基于双重碳氢活化的γ,δ-不饱和酰胺与炔烃的脱氢环化反应

吡啶酮是一类重要的含氮杂环骨架,广泛存在于天然产物和药物分子中,是重要的化学转化中间体,其合成与修饰是现代医药学及化学领域的研究热点之一。杂环母核的官能团化修饰是该类化合物较为常见的衍生方式,但要求特定位点的反应基团预组装。相较而言,两个片段分子的直接偶联环化,是更为直接且具备较高实用性的合成类似杂环分子库的方式。近年来,过渡金属催化的丙烯酰胺与炔烃的氧化偶联制备吡啶酮类化合物取得了长足进展,关键活化步骤为过金属催化剂对酰胺β位sp2碳氢键的活化。然而,通过对更加易得的烷基酰胺进行sp3碳氢键活化制备杂环骨架依然具有较高的挑战性。其原因主要在于较低的α-酸性使得酰胺的脱氢反应变得异常困难。本课题组最近报道了温和条件下,铱催化的酰胺、酸及酮的空气脱氢反应。反应中产生的烯丙基-铱中间体被认为提高了酰胺的α-酸性,从而加速了脱氢过程。在此基础上,我们报道一种铑(Ⅲ)催化的γ,δ-不饱和酰胺与炔烃类化合物的脱氢环化新方法,制备一系列多取代的吡啶酮类化合物。催化循环历经酰胺导向铑(Ⅲ)对底物β位点的sp3碳氢活化,进而脱氢生成共轭的双烯酰胺中间体,随后酰胺基团再次导向铑(Ⅲ)对β位的sp2碳氢活化,进而与炔烃进行插入,环化获得吡啶酮。该反应对各种官能团具有较好的容忍性。γ-烯基结构不但促进第一步的酰胺脱氢,而且是杂环产物后修饰的重要位点。机理实验表明双烯酰胺的确为反应中间体之一。核磁实验显示酰胺脱氢迅速,而控制实验则表明炔烃的插入过程的选择性与其电性有密切的关系,有可能参与了该反应的速控步。     

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对准光学谐振腔诊断等离子体的传统诊断方法进行了改进,提出一种可用于诊断瞬态等离子体的实时诊断方法。通过实验证明,矢量网络分析仪点频测试(CW Sweep)对信号相位变化的测量速度足够快,可以跟上等离子体鞘套和尾迹的变化速度,因此利用该方法诊断等离子体鞘套和尾迹是可行的。通过对诊断系统性能的评估,表明诊断装置具有较高的实时性,对等离子体电子浓度有较宽的测量范围,测量范围可达10-1~1015m-3。     

行波管内不连续性的简易模型分析

 根据行波管内微波信号在输能装置和切断衰减器处两个不连续性之间来回反射的物理现象，建立行波管输出段的简易网络串模型，并对行波管输出段传输特性参数的幅频特性、相频特性进行计算分析。结果表明：输能装置和切断衰减器的不连续性是造成幅相一致性行波管相位不可补偿的重要因素之一。     

High quality PdTe_2 thin films grown by molecular beam epitaxy

PdTe_2,a member of layered transition metal dichalcogenides(TMDs),has aroused significant research interest due to the coexistence of superconductivity and type-II Dirac fermions.It provides a promising platform to explore the interplay between superconducting quasiparticles and Dirac fermions.Moreover,PdTe_2 has also been used as a substrate for monolayer antimonene growth.Here in this paper,we report the epitaxial growth of high quality PdTe_2 films on bilayer graphene/SiC(0001)by molecular beam epitaxy(MBE).Atomically thin films are characterized by scanning tunneling microscopy(STM),X-ray photoemission spectroscopy(XPS),low-energy electron diffraction(LEED),and Raman spectroscopy.The band structure of 6-layer PdTe_2 film is measured by angle-resolved photoemission spectroscopy(ARPES).Moreover,our air exposure experiments show excellent chemical stability of epitaxial PdTe_2 film.High-quality PdTe_2 films provide opportunities to build antimonene/PdTe_2 heterostructure in ultrahigh vacuum for future applications in electronic and optoelectronic nanodevices.     

