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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?1T?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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Experimental assessment of the thermal load induced by fast laser pulses on micro- and nanostructures through IR imaging is currently too slow and lacks the spatial resolution to be useful. In this paper, we introduce a method based on measuring the laser-induced yields of ions to compare the thermal loads on nanofabricated silicon structures, when exposed to nanosecond laser pulses. The laser fluences at which the ion yields of, for example, sodiated and potassiated peptides ions are equal for two different structures correspond to equivalent thermal loads. Using alkalinated peptides is a convenient choice because the corresponding ion intensities are easily measured up to the melting point of silicon. As an example, we compare the nanosecond laser heating of silicon nanopost arrays with diverse post diameters and periodicities. Assessment of the thermal load through ion yield measurements can also be used to verify model assumptions for heat transport regimes in nanostructures.  相似文献   
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We present a refinement of Ramsey numbers by considering graphs with a partial ordering on their vertices. This is a natural extension of the ordered Ramsey numbers. We formalize situations in which we can use arbitrary families of partially-ordered sets to form host graphs for Ramsey problems. We explore connections to well studied Turán-type problems in partially-ordered sets, particularly those in the Boolean lattice. We find a strong difference between Ramsey numbers on the Boolean lattice and ordered Ramsey numbers when the partial ordering on the graphs have large antichains.  相似文献   
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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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高聚合度Ⅱ-型聚磷酸铵的合成   总被引:3,自引:0,他引:3  
傅亚  陈君和  贾云  郭莉平 《合成化学》2005,13(6):610-613
用聚合反应-热处理两段工艺合成了高聚合度的聚磷酸铵(APP)阻燃材料,其结构经XRD,粒度及平均聚合度表征。优化反应条件为:磷酸氢二铵1mol,n(磷酸氢二铵):n(五氧化二磷):n(脲):1.0:1.0:0.3.干燥氨气氛下于290℃反应30min,再经250℃-280℃后处理100min-110min。APP的平均聚合度大于150,粒度小于50μm。  相似文献   
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