinforced concrete structures. Many applications of this new material were realized at that time, both from a theoretical and practical point of view. With reference to bridges, the engineer Robert Maillart achieved a new concept of arched bridges, characterized by very stiff deck beams and slender and wide vaults, i.e., the "Deck-Stiffened Arch". The paper deals with the study of such bridge typology, particularly widespread in Italy around the 50s of the 20th century. While, nowadays, calculation tools allow developing very refined structural modelling, in the past very simple structural schemes were adopted in the design phase in order to simplify the calculation effort. The study starts from a "simulated design" of such a bridge typology adopting a reliable geometry and following the design rules and the simplified structural schemes of the time and, then, by means of a refined three-dimensional model, the performance of a typical "Maillart-Type Arch" bridge is analysed

    Dual photosensitizer cycles working synergistically in a C(sp)-C(sp3) cross-coupling reaction

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    Funding: Authors thank the University of St Andrews, Syngenta and the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT) for financial support [Ph.D. studentship to “M.B.”; Grant code: EP/L016419/1]. We thank Umicore AG for the gift of materials. E.Z.-C. and P.C. acknowledge the European Union H2020 research and innovation program under the Marie SkƂodowska Curie Grant Agreement (PhotoReAct, No 956324).To assess the value and reactivity of new photocatalysts (PCs), their performance should be evaluated in one or more established reactions and benchmarked against the performance using known PCs. Here, we evaluated our recently developed PC, pDTCz- DPmS, in a C(sp)-C(sp3) cross-coupling reaction that had been documented in the literature. Previous findings indicated this reaction could not proceed in the absence of PC; however, under our conditions this was not the case. Without PC, a moderate product yield was obtained, while this yield increased significantly upon addition of pDTCz-DPmS. UV-Vis absorption studies indicated that the Hantzsch ester (HE) additive was acting as a competitive absorber of the light from the excitation source, and quenching studies confirmed that the HE was quenched by the radical precursor, N-(acyloxy)phthalimide. Mechanistic investigations established that two parallel photosensitization pathways were in operation; a reductive quenching photocatalytic pathway (using pDTCz-DPmS) and a sacrificial photoreductant pathway (employing HE). These pathways work synergistically to enhance the yield of target product.Publisher PDFPeer reviewe

    Dual Photoredox and Nickel Catalysed Reductive Coupling of Alkynes and Aldehydes

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    A regioselective vinylation of aromatic and aliphatic aldehydes promoted by the merging of photoredox and nickel catalysis is here reported. A comprehensive investigation on the reaction conditions allowed the disclosure of a valid and reproducible protocol based on a nickel-mediated reductive coupling approach under visible light irradiation. The employment of 3CzClIPN (2,4,6-tris(carbazol-9-yl)-5-chloro-isophthalonitrile) as the photocatalyst and Hantzsch's ester as the sacrificial organic reductant replace the use of boron-, silicon- or zinc-based reducing agents, making this method a worthy alternative to the already known protocols. The developed mild reaction conditions allow the access to a wide range of substituents decorating both the aldehyde and the alkyne. Moreover, careful photophysical investigations shed light on the mechanism of the reaction

    Effect of the iodine atom position on the phosphorescence of BODIPY derivatives: a combined computational and experimental study

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    A new BODIPY derivative (o-I-BDP) containing an iodine atom in the ortho position of the meso-linked phenyl group was prepared. Photophysical and electrochemical properties of the molecule were compared to previously reported iodo BODIPY derivatives, as well as to the non-iodinated analog. While in the case of derivatives featuring iodine substituents in the BODIPY core, efficient population of the triplet state is accompanied by a substantial positive shift of the reduction potential compared to pristine BODIPY, o-I-BDP displays phosphorescence and simultaneously maintains the electrochemical properties of unsubstituted BODIPYs. A theoretical investigation was settled to analyze results and rationalize the influence of iodine position on electronic and photophysical properties, with the purpose of preparing a fully organic phosphorescent BODIPY derivative. TD-DFT and spin-orbit coupling calculations shed light on the subtle effects played by the introduction of iodine atom in different positions of BODIPY