Fe(Ⅲ)-H2O2-丽春红-1,10-菲罗啉体系催化动力学光度法测定痕量铁

基于pH4.0的弱酸性介质中铁离于对过氧化氢氧化丽春红的褪色反应的催化作用,提出了催化动力学光度法测定痕量铁的新方法.研究了该方法的适宜反应条件,方法的检出限为7.9×10-7g·L-1,线性范围为0～1.5μg/25ml,方法用于水中痕量铁的测定,结果满意.     

基于移动Agent的智能交易安全风险控制机制研究

在移动网络交易中,交易双方的互信是网络交易能够顺利进行的前提和关键,实体间的信任度量涉及到交易额、交易时间、消费实体个人相关信息及其对信任的风险态度等因素,通常难以准确地进行量化计算.为探明这种互信关系的本质特点,基于多Agent系统协同理论,提出了基于移动Agent的动态互信计算模型,实现了对信任的定性与定量的转换;...     

Edge-and strain-induced band bending in bilayer-monolayer Pb_2Se_3 heterostructures

By using scanning tunneling microscope/microscopy(STM/STS), we reveal the detailed electronic structures around the sharp edges and strained terraces of lateral monolayer-bilayer Pd₂Se₃ heterostructures. We find that the edges of such heterostructures are well-defined zigzag type. Band bending and alignment are observed across the zigzag edge, forming a monolayer-bilayer heterojunction. In addition, an n-type band bending is induced by strain on a confined bilayer Pd₂Se₃ terrace. These results provide effective toolsets to tune the band structures in Pd₂Se₃-based heterostructures and devices.     

The 50 nm-thick yttrium iron garnet films with perpendicular magnetic anisotropy

Yttrium iron garnet (YIG) films possessing both perpendicular magnetic anisotropy (PMA) and low damping would serve as ideal candidates for high-speed energy-efficient spintronic and magnonic devices. However, it is still challenging to achieve PMA in YIG films thicker than 20 nm, which is a major bottleneck for their development. In this work, we demonstrate that this problem can be solved by using substrates with moderate lattice mismatch with YIG so as to suppress the excessive strain-induced stress release as increasing the YIG thickness. After carefully optimizing the growth and annealing conditions, we have achieved out-of-plane spontaneous magnetization in YIG films grown on sGGG substrates, even when they are as thick as 50 nm. Furthermore, ferromagnetic resonance and spin pumping induced inverse spin Hall effect measurements further verify the good spin transparency at the surface of our YIG films.     

跳扩散模型在保险公司投资策略中的应用

利用随机控制理论、HJB方程、最优决策理论等数学工具,研究保险公司保费收入的投资策略问题.假定保险公司盈余过程服从跳扩散过程,保险公司将(1-q)比例的资金投向金融资产,比例q向其它保险公司购买保险(再保险).在目标函数为终止时刻财富期望效用最大的情况下构建一个包含q的HJB方程,基于常利率和随机利率,分别验证了q的存在性,并给出了最优投资策略的显示解和各重要参数对最优投资策略的影响.     

High quality sub-monolayer,monolayer, and bilayer graphene on Ru（0001）

High quality sub-monolayer, monolayer, and bilayer graphene were grown on Ru(0001). For the sub-monolayer graphene, the size of graphene islands with zigzag edges can be controlled by the dose of ethylene exposure. By increasing the dose of ethylene to 100 Langmuir at a high substrate temperature(800℃), high quality single-crystalline monolayer graphene was synthesized on Ru(0001). High quality bilayer graphene was formed by further increasing the dose of ethylene while reducing the cooling rate to 5℃/min. Raman spectroscopy revealed the vibrational states of graphene, G and 2D peaks appeared only in the bilayer graphene, which demonstrates that it behaves as the intrinsic graphene. Our present work affords methods to produce high quality sub-monolayer, monolayer, and bilayer graphene, both for basic research and applications.