26 research outputs found

    Cosmic-ray-mediated Formation of Benzene on the Surface of Saturn's Moon Titan

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    The aromatic benzene molecule (C_6H_6)—a central building block of polycyclic aromatic hydrocarbon molecules—is of crucial importance for the understanding of the organic chemistry of Saturn's largest moon, Titan. Here, we show via laboratory experiments and electronic structure calculations that the benzene molecule can be formed on Titan's surface in situ via non-equilibrium chemistry by cosmic-ray processing of low-temperature acetylene (C_2H_2) ices. The actual yield of benzene depends strongly on the surface coverage. We suggest that the cosmic-ray-mediated chemistry on Titan's surface could be the dominant source of benzene, i.e., a factor of at least two orders of magnitude higher compared to previously modeled precipitation rates, in those regions of the surface which have a high surface coverage of acetylene

    Chemical dynamics of triacetylene formation and implications to the synthesis of polyynes in Titan's atmosphere

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    For the last four decades, the role of polyynes such as diacetylene (HCCCCH) and triacetylene (HCCCCCCH) in the chemical evolution of the atmosphere of Saturn's moon Titan has been a subject of vigorous research. These polyacetylenes are thought to serve as an UV radiation shield in planetary environments; thus, acting as prebiotic ozone, and are considered as important constituents of the visible haze layers on Titan. However, the underlying chemical processes that initiate the formation and control the growth of polyynes have been the least understood to date. Here, we present a combined experimental, theoretical, and modeling study on the synthesis of the polyyne triacetylene (HCCCCCCH) via the bimolecular gas phase reaction of the ethynyl radical (CCH) with diacetylene (HCCCCH). This elementary reaction is rapid, has no entrance barrier, and yields the triacetylene molecule via indirect scattering dynamics through complex formation in a single collision event. Photochemical models of Titan's atmosphere imply that triacetylene may serve as a building block to synthesize even more complex polyynes such as tetraacetylene (HCCCCCCCCH)

    Double Blind Study Investigating the Effect of Different Voice Prostheses on Ease of Swallowing and Residue Post Laryngectomy.

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    Voice prostheses have been examined for their effect on voice production but there is little datum on their effect on swallow function. This study investigated the difference between six commonly available voice prostheses in terms of swallowing. Laryngectomy patients had up to six voice prostheses placed in a random order over two visits. Swallowing was evaluated for each prosthesis using FEES (Fibreoptic Endoscopic Evaluation of Swallowing). After each prosthesis trial, patients self-evaluated their experience of swallowing. Three independent experts indicated which prosthesis they considered best for swallowing for each patient and judged residue on the voice prosthesis and in the upper esophagus. Raters were blinded to participant details, voice prosthesis type and scores of other raters. On patient self-evaluation, scores were equally distributed across all prostheses for swallowing. Experts most frequently chose the Blom Singer Low pressure and Blom Singer Classic Indwelling voice prostheses as best for swallowing but consensus was poor for most patients. Experts found that the Blom Singer Classic Indwelling and the Provox Vega had least residue on the voice prosthesis on thin liquid (p ≤ 0.001) and soft (p = 0.001), respectively. Experts also found that the Blom Singer Low Pressure had least residue in the upper esophagus on soft consistency (p ≤ 0.001). While self-evaluation by patients did not identify a consistently preferred prosthesis for swallow, many patients expressed personal preferences, suggesting benefits to involving patients in the choice of prosthesis. Some voice prostheses may be associated with lower levels of residue on the prosthesis and upper esophagus with certain consistencies

    Comparison of Maximum Power Point Tracking Techniques Used in Photovoltaic System

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    Among the various renewable energy sources, photovoltaic (PV) systems are experiencing a great expansion, due to their low polluting levels, the abundance of solar energy and the cost decreasing of PV technologies, attracting research and investments in the field. The maximum power generated in a PV panel varies according to irradiation and temperature. Since the conversion efficiency of photovoltaic modules is low, it is necessary to implement sophisticated control techniques for monitoring the maximum power point (MPPT). Maximum power point tracking techniques are automatic control algorithms that adjust power interfaces to achieve the maximum power generation, during variations in irradiation, temperature, and characteristics of the photovoltaic module. The purpose of the MPPT is to adjust the solar panel operating voltage near the maximum power point (MPP) according to environmental conditions. This technique has become an essential component in photovoltaic power system designs. This article presents comparison of the performance of various MPPT tracking methods in photovoltaic systems using the MATLAB/Simulink software and a comparative approach