    Light-Induced Access to Carbazole-1,3-dicarbonitrile: A Thermally Activated Delayed Fluorescent (TADF) Photocatalyst for Cobalt-Mediated Allylations

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    The stability of a photocatalyst under irradiation is important in photoredox applications. In this work, we investigated the stability of a thermally activated delayed fluorescence (TADF) photocatalyst {3DPAFIPN [2,4,6-tris(diphenylamino)-5-fluoroisophthalonitrile]}, recently employed in photoredox-mediated processes, discovering that in the absence of quenchers the chromophore is unstable and is efficiently converted by irradiation with visible light into another species based on the carbazole-1,3-dicarbonitrile moiety. The new species obtained is itself a TADF emitter and finds useful applications in photoredox transformations. At the excited state, it is a strong reductant and was efficiently applied to cobalt-mediated allylation of aldehydes, whereas other TADFs (4CzIPN and 3DPAFIPN) failed to promote efficient photocatalytic cycles

    Growth defects and loss-of-function in synthetic gene circuits

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    Synthetic gene circuits perturb the physiology of their cellular host. The extra load on endogenous processes shifts the equilibrium of resource allocation in the host, leading to slow growth and reduced biosynthesis. Here we built integrated host-circuit models to quantify growth defects caused by synthetic gene circuits. Simulations reveal a complex relation between circuit output and cellular capacity for gene expression. For weak induction of heterologous genes, protein output can be increased at the expense of growth defects. Yet for stronger induction, cellular capacity reaches a tipping point, beyond which both gene expression and growth rate drop sharply. Extensive simulations across various growth conditions and large regions of the design space suggest that the critical capacity is a result of ribosomal scarcity. We studied the impact of growth defects on various gene circuits and transcriptional logic gates, which highlights the extent to which cellular burden can limit, shape, and even break down circuit function. Our approach offers a comprehensive framework to assess the impact of host-circuit interactions in silico, with wide-ranging implications for the design and optimization of bacterial gene circuits

    Study of an Impact Mill-Based Mechanical Method for NdFeB Magnet Recycling

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    Nowadays, the circular economy is gaining more and more attention in sectors where the raw material supply is critical for both cost and geo-political reasons. Moreover, the environmental impact issue calls for recycling. From this perspective, the recovery of rare earth elements represents a strategic point. On the other hand, the high cost and the dangerous standard recovery methods that apply to NdFeB magnets limits options for traditional recycling. A new mechanical method is proposed, not requiring hydrogen, high temperature, or chemical processes, but instead using an impact mill designed to operate in vacuum. A traditional impact mill operating in a glove box filled with Ar atmosphere has also been used for comparison. The obtained NdFeB powders were analyzed in terms of magnetic properties and chemical composition, particularly in terms of the oxygen content

    Tailoring colors by O-annulation of polycyclic aromatic hydrocarbons

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    The synthesis of O-doped polyaromatic hydrocarbons, in which two polycyclic aromatic hydrocarbon subunits are bridged through one or two O atoms, has been achieved. This includes high-yielding ring-closure key steps that, depending on the reaction conditions, yield the formation of either furanyl or pyranopyranyl linkages through intramolecular C-O bond formation. Comprehensive photophysical measurements in solution showed that these molecules feature exceptionally high emission yields and tunable absorption properties throughout the UV-vis spectral region. Electrochemical investigations showed that in all cases the O-annulation increases the electron donor capabilities by raising the HOMO energy level with the LUMO energy level being less affected. Moreover, third-order NLO measurements of solutions or thin films containing the dyes displayed very good second hyperpolarizibility values. Importantly, PMMA films containing the pyranopyranyl derivatives displayed weak linear absorption and NLO absorption compared to the nonlinearity and NLO refraction, respectively, revealing to be exceptional organic materials for photonic devices
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