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81.
We established that acetylacetone and acetone photolytically sensitize norbornene to undergo an efficient radical addition
of solvent (ranging from hexane, cyclic ethers, haloalkanes, acetone, alcohols and acetonitrile) across the double bond. In
view of its synthetic applicability, sensitized photoreactions of norbornene were reviewed and their mechanisms were compared.
Photolysis of acetylacetone in the presence of norbornene in hexane induced i) acetylacetone to cycloadd to norbornene giving
the expected 1,5-diketone, and ii) sensitization by triplet excited acetylacetone to generate reactive norbornene, which underwent
dimerization as well as the addition of a solvent molecule by radical chain processes. In other solvents, the radical chain
addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts
to norbornene. While the excited species of acetylacetone for the sensitization was deduced to be its spectroscopic triplet
excited state, that for the cycloaddition should involve a different one which may be a twisted triplet acetylacetone; sensitization
experiments showed that the cycloaddition did not occur from the spectroscopic triplet state. Triplet excited acetone sensitized
norbornene to undergo the same solvent addition more efficiently and cleanly than acetylacetone did. In view of various conflicts
existing in the proposed energy transfer mechanism, the sensitized norbornene reactions were rationalized with electron transfer
and a cation radical chain mechanism. 相似文献
82.
83.
PbI_2可以单独形成玻璃。PbI_2-PbBr_2-KCl三元系统玻璃具有良好的玻璃形成能力。通过恰当的热处理,不仅可获得透红外性能与原始玻璃一致的微晶玻璃,同时还可克服自发析晶倾向和大幅度地提高玻璃的显微硬度。以此三元系统为基础,有望开发出一类具有实用前景的透红外玻璃材料。 相似文献
84.
85.
采用分枝理论推导非线性系统两变量P和PI控制下的分枝特性,所导得的几个定理阐明了简单分枝点和Hopf分枝点的位置和性质。一个简化精馏塔模型用于演示这一过程,展示出精馏塔系统在闭环时,可能出现多态和极限环。 相似文献
86.
One of the shortcomings of R&D evaluation is a lack of emphasis on analytical assessment of the value of an on-going R&D project. This paper addresses the problem concerning the distributive aspect of access to superior knowledge. Decision tree analysis and probability models appear to be appropriate tools for assessing the values of an intermediate result and patent reward of a firm's R&D decision in an environment of perfect information and oligopolistic competition. The assessed values are used as minimum prices acceptable to the firm when the knowledge is disseminated to the public. This paper will attempt to resolve this problem through the determination of the appropriate values of the reservation price of the first-stage invention in terms of the final reward and of a patent reward for which the inventor is willing to apply. 相似文献
87.
介绍了国内第一个综采放顶煤开采矿区铁路线下压煤试验面的成功经验,总结了试采中对铁路所采取的各种分析和维护措施,分析了该采煤方法下的地在移动和变形特点,为我国“三下”采煤领域提供了具有特色的成功实例。 相似文献
88.
89.
To incorporate an acceptor type polythiophene segment onto a supramolecular block copolymer for potential light harvesting applications, effective synthetic routes for the end‐functionalized and acceptor‐substituted polythiophenes are critical. The Ullmann coupling reaction can be utilized to obtain electron‐deficient polythiophenes and to attach terminal thiophene units that carry functional groups. In this article, the reactions involving a 2,5‐dibromothiophene monomer containing an electron‐withdrawing fluorinated ester and 5‐bromo‐2‐thiophenecarboxaldehyde (the end‐capper) were studied in detail. It was found that the Ullmann coupling reaction of the dibromide is very fast (completed in a few minutes) and the terminal bromine group does not survive long under the reaction condition. These findings lead to the development of an effective procedure for aldehyde end‐capping of electron‐deficient polythiophenes. Polymers with molecular weights around 4000 Da are routinely obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 41–47, 2007 相似文献
90.
Q.-Y. Shao A.-D. Li J.-B. Cheng H.-Q. Ling D. Wu Z.-G. Liu N.-B. Ming C. Wang H.-W. Zhou B.-Y. Nguyen 《Applied Physics A: Materials Science & Processing》2005,81(6):1181-1185
LaAlO3 (LAO) gate dielectric films were deposited on Si substrates by low-pressure metalorganic chemical vapor deposition. The interfacial structure and composition distribution were investigated by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), secondary-ion mass spectroscopy (SIMS), and Auger-electron spectroscopy (AES). HRTEM confirms that there exists an interfacial layer between LAO and Si in most samples. AES, SIMS, and XPS analyses indicate that the interfacial layer is compositionally graded La–Al silicate and the Al element is severely deficient close to the Si surface. Electrical properties of LAO films were evaluated. No evident difference in electrical properties between samples with and without native SiO2 layers was observed. The electrical properties are discussed in terms of LAO growth mechanisms, in relation to the interfacial structure. PACS 73.40.Qv; 81.15.Gh; 77.55.+f; 68.35.-p 相似文献