钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

与芳香胺相比,芳香硝基化合物具有廉价易得、官能团兼容性好等优点,作为氮源在下游含氮化学品合成中具有广泛的应用.目前烯烃羰化酰胺化反应绝大多数以胺类化合物为氮源,其中直链和支链酰胺产物的选择性主要是通过具有特定电子和位阻特性的配体调控实现.已报道的芳香硝基化合物的还原酰胺化反应研究中,需要外加还原剂或者利用金属羰基化合物Mo(CO)6释放的CO为羰基源和还原剂.本文发展了一种毋须外加还原剂的钯催化芳香硝基化合物与烯烃的还原羰化酰胺化反应新方法.研究发现,钯金属催化剂(特别是离子型)的抗衡阴离子是还原羰化酰胺化反应中化学选择性和羰化区域选择性的关键因素.抗衡阴离子为氯离子、硼酸为助剂时,最优钯前驱物K2PdCl4的产物主要为支链酰胺,此时不同的膦配体并不能调控其区域选择性,这与胺的烯烃酰胺化反应可以通过配体调控羰化的区域选择性表现出明显的不同.含氮中间体原位捕捉、硝基化合物还原下游可能中间体对照实验等研究表明,芳香硝基化合物在以一氧化碳为还原剂的催化还原体系下被完全脱氧还原为氮烯(Ar-N:),再经过烯酰胺中间体进一步烯键还原得到相应的支链酰胺;当离子型钯前驱物的抗衡阴离子配位性较弱时,最优钯前驱物为Pd(CH3CN)4(OTf)2时,以直链酰胺为主要产物,此时不同的膦配体可以调控酰胺化的区域选择性.同样的机理研究表明,在该催化剂体系下芳香硝基化合物首先被还原为芳基胺,然后再发生与现有报道类似的胺类化合物的烯烃羰化酰胺化反应.这两个催化反应体系都表现出了较好的底物适用性,并且可以高效地应用于除草剂(敌稗)的一步合成.本文为以硝基化合物为起始氮源,通过催化控制生成特定含氮中间体,从而可控合成不同的含氮化学品提供了一条新思路.     

Copyright protection in digital museum based on digital holography and discrete wavelet transform

A new method to protect the copyright of digital museum based on digital holography is proposed. The Fresnel hologram of watermark image is embedded in the object to be protected through discrete wavelet transform （DWT）. After the watermark detection, the copyright information appears in the reconstructed hologram. With the higher redundancy feature in the hologram, the proposed technique can actually survive several kinds of image processing. Experimental results prove that the presented method has good robustness in image protection.     

磷化氢与烯烃反应的原位NMR谱研究

本文应用加压原位(in-situ)核磁共振技术,在反应温度70～75℃,压力1.0～2.0MPa,氘代苯为溶剂,偶氮二异丁腈(AIBN)为引发剂的条件下探索了磷化氢与丙烯腈,4-乙烯基吡啶,烯丙基胺,丙烯酰胺,氨基吡啉和N-乙烯基咔唑的自由基加成反应,结果表明除氨基吡啉之外的其它五种含氮化合物均能与磷化氢发生反应,从而找到合成含氮有机膦的良好路线。     

全国发光物理基础理论讨论会在合肥召开

受中国物理学会发光分科学会的委托,中国科技大学物理系于今年四月下旬在合肥主办了这个基础理论讨论会。一方面,作为学会的经常性学术活动之一,其目的在于从理论和实际的结合上同时促进我国发光实验研究和理论研究的提高和发展;另一方面,由于序列性(三年一度)的国际发光会议将于1987年在北京召开(ICL’87),这次讨论     

Improvement of Security of Three-Party Quantum Secure Direct Communication Based on GHZ States

A protocol for three-party quantum secure direct communication based on Greenberger-Horne-Zeilinger （GHZ） states was recently proposed by 3in et al. [Phys. Lett. A 354 （2006） 67] By analysing the protocol we find some security loopholes, e.g. one bit of secret messages of a party （Alice in the original paper） can always be leaked straight to the public without any eavesdropping. These problems suggested previously are discussed and possible solutions are presented to improve the security of the original protocol.     

Experimental Study on Electrostatic with Two Guiding of Supersonic D20 Molecular Beam Charged Wires

We demonstrate the guiding of a supersonic heavy-water （D2O） molecular beam using a hollow electrostatic field generated by the combination of two parallel charged-wires and two grounded metal-plates, and report some new and preliminary experimental results. In the experiment, we detect the guiding signals by using the method of time-of-flight mass spectrum and study the dependence of the relative transmission of the beam guide on the guiding voltage. Our study shows that the relative transmission of the beam guide is increased linearly with increasing guiding voltage Vguid, and the number of the guided D20 molecules is at least increased by 89.4% when the guiding voltage is ＋20.0k V. Finally, some potential applications of our guiding scheme in the molecule optics are briefly discussed.     

Hydrogen Passivation Effect on Enhanced Luminescence from Nanocrystalline Si/SiO2 Multilayers

Nanocrystalline Si/SiO2 multilayers are prepared by thermally annealing amorphous Si/SiO2 stacked structures. The photoluminescence intensity is obviously enhanced after hydrogen passivation at various temperatures. It is suggested that the hydrogen trapping and detrapping processes at different temperatures strongly influence the passivation effect. Direct experimental evidence is given by electron spin resonance spectra that hydrogen effectively reduces the nonradiative defect states existing in the Si nanocrystas/SiO2 system which enhances the radiative recombination probability. The luminescence characteristic shows its stability after hydrogen passivation even after aging eight months.     

利用宇宙线对BESⅢ量能器CsⅠ（Tl）晶体探测器单元的测量

利用宇宙射线进行探测器模型的性能测试是高能物理普遍采用的方法，其中最重要的步骤之一就是确定宇宙线入射的准确位置和径迹．多数采用丝室探测器来进行宇宙线的精确定位，需要很高的造价和复杂的电子学系统．本文介绍一种简单的定位方法，采用塑料闪烁体条加波移剂光纤编码读出的方式，可以实现精度为1cm的定位．据此建立了一套实验装置，对BESⅢ电磁量能器CsⅠ（Tl）晶体探测器单元的光输出强度和不均匀性进行了测量．     

应力导致InAs/In0.15Ga0.85As量子点结构中 In0.15Ga0.85As阱层的合金分解效应研究

利用固源分子束外延技术,在In0.15Ga0.85As/GaAs量子阱生长了两个InAs/In0.15Ga0.85As量子点(DWELL)样品.通过改变其中一个InAs DWELL样品中的In0.15Ga0.85As阱层的厚度和生长温度,获得了量子点尺寸增大而且尺寸分布更均匀的结果.结合光致发光光谱(PL)和压电调制光谱(PzR)实验结果,发现该样品量子点的光学性质也同时得到了极大的优化.基于有效质量近似的数值计算结果表明:量子点后生长过程中应力导致In0.15Ga0.85As阱层合金分解机理是导致量子点尺寸和光学性质得到优化的主要原因.