859 resultados para BORON-CENTERED RADICALS


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Long lived: Carbonyloxyl radicals (RCO2 .) are reactive intermediates that play key roles in initiating polymerization reactions. This reactivity also makes their direct observation difficult. For the first time a persistent organic RCO2 . radical is detected in the gas phase, its extraordinary longevity is attributed to the high barrier towards fragmentation owing to the endothermicity of the decarboxylation products. Grant Numbers ARC/DP0986738, ARC/DP120102922, ARC/DE120100467

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The reactions of distonic 4-(N, N, N-trimethylammonium)-2-methylphenyl and 5-(N, N, N-trimethylammonium)-2-methylphenyl radical cations (m/z 149) with O-2 are studied in the gas phase using ion-trap mass spectrometry. Photodissociation (PD) of halogenated precursors gives rise to the target distonic charge-tagged methylphenyl radical whereas collision-induced dissociation (CID) is found to produce unreactive radical ions. The PD generated distonic radicals, however, react rapidly with O-2 to form \[M + O2](center dot+) and \[M + O-2 - OH](center dot+) ions, detected at m/z 181 and m/z 164, respectively. Quantum chemical calculations using G3SX(MP3) and M06-2X theories are deployed to examine key decomposition pathways of the 5-(N, N, N-trimethylammonium)-2-methylphenylperoxyl radical and rationalise the observed product ions. The prevailing product mechanism involves a 1,5- H shift in the peroxyl radical forming a QOOH-type intermediate that subsequently eliminates (OH)-O-center dot to yield charge-tagged 2-quinone methide. Our study suggests that the analogous process should occur for the neutral methylphenyl + O-2 reaction, thus serving as a plausible source of (OH)-O-center dot radicals in combustion environments. Grants: ARC/DP0986738, ARC/DP130100862

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In this paper, we describe an interactive artwork that uses large body gestures as its primary interactive mode. The artist intends the work to provoke active reflection in the audience by way of gesture and content. The technology is not the focus, rather the aim is to provoke memory, to elicit feelings of connective human experiences in a required-to-participate audience. We find the work provokes a diverse and contradictory set of responses. The methods used to understand this include qualitative methods common to evaluating interactive art works, as well as in-depth discussions with the artist herself. This paper is relevant to the Human - Centered Computing track because in all stages of the design of the work - as well as the evaluation - the focus is on the human aspect; the computing is designed to enable all-too-human responses.

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This paper examines the role of visual information in a remote help-giving situation involving the collaborative physical task of designing a prototype remote control. We analyze a set of video recordings captured within an experimental setting. Our analysis shows that using gestures and relevant artefacts and by projecting activities on the camera, participants were able to discuss several design-related issues. The results indicate that with a limited camera view (mainly faces and shoulders), participants' conversations were centered at the physical prototype that they were designing. The socially organized use of our experimental setting provides some key implications for designing future remote collaborative systems.