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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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R.-D. Herzberg N. Amzal J.E. Bastin F. Becker P.M.T. Brew P.A. Butler A.J.C. Chewter J.F.C. Cocks O. Dorvaux K. Eskola J. Gerl P.T. Greenlees N.J. Hammond K. Hauschild K. Helariutta F. Heßberger M. Houry A. Hürstel R.D. Humphreys G.D. Jones P.M. Jones R. Julin S. Juutinen H. Kankaanpää H. Kettunen T.L. Khoo W. Korten P. Kuusiniemi Y. Le Coz M. Leino A.P. Leppänen C.J. Lister R. Lucas M. Muikku P. Nieminen R.D. Page T. Page P. Rahkila P. Reiter Ch. Schlegel C. Scholey G. Sletten O. Stezowski Ch. Theisen W.H. Trzaska J. Uusitalo H.J. Wollersheim 《The European Physical Journal A - Hadrons and Nuclei》2002,15(1-2):205-208
In-beam conversion electron spectroscopy experiments have been performed on the transfermium nuclei 253, 254No using the conversion electron spectrometer SACRED in nearly collinear geometry in conjunction with the gas-filled separator
RITU at the University of Jyv?skyl?. The experimental setup is discussed and the spectra are compared to Monte Carlo simulations.
The implications for the ground-state configuration of 253No are discussed.
Received: 21 March 2002 / Accepted: 16 May 2002 / Published online: 31 October 2002
RID="a"
ID="a"e-mail: rdh@ns.ph.liv.ac.uk
RID="b"
ID="b"Present address: GANIL, F-14021 Caen, France.
RID="c"
ID="c"Permanent address: IReS Strasbourg, IN2P3-CNRS, F-67037-Strasbourg, France.
RID="d"
ID="d"Present address: CEA/DIF DCRE/SDE/LDN F-91680 Bruyeres-le-Chatel.
RID="e"
ID="e"Present address: Daresbury Laboratory, Daresbury WA4 4AD, UK.
RID="f"
ID="f"Permanent address: IPN Lyon, IN2P3-CNRS, F-69037 Lyon, France. 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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Optical fields with scale- and shape-invariant transverse intensity profiles consisting of a prescribed distribution of bright spots are introduced. Approximations of such fields are demonstrated by means of binary annular-aperture diffractive elements. 相似文献
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Prof. Lorenzo Franco Prof. Abdirisak Ahmed Isse Prof. Antonio Barbon Prof. Lina Altomare MSc. Viivi Hyppönen Dr. Jessica Rosa Dr. Venla Olsson Prof. Mikko Kettunen Prof. Lucio Melone 《Chemphyschem》2023,24(19):e202300100
This paper reports the synthesis, characterization and in vivo application of water-soluble supramolecular contrast agents (Mw: 5–5.6 kDa) for MRI obtained from β-cyclodextrin functionalized with different kinds of nitroxide radicals, both with piperidine structure ( CD2 and CD3 ) and with pyrrolidine structure ( CD4 and CD5 ). As to the stability of the radicals in presence of ascorbic acid, CD4 and CD5 have low second order kinetic constants (≤0.05 M−1 s−1) compared to CD2 (3.5 M−1 s−1) and CD3 (0.73 M−1 s−1). Relaxivity (r1) measurements on compounds CD3 - CD5 were carried out at different magnetic field strength (0.7, 3, 7 and 9.4 T). At 0.7 T, r1 values comprised between 1.5 mM−1 s−1 and 1.9 mM−1 s−1 were found while a significant reduction was observed at higher fields (r1≈0.6-0.9 mM−1 s−1 at 9.4 T). Tests in vitro on HEK293 human embryonic kidney cells, L929 mouse fibroblasts and U87 glioblastoma cells indicated that all compounds were non-cytotoxic at concentrations below 1 μmol mL−1. MRI in vivo was carried out at 9.4 T on glioma-bearing rats using the compounds CD3 - CD5 . The experiments showed a good lowering of T1 relaxation in tumor with a retention of the contrast for at least 60 mins confirming improved stability also in vivo conditions. 相似文献