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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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F. Schiffner 《Monatshefte für Mathematik》1901,12(1):177-184
Ohne Zusammenfassung 相似文献
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We report the calculation of12C16O molecular constants and rotational-vibrational transition frequencies of the electronic ground state with improved accuracy. It is based on a recent paper containing results of accurate frequency measurements of a few CO lines. By using these data new rotational constants have been determined, they are then utilized to calculate band center frequencies of four bands. Futhermore, four vibrational constants were computed by means of the calculated band center frequencies. Tables of band center frequencies, andP andR branch transition frequencies are given for the bands 1–0 to 20–19. It was not possible to obtain standard deviations of line frequencies. It is shown, however, that the best molecular constants published lead to line frequencies with deviations of a few hundred MHz. Line frequencies calculated with the new molecular constants coincide exactly with frequencies measured. Finally, it is shown that there are pairs of transitions whose frequencies are close together. By measuring frequency differences of a number of such pairs it should be possible to further improve CO molecular constants. 相似文献
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In recent years in the fields of statistics and machine learning an increasing amount of so called local classification methods has been developed. Local approaches to classification are not new, but have lately become popular. Well-known examples are the $k$ nearest neighbors method and classification trees. However, in most publications on this topic the term “local” is used without further explanation of its particular meaning. Only little is known about the properties of local methods and the types of classification problems for which they may be beneficial. We explain the basic principles and introduce the most important variants of local methods. To our knowledge there are very few extensive studies in the literature that compare several types of local methods and global methods across many data sets. In order to assess their performance we conduct a benchmark study on real-world and synthetic tasks. We cluster data sets and considered learning algorithms with regard to the obtained performance structures and try to relate our theoretical considerations and intuitions to these results. We also address some general issues of benchmark studies and cover some pitfalls, extensions and improvements. 相似文献
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Z.M. Babar Wan Mohd Azizi Solachuddin JA Ichwan Qamar Uddin Ahmed Abul Kalam Azad Imranul Mawa 《Natural product research》2019,33(15):2266-2270
The current study provides a way of extraction for both active NSO and WSE from Nigella sativa seeds using 98% methanol. About 1?kg of ground seeds was macerated by 1:2.5 w/v (g/mL) for 72?hours. After rotary evaporation and 7 days of continuous drying and chilling at 50 and 4?°C, NSO and WSE were obtained at the same instant. Solubility tests of 24 solvents and 11 thin layer chromatographic analyses while 2, 2-diphenyl-1-picrylhydrazyl free radical scavenging assay of NSO (73.66) , WSE (33.32) and NSO?+?WSE (78.22) against ascorbic acid (IC50?=?4.28?mg/mL) was performed. WSE was found to be highly soluble in water and 5% NaOH exhibiting the same Rf value of 0.95 for EtOH:DMSO (9:1) against the honey. WSE has revealed more than twofold higher anti-oxidant activity than others. Formulation of WSE with Tualang honey may provide better targeted hydrophilic drug delivery systems. 相似文献
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