50 research outputs found

    Exploring mobile news reading interactions for news app personalisation

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    As news is increasingly accessed on smartphones and tablets, the need for personalising news app interactions is apparent. We report a series of three studies addressing key issues in the development of adaptive news app interfaces. We first surveyed users' news reading preferences and behaviours; analysis revealed three primary types of reader. We then implemented and deployed an Android news app that logs users' interactions with the app. We used the logs to train a classifier and showed that it is able to reliably recognise a user according to their reader type. Finally we evaluated alternative, adaptive user interfaces for each reader type. The evaluation demonstrates the differential benefit of the adaptation for different users of the news app and the feasibility of adaptive interfaces for news apps

    Synthesis of marmycin A and investigation into its cellular activity

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    Anthracyclines such as doxorubicin are used extensively in the treatment of cancers. Anthraquinone-related angucyclines also exhibit antiproliferative properties and have been proposed to operate via similar mechanisms, including direct genome targeting. Here, we report the chemical synthesis of marmycin A and the study of its cellular activity. The aromatic core was constructed by means of a one-pot multistep reaction comprising a regioselective Diels-Alder cycloaddition, and the complex sugar backbone was introduced through a copper-catalysed Ullmann cross-coupling, followed by a challenging Friedel-Crafts cyclization. Remarkably, fluorescence microscopy revealed that marmycin A does not target the nucleus but instead accumulates in lysosomes, thereby promoting cell death independently of genome targeting. Furthermore, a synthetic dimer of marmycin A and the lysosome-targeting agent artesunate exhibited a synergistic activity against the invasive MDA-MB-231 cancer cell line. These findings shed light on the elusive pathways through which anthraquinone derivatives act in cells, pointing towards unanticipated biological and therapeutic applications

    Synthesis of Triangular Tripalladium Cations as Noble-Metal Analogues of the Cyclopropenyl Cation

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    The first C-3-symmetric 44-core-valence-electron triangular palladium clusters, [{(SAr)(PAr3)Pd}(3)](+), have been synthesized by activation of the CS bond of isothioureas. Owing to delocalized metal-metal bonding, these stable complexes are the first noble-metal analogues of the -aromatic cyclopropenyl cation [C3H3](+), with their all-metal aromaticity involving d-type atomic orbital

    Intramolecular homolytic substitution of sulfinates and sulfinamides : a computational study

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    Ab initio and density functional theory (DFT) calculations predict that intramolecular homolytic substitution by alkyl radicals at the sulfur atom in sulfinates proceeds through a smooth transition state in which the attacking and leaving radicals adopt a near collinear arrangement. When forming a five-membered ring and the leaving radical is methyl, G3(MP2)-RAD//ROBHandHLYP/6-311++G(d,p) calculations predict that this reaction proceeds with an activation energy (ΔE1‡) of 43.2 kJ mol−1. ROBHandHLYP/6-311++G(d,p) calculations suggest that the formation of five-membered rings through intramolecular homolytic substitution by aryl radicals at the sulfur atom in sulfinates and sulfinamides, with expulsion of phenyl radicals, proceeds with the involvement of hypervalent intermediates. These intermediates further dissociate to the observed products, with overall energy barriers of 45–68 kJ mol−1, depending on the system of interest. In each case, homolytic addition to the phenyl group competes with substitution, with calculated barriers of 51–78 kJ mol−1. This computational study complements and provides insight into previous experimental observations

    Intramolecular homolytic substitution of seleninates: a computational study

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    Ab initio and density functional theory (DFT) calculations predict that intramolecular homolytic substitution by alkyl radicals at the selenium atom in seleninates proceeds through smooth transition states in which the attacking and leaving radicals adopt a near collinear arrangement. When forming a five-membered ring and the leaving radical is methyl, G3(MP2)-RAD calculations predict that this reaction proceeds with an activation energy (DE 1) of 30.4 kJ mol-1. ROBHandHLYP/6-311++G(d,p) calculations suggest that the formation of five-membered rings through similar intramolecular homolytic substitution by aryl radicals, with expulsion of phenyl radicals, proceeds with the involvement of a hypervalent intermediate. This intermediate further dissociates to the observed products, with overall energy barriers of about 40 kJ mol-1. Homolytic addition to the phenyl group was found not to be competitive with substitution, with a calculated barrier of 57.6 kJ mol-1. This computational study provides insight into homolytic substitution chemistry involving seleninates

    The Study of the Full Cycle of Gesture Interaction, The Continuum between 2D and 3D

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    International audienceThe goal of HCI researchers is to make interaction with computer interfaces simpler, efficient and more natural. In a context of object manipulation, we think that reaching this goal requires the ability to predict and recognize how humans grasp then manipulate objects. This is based on studies explaining human vision, reach, grasp taxonomies and manipulations. In this paper, we study the full cycle of gesture interaction using different points of view, then attempt to organize them using Norman's theory of Human Action, we link the psychology of object sensing to HCI goals and propose a simplification of gestures classes into four principal families. Our simplification of gestures classes still allow the expression of more detailed subclasses differentiated by the gesture properties

    Palladium-catalysis to dihydrodibenzoazepine derivatives: synthesis, structure and theoretical calculations

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    IND-OR-08 Palladium-catalysis to Dihydrodibenzoazepine Derivatives: Synthesis, Structure and Theoretical Calculations In the framework of our research aimed at developing efficient methods for the construction of complex molecules through a series of metal-controlled steps, starting from a pool of simple molecules [1] we have worked out a one-pot process for the synthesis of dihydrodibenzoazepines, an important class of seven-membered heterocycles with pharmacological activity [2]. The process consists of the reaction of one molecule of aryl iodide, one of a bromoaniline and one of norbornene at 105 °C in DMF under the catalytic action of palladium(0)/triarylphosphine. Several steps occur, including the initial oxidative addition of the aryl halide to palladium(0), norbornene insertion, palladacycle formation, new oxidative addition, this time involving bromoaniline, o-aminoaryl migration onto the norbornyl site of the palladacycle, azepine ring closure by reaction of the amino group with the palladium-bonded arene carbon [3]. All steps occur chemo- and regio-selectively and are compatible with a variety of substituents. Thus it has been possible to obtain compounds of the type reported in Figure 1 (R1 = H, alkyl, alkoxy, R2 = H, alkyl, Cl, carbalkoxy, R3 = alkyl, Cl, F) in high yields. The structure of two members of this class (R1 = Me, R2, R3 = H; R1 = Me, R2 = 7-Me, R3 = H) has been determined by single-crystal X-ray diffraction [4]. Theoretical calculations indicate the critical role played by the chelating amino group in directing the reaction pathway to the seven-membered ring formation [5]. [1] M.Catellani, E.Motti, and N.Della Ca’, Acc.Chem.Res., 41, 2008, 1512. [2] a) D.Tsvelikhovsky, and S.L.Buchwald, J.Am.Chem.Soc., 132, 2010, 14048 and references therein. [3] G.Maestri, E.Motti, N.Della Ca’, M.Malacria, E.Derat, and M.Catellani, J.Am.Chem.Soc., 133, 2011, 8574. [4] B.M.Aresta, M.Catellani, N.Della Ca’, C.Cuocci, S. Maggi, E. Motti, this Conference. [5] N.Della Ca’, G.Maestri, M.Malacria, E.Derat, and M.Catellani, submitted
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