    Formation Mechanisms of Naphthalene and Indene: From the Interstellar Medium to Combustion Flames

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    The article addresses the formation mechanisms of naphthalene and indene, which represent prototype polycyclic aromatic hydrocarbons (PAH) carrying two six-membered and one five- plus a six-membered ring. Theoretical studies of the relevant chemical reactions are overviewed in terms of their potential energy surfaces, rate constants, and product branching ratios; these data are compared with experimental measurements in crossed molecular beams and the pyrolytic chemical reactor emulating the extreme conditions in the interstellar medium (ISM) and the combustion-like environment, respectively. The outcome of the reactions potentially producing naphthalene and indene is shown to critically depend on temperature and pressure or collision energy and hence the reaction mechanisms and their contributions to the PAH growth can be rather different in the ISM, planetary atmospheres, and in combustion flames at different temperatures and pressures. Specifically, this paradigm is illustrated with new theoretical results for rate constants and product branching ratios for the reaction of phenyl radical with vinylacetylene. The analysis of the formation mechanisms of naphthalene and its derivatives shows that in combustion they can be produced via hydrogen-abstraction-acetylene-addition (HACA) routes, recombination of cyclopentadienyl radical with itself and with cyclopentadiene, the reaction of benzyl radical with propargyl, methylation of indenyl radical, and the reactions of phenyl radical with vinylacetylene and 1,3-butadiene. In extreme astrochemical conditions, naphthalene and dihydronaphthalene can be formed in the C<sub>6</sub>H<sub>5</sub> + vinylacetylene and C<sub>6</sub>H<sub>5</sub> + 1,3-butadiene reactions, respectively. Ethynyl-substituted naphthalenes can be produced via the ethynyl addition mechanism beginning with benzene (in dehydrogenated forms) or with styrene. The formation mechanisms of indene in combustion include the reactions of the phenyl radical with C<sub>3</sub>H<sub>4</sub> isomers allene and propyne, reaction of the benzyl radical with acetylene, and unimolecular decomposition of the 1-phenylallyl radical originating from 3-phenylpropene, a product of the C<sub>6</sub>H<sub>5</sub> + propene reaction, or from C<sub>6</sub>H<sub>5</sub> + C<sub>3</sub>H<sub>5</sub>

    Prevalence of Vocal Fold Pathologies Among First-Year Singing Students Across Genres

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    The purpose of the study was to compare the prevalence of vocal fold pathologies among first-year singing students from the classical, musical theatre, and contemporary commercial music (CCM) genres. Prospective cohort study. Videostroboscopic examinations were rated by blinded expert raters. Vocal pathology was defined as a vocal fold abnormality on the membranous or cartilaginous portions of the vocal folds or hypomobility. Consensus among three of four raters confirmed presence of pathology. Association between genre of singer and presence of pathology, interrater reliability, and intrarater reliability were calculated. Differences in singing voice handicap, and voice use and vocal hygiene were compared. Fifty-seven participants were included. Seventeen percent of CCM, 40% of musical theatre, and 0% of classical singers were found to have vocal fold pathology. Interrater reliability was 0.522 between all four raters, 0.591 between the two laryngologists, and 0.581 between the two speech-language pathologists, showing a moderate agreement (P < .0001). Intrarater reliability was 1.000 (P < .0001) for the two laryngologists and 0.452 (P = .949) and 0.622 (P = .828) for the two speech-language pathologists. Singing Voice Handicap Index-10 data across genre showed differences between CCM and classical singers. No significant differences were found in voice usage or vocal hygiene. No classical students were found to have vocal fold pathology, whereas CCM and musical theatre students had significantly higher prevalence of pathologies. Voice use, vocal hygiene, and physiologic phonatory differences among classical, musical theatre, and CCM genres may be risk factors for development of vocal pathology. 2b Laryngoscope, 2019
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