Search results for "Reaction"
showing 10 items of 6134 documents
Unraveling the kinetics and molecular mechanism of gas phase pyrolysis of cubane to [8]annulene
2020
The kinetic and electron density flows are studied theoretically for the gas phase pyrolysis of cubane via its cage opening to reach bicyclooctatriene and then thermal rearrangement of bicyclooctatriene to produce [8]annulene which is the experimentally observed major product. The observed kinetic data at the MN15-L/maug-cc-pVTZ level of theory were in good agreement with the experimental results as compared to the CBS-QB3 method. The cage opening and the thermal rearrangement steps at the experimentally employed temperature of 520 K were exergonic and exothermic. The atmospheric rate constants calculated by means of the RRKM theory show that the cage opening is the rate-determining step. T…
A novel radiation exposure control apparatus for microwave assisted chemical reactions
2004
AbstractA radiation exposure control apparatus is used for microwave (2.45 GHz) treatment of chemical reactions in controlled and reproducible conditions. A spectrophotometer has been interfaced with the microwave set-up in order to monitor the reaction evolution in situ. Both numerical and experimental dosimetries are carried out in order to evaluate the field distribution within the sample. Finally, particular working conditions are suggested.
Gamma radiation induced polymerization of vinyl monomers in dense CO2
2002
Abstract The dispersion polymerization of methyl methacrylate in dense carbon dioxide, initiated by γ-rays, utilizing different polysiloxanes as polymeric stabilizers, was investigated. The progress of the reaction, as a function of the irradiation dose, was also studied and the occurrence of a gel effect has been detected. For comparison, the dispersion polymerization has been carried out in supercritical conditions ( T =65°C and 38 MPa) in the presence of 2,2′-azobis(isobutyronitrile) (AIBN) as initiator. High molecular weight polymer (M w > 1000 kg/mol) with narrow molecular weight distribution has been obtained both with γ-rays and AIBN. The electron scanning micrographs show that regul…
Determination of gas temperature of high-frequency low-temperature electrodeless plasma using molecular spectra of hydrogen and hydroxyl-radical
2012
Abstract In this study we determine gas temperature of He+H 2 , Ar+H 2 and Ne+H 2 high frequency electrodeless lamps using intensity distribution in rotational spectra of hydrogen molecule and hydroxyl radical. The measurement results show that OH rotational spectra can be successfully used for estimation of gas temperature of the high-frequency electrodeless lamps at very small amounts of hydrogen present in plasma. The analysis of the measurement results leads to the conclusion that in “pure” plasma the applied energy is used to heat plasma, while for the plasma with hydrogen addition the energy is used in chemical reactions.
Glow Rate Technique for Spectroscopy of Complex Thermostimulated Relaxation Processes
1996
The glow rate technique (GRT) developed for the analysis of complex trap spectra, is the extension of the known heating rate method to the full glow curve. It is shown that using two glow curves measured at different heating rate constants, a special mean activation energy of simultaneously emptied traps can be obtained as a function of temperature or emitted light sum to a good approximation. Expressions have been derived for the calculation of the mean activation energy function from data measured using a linear, logarithmic or a hyperbolic heating mode. Theoretical expressions for the mean activation energy function have been obtained and discussed for arbitrary trap distribution functio…
Stoichiometric and kinetic study of the 99Tc-DMSA complex obtained with stannous excess: A possible model for the physico-chemical behaviour of the r…
1982
A stoichiometric and kinetic study was made of the 99mTc-DMSA complex obtained in the presence of large amounts of Sn2+. It is demonstrated that the Tc oxidation state is 3+. It is established that the complex degrades to another one if there is an Sn2+ deficiency. These results were confirmed by spectroscopic and spectrophotometric methods.
Mechanisms of interference of p-diphenols with the Trinder reaction
2020
p-Diphenols, such as homogentisic acid, gentisic acid, etamsylate, and calcium dobesilate, interfere with diagnostic tests utilizing the Trinder reaction but the mechanisms of these effects are not fully understood. We observed substantial differences both in oxidation of p-diphenols by horseradish peroxidase and their influence on oxidation of 4-aminoantipyrine and various phenolic substrates. Homogentisic acid was rapidly oxidized by the enzyme and completely blocked chromophore formation. Enzymatic oxidation of the remaining p-diphenols was slow and they only moderately inhibited chromophore formation. However, in the presence of standard substrates all tested p-diphenols were rapidly co…
The Source of the Carbon Monoxide in the Classical Belousov-Zhabotinsky Reaction
2007
CO and CO2 evolution was measured in a cerium and in a ferroin-catalyzed Belousov−Zhabotinsky (BZ) reaction. These gases were stripped from the reaction mixture by a N2 carrier gas, mixed with H2, converted to methane on a Ni catalyst, and then measured by a flame ionization detector (FID). CO could be detected separately by absorbing CO2 on a soda lime column. In separate experiments it was proven that CO is produced in a reaction of BrO2• radicals with bromomalonic acid (BrMA). To this end BrO2• radicals were generated in two different ways: (i) in the reaction HBrO2 + HBrO3 ↔ 2 BrO2• + H2O and (ii) by reducing HBrO3 to BrO2• by Fe2+. It was found that •OH radicals produced by Fenton's r…
Progress on nuclear reaction rates affecting the stellar production of 26Al
2023
Abstract The radioisotope 26Al is a key observable for nucleosynthesis in the Galaxy and the environment of the early Solar System. To properly interpret the large variety of astronomical and meteoritic data, it is crucial to understand both the nuclear reactions involved in the production of 26Al in the relevant stellar sites and the physics of such sites. These range from the winds of low- and intermediate-mass asymptotic giant branch stars; to massive and very massive stars, both their Wolf–Rayet winds and their final core-collapse supernovae (CCSN); and the ejecta from novae, the explosions that occur on the surface of a white dwarf accreting material from a stellar companion. Several r…
Conformational preferences and synthesis of isomers Z and E of oxazole-dehydrophenylalanine
2016
Dehydrophenylalanine, ΔPhe, is the most commonly studied α,β-dehydroamino acid. In nature, further modifications of the α,β-dehydroamino acids were found, for example, replacement of the C-terminal amide group by oxazole ring. The conformational properties of oxazole-dehydrophenylalanine residue (ΔPhe-Ozl), both isomers Z and E, were investigated. To determine all possible conformations, theoretical calculations were performed using Ac-(Z/E)-ΔPhe-Ozl(4-Me) model compounds at M06-2X/6-31++G(d,p) level of theory. Ac-(Z/E)-ΔPhe-Ozl-4-COOEt compounds were synthesized and the conformational preferences of each isomer, Z and E, were investigated using FTIR and NMR-NOE in solutions of increasing p…