The reaction pattern of norbornene with excited state carbonyl compounds: Photochemical preparations of norbornene derivatives

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 In other solvents, the radical chain addition of solvent dominated the photoreaction, and superseded the cycloaddition, to give excellent to good yields of adducts to norbornene.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.     

N_2和O_2纯转动拉曼光谱(PRRS)的温度特性

计算了N2 和O2 的PRRS ,讨论了其温度特性。提出通过测量N2 和O2 的PRRS计算大气温度的方法。     

The Assessment of Reservation Prices of an Intermediate R&D Result and Patent Reward Under Oligopolistic Competitive Behaviour

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.     

Efficient synthesis of an aldehyde‐capped polythiophene containing fluorinated electron‐withdrawing groups

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     

Interfacial structure and electrical properties of LaAlO3 gate dielectric films on Si by metalorganic chemical vapor deposition

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     

一个推广的Hardy-Hilbert型不等式及其逆式

本文引入单参数λ及应用Beta函数,给一个Hardy-Hilbert型不等式以具有最佳常数因子的推广,作为应用,给出了它的逆向形式．     

激光打孔对氮化铝绝缘性能的影响

氮化铝陶瓷具有优良的绝缘和导热性能,是传导冷却超导电力装置绝缘与导热连接件的首选,激光切割是对其进行加工的最有效方法,但激光切割可能对其绝缘性能产生影响,进而影响超导电力装置的安全运行。基于此,通过对激光打孔前后氮化铝基片孔周区域绝缘电阻的测量、金相结构和扫描电镜成分的比较,分析了激光打孔对氮化铝绝缘性能的影响,并总结了选用氮化铝基片作为超导电力装置电流引线的绝缘与导热垫片应注意的问题。     

氮化铝薄膜的光学性能

分别使用X衍射仪和紫外（190 nm～800 nm）分光光度仪,测量了用分子束外延法生长在SiC（001）基底面上的AIN薄膜的X衍射、透射谱和不同温度下的吸收谱.X衍射表明:实验所用的AIN薄膜在c-轴存在应变和应力，该应变和应力主要是由于AIN的晶格常量与基底SiC的晶格常量不匹配所致.透射谱表明:AIN薄膜的禁带宽度大约为6.2eV；而其对应的吸收谱在6.2eV处存在一个明显的台阶,此台阶被认为是AIN薄膜中的带边自由激子吸收所产生,忽略激子的结合能(与禁带宽度相比),则该值就对应为AIN的禁带宽度.而其对应的不同温度下（10 k～293 k）的吸收谱的谱线的形状和位置无明显的变化表明:温度对AIN薄膜的禁带宽度亦无明显的影响，这主要是由于在AIN薄膜中存在着应力所致.     

Transverse Effects in Slow Light Propagation

The effect of finite control beam on the transverse spatial profile of the slow light propagation in an electromagnetically induced transparency medium is studied. From the second-order wave equation and linear response of an EIT medium to the signal field, we find it is possible to produce an effective waveguide for the signal field. The existence and properties of a set of localized, stationary transverse modes are demonstrated. Especially, by carefully manipulating the profile of the control beam, we can realize single-mode propagation for the signal field, which may be important for potential applications.