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Thermal cis, trans geometrical isomerization theoretically involves a 90° twisted, singlet diradical-like transition state which may serve as a base for the examination of structural perturbations. Although thermal rearrangement of hexa-1, trans-3,5-triene (and all-trans octa-2,4,6-triene) to the cis isomer cannot be followed directly owing to subsequent cyclization and 1,5 hydrogen shifts, activation parameters for disappearance have been determined. Experimental complications and mechanistic uncertainties which make interpretation difficult are removed in the bicyclic hexatriene, cyclopentenylidenecyclopentene. These geometrical isomers undergo uncomplicated thermal cis, trans isomerization in vessels of lead-potash glass: log k1 = 12·03±0·32?41·7±0·8/(0·004575Tabs). Extraction of a value for allylic delocalization energy from the behavior of hexa-1, trans-3,5-triene [log k1 = 12·91 ± 0·47?44·3±1·2/(0·004575 Tabs)] requires corrections of the Dewar-Schmeising type for changes in hybridization of the σ bonds. Depending on whether ethylene or trans-butene is taken as standard, values of 12·2 and 13·1 kcal/mol are obtained (estimated uncertainty ± 2 kcal/mol). 相似文献
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F. J. Doering 《Reaction Kinetics and Catalysis Letters》1989,39(1):1-6
A preliminary attempt to modify a molybdena-silica for ethylene homologation was performed by adding copper. Ethylene homologation (3C2H42C3H6) was enhanced 2.5 times on copper doped catalyst. Contrary to this, ethylene metathesis (C2H4–12C2+C2H4–13C22C2H4–13C1) was suppressed in the presence of copper. The selectivity of the homologation to metathesis was increased 7.5 times.
- , (3C2H42C3H6), . 2,5 , (C2H4–12C2+C2H4–13C22C2H4–13C1) . 7,5 .相似文献
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K. Doering 《Talanta》1974,21(4):312-314
A rapid method is described for the determination of thorium and lanthanum in non-silicate glasses. It is suitable for routine use in a works laboratory. The samples are dissolved in nitric acid. The thorium content is calculated from the measured heat of precipitation of thorium iodate, and the lanthanum content by difference from the heat of precipitation of both thorium and lanthanum oxalates together. The apparatus is calibrated by using standard solutions of the two metal ions. The standard deviations for the middle of the range (around 250 mg of the oxides) were 3·1 mg for ThO2 and 1·7 mg for La2O3. An analysis takes about 1·5 hr. 相似文献
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Infinite Prandtl Number Convection 总被引:1,自引:0,他引:1
We prove an inequality of the type NCR
1/3(1+log+
R)2/3 for the Nusselt number N in terms of the Rayleigh number R for the equations describing three-dimensional Rayleigh–Bénard convection in the limit of infinite Prandtl number. 相似文献
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Lennard?P?NilesEmail author Kristen?J?Armstrong Lyda?M?Rincón Castro Chung?V?Dao Rohita?Sharma Catherine?R?McMillan Laurie?C?Doering David?L?Kirkham 《BMC neuroscience》2004,5(1):41
Background
In order to optimize the potential benefits of neural stem cell (NSC) transplantation for the treatment of neurodegenerative disorders, it is necessary to understand their biological characteristics. Although neurotrophin transduction strategies are promising, alternative approaches such as the modulation of intrinsic neurotrophin expression by NSCs, could also be beneficial. Therefore, utilizing the C17.2 neural stem cell line, we have examined the expression of selected neurotrophic factors under different in vitro conditions. In view of recent evidence suggesting a role for the pineal hormone melatonin in vertebrate development, it was also of interest to determine whether its G protein-coupled MT1 and MT2 receptors are expressed in NSCs. 相似文献10.