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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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G. F. D'alelio W. A. Fessler Y. Giza D. M. Feigl A. Chang M. Saha 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(1):159-185
Transamidation reactions of nonpolymerizing systems involving benzamides, phthalimides, arylsulfonamides, benzenedisulfonamides and -disulfonim-ides, and saccharins are described. The study includes reactions of both N-substituted and unsubstituted amides and imides with anilines and aniline hydrochlorides. An evaluation of the results of these reactions, aimed at establishing the optimum conditions for transamidations in polymerizing systems, is also presented. 相似文献
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Eller S Trettenbrein B Fessler M Haringer S Ruggenthaler M Gutmann R van der Veer WE Kopacka H Müller T Obendorf D Brüggeller P 《Dalton transactions (Cambridge, England : 2003)》2011,40(15):3815-3829
The bis(bidentate) phosphine cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane (dppcb) has been used for the synthesis of a series of novel heterodimetallic complexes starting from [Ru(bpy)(2)(dppcb)]X(2) (1; X = PF(6), SbF(6)), so-called dyads, showing surprising photochemical reactivity. They consist of [Ru(bpy)(2)](2+)"antenna" sites absorbing light combined with reactive square-planar metal centres. Thus, irradiating [Ru(bpy)(2)(dppcb)MCl(2)]X(2) (M = Pt, 2; Pd, 3; X = PF(6), SbF(6)) dissolved in CH(3)CN with visible light, produces the unique heterodimetallic compounds [Ru(bpy)(CH(3)CN)(2)(dppcb)MCl(2)]X(2) (M = Pt, 7; Pd, 8; X = PF(6), SbF(6)). In an analogous reaction the separable diastereoisomers (ΔΛ/ΛΔ)- and (ΔΔ/ΛΛ)-[Ru(bpy)(2)(dppcb)Os(bpy)(2)](PF(6))(4) (5/6) lead to [Ru(bpy)(CH(3)CN)(2)(dppcb)Os(bpy)(2)](PF(6))(4) (9), where only the RuP(2)N(4) moiety of 5/6 is photochemically reactive. By contrast, in the case of [Ru(bpy)(2)(dppcb)NiCl(2)]X(2) (4; X = PF(6), SbF(6)) no clean photoreaction is observed. Interestingly, this difference in photochemical behaviour is completely in line with the related photophysical parameters, where 2, 3, and 5/6, but not 4, show long-lived excited states at ambient temperature necessary for this type of photoreaction. Furthermore, the photochemical as well as the photophysical properties of 2-4 are also in accordance with their single crystal X-ray structures presented in this work. It seems likely that differences in "steric pressure" play a major role for these properties. The unique complexes 7-9 are also fully characterized by single-crystal X-ray structure analyses, clearly showing that the stretching vibration modes of the ligand CH(3)CN, present only in 7-9, cannot be directly influenced by "steric pressure". This has dramatic consequences for their photophysical parameters. The trans-[Ru(bpy)(CH(3)CN)(2)](2+) chromophore of 9 acts as efficient "antenna" for visible light-driven energy transfer to the Os-centred "trap" site, resulting in k(en) ≥ 2 × 10(9) s(-1) for the energy transfer. Since electron transfer is made possible by the use of this intervening energy transfer, in dyads like 2-4 highly reactive M(0) species (M = Pt, Pd, Ni) could be generated. These species are not stable in water and M(II) hydride intermediates are usually formed, further reacting with H(+) to give H(2). Thus, derivatives of 3, namely [M(bpy)(2)(dppcb)Pd(bpy)](PF(6))(4) (M = Os, Ru) dissolved in 1:1 (v/v) H(2)O-CH(3)CN produce H(2) during photolysis with visible light. 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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The accuracy of measuring voxel intensity changes between stimulus and rest images in fMRI echo-planar imaging (EPI) data is severely degraded in the presence of head motion. In addition, EPI is sensitive to susceptibility-induced geometric distortions. Head motion causes image shifts and associated field map changes that induce different geometric distortion at different time points. Conventionally, geometric distortion is "corrected" with a static field map independently of image registration. That approach ignores all field map changes induced by head motion. This work evaluates the improved motion correction capability of mapping slice to volume with concurrent iterative field corrected reconstruction using updated field maps derived from an initial static field map that has been spatially transformed and resampled. It accounts for motion-induced field map changes for translational and in-plane rotation motion. The results from simulated EPI time series data, in which motion, image intensity and activation ground truths are available, show improved accuracy in image registration, field corrected image reconstruction and activation detection. 相似文献