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An experimental study of the thermal decomposition of a β‐hydroxy alkene, 3‐methyl‐3‐buten‐1‐ol, in m‐xylene solution, has been carried out at five different temperatures in the range of 513.15–563.15 K. The temperature dependence of the rate constants for the decomposition of this compound in the corresponding Arrhenius equation is given by ln k (s?1) = (25.65 ± 1.52) ? (17,944 ± 814) (kJ·mol?1)·T?1. A computational study has been carried out at the M05–2X/6–31+G(d,p) level of theory to calculate the rate constants and the activation parameters by the classical transition state theory. There is a good agreement between the experimental and calculated rate constants and activation Gibbs energies. The bonding characteristics of reactant, transition state, and products have been investigated by the natural bond orbital analysis, which provides the natural atomic charges and the Wiberg bond indices. Based on the results obtained, the mechanism proposed is a one‐step process proceeding through a six‐membered cyclic transition state, being a concerted and slightly asynchronous process. The results have been compared with those obtained previously by us (Struct Chem 2013, 24, 1811–1816) for the thermal decomposition of 3‐buten‐1‐ol, in m‐xylene solution. We can conclude that in the compound studied in this work, 3‐methyl‐3‐buten‐1‐ol, the effect of substitution at position 3 by a weakly activating CH3 group is the stabilization of the transition state formed in the reaction and therefore a small increase in the rate of thermal decomposition. 相似文献
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Abstract Due to the wide use of polymers in medicine, researchers are required to solve a very important problem–to understand the interaction between materials of nonphysiological origin and the surrounding biological liquids, and tissues, particularly blood. 相似文献
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Trinczek M Gorelov A Melconian D Alford WP Asgeirsson D Ashery D Behr JA Bricault PG D'Auria JM Deutsch J Dilling J Dombsky M Dubé P Eaton S Fingler J Giesen U Gu S Häusser O Jackson KP Lee B Schmid JH Stocki TJ Swanson TB Wong W 《Physical review letters》2003,90(1):012501
A new technique, full neutrino momentum reconstruction, is used to set limits on the admixture of heavy neutrinos into the electron neutrino. We measure coincidences between nuclear recoils and positrons from the beta decay of trapped radioactive atoms and deduce the neutrino momentum. A search for peaks in the reconstructed recoil time-of-flight spectrum as a function of positron energy is performed. The admixture upper limits range from 4 x 10(-3) to 2 x 10(-2) and are the best direct limits for neutrinos (as opposed to antineutrinos) for the mass region of 0.7 to 3.5 MeV. 相似文献
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Chemical oxidation is useful for solubilizing and separating endohedral metallofullerenes, as demonstrated here by a separation of three categories of Gd@C2n species and by the solubilization of Tm@C60+ and Tm@C70+ for the first time. 相似文献
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We present the dispersion relations for quasiparticle excitations about the color-flavor locked ground state of QCD at high baryon density. In the presence of condensates which pair light and strange quarks there need not be an energy gap in the quasiparticle spectrum. This raises the possibility of gapless color superconductivity, with a Meissner effect but no minimum excitation energy. Analysis within a toy model suggests that gapless color superconductivity may occur only as a metastable phase. 相似文献
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Saripella R Loizou PC Thibodeau L Alford JA 《The Journal of the Acoustical Society of America》2011,130(5):3028-3037
Weak consonants (e.g., stops) are more susceptible to noise than vowels, owing partially to their lower intensity. This raises the question whether hearing-impaired (HI) listeners are able to perceive (and utilize effectively) the high-frequency cues present in consonants. To answer this question, HI listeners were presented with clean (noise absent) weak consonants in otherwise noise-corrupted sentences. Results indicated that HI listeners received significant benefit in intelligibility (4 dB decrease in speech reception threshold) when they had access to clean consonant information. At extremely low signal-to-noise ratio (SNR) levels, however, HI listeners received only 64% of the benefit obtained by normal-hearing listeners. This lack of equitable benefit was investigated in Experiment 2 by testing the hypothesis that the high-frequency cues present in consonants were not audible to HI listeners. This was tested by selectively amplifying the noisy consonants while leaving the noisy sonorant sounds (e.g., vowels) unaltered. Listening tests indicated small (~10%), but statistically significant, improvements in intelligibility at low SNR conditions when the consonants were amplified in the high-frequency region. Selective consonant amplification provided reliable low-frequency acoustic landmarks that in turn facilitated a better lexical segmentation of the speech stream and contributed to the small improvement in intelligibility. 相似文献