A domino desulfitative coupling and decarboxylative coupling of 3, 4-dihydropyrimidine-2-thiones with copper(I) carboxylates

A novel and general carbon-nitrogen and carbon-carbon cross-coupling reaction between 3,4-dihydropyrimidine-2-thiones and copper(I) carboxylates were performed in the presence of palladium acetate. The copper(I) carboxylates act not only as desulfurative reagents but also as sources of carbon nucleophiles. A wide array of highly substituted and functionalized pyrimidines scaffolds were synthesized in good yields.     

二维光子晶体全光异或门的设计及研究

分析了二维光子晶体马赫-曾德尔干涉仪的传输特性，将二维光子晶体波导、环形腔和马赫-曾德尔干涉仪有效结合，提出了一种基于二维光子晶体马赫-曾德尔干涉仪的异或门设计。用平面波展开法分析二维光子晶体能带结构，并用时域有限差分法验证光信号在该器件中的电场稳态分布。结果表明，该结构能够实现异或逻辑，且具有高逻辑对比度7.88 dB，快速响应周期0.388 ps和高传输速率7.87 Tbit/s；并且该器件结构尺寸仅为13 μm×14 μm，易于集成。该异或逻辑结构中引入了二维光子晶体马赫-曾德尔干涉仪，使得光子晶体逻辑门结构的设计更加多样，并为二维光子晶体半加器与全加器的设计提供了基础，具有重要的研究意义。     

4'-磺酰腙苯并-15-冠-5的合成及阴离子识别研究

由苯并-15-冠-5经磺酰化、肼解两步合成了4’-磺酰肼苯并-15-冠-5(2).后者与芳香醛在室温下发生缩合制得了一系列未见文献报道的冠醚化磺酰腙类化合物3a～3h,产物经元素分析,IR,1H NMR,13C NMR,MS确证了其结构.利用紫外-可见吸收光谱考查了其对不同阴离子的识别作用,结果表明,化合物3d,3e,3h对碱性较强的阴离子有较强的选择性识别作用.     

离子液体支载稀土催化剂催化 2,2-二甲基-三亚甲基碳酸酯均聚及其与ε-己内酯的共聚

首次合成了离子液体支载稀土催化剂,并探讨了其催化2,2-二甲基-三亚甲基碳酸酯(DTC)均聚及其与ε-己内酯(ε-CL)的共聚,结果表明该新型催化剂能有效地催化DTC的均聚及其与ε-CL的共聚.研究了不同稀土以及加料顺序等反应条件对聚合的影响,发现轻稀土的催化活性比重稀土高,其中离子液体支载La催化剂的催化活性最高,而通过控制不同的加料顺序可以制备DTC和ε-CL的无规及嵌段共聚物.对共聚物结构进行了表征.     

高分子填料在生物法处理废水中的应用进展

对生物法处理废水用的高分子填料进行了综述。首先,从无机高分子填料、有机高分子填料两方面介绍了其应用特点及对废水中有机物的作用机理和去除效果;其次,介绍了新型生物填料,主要从生物亲和亲水磁性填料和酶促生物填料两方面介绍其在废水处理中的应用。     

开链冠醚Schiff碱-稀土配合物的合成、表征及近红外发光光谱研究

合成了3个新型开链冠醚Schiff碱-稀土离子三元配合物RE(H2L)(Mq)(NO3)3,其中RE=Nd3 ,Er3 ,Yb3 ,配体H2L=N,N-双(邻羟苯亚甲基)-3,6-二氧杂-1,8-二氨基辛烷,Mq为8-羟基喹哪啶.采用元素分析、红外光谱(IR)、紫外-可见吸收光谱(UV-vis)、热重-差热分析(TG-DTG)等手段对配合物的组成结构进行了表征.测定了3种新型结构稀土三元配合物在不同温度(77 K和300 K)时的近红外发光光谱.     

Quantum chemical study on the abstraction reaction of alkylidenegermylene with oxirane and thiirane

The mechanisms of theion reaction of alkylidenegermylene with oxirane and thiirane have been characterized detail in using density functional theory, as well as ab initio method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies were calculated by CCSD(T)/6-311G(d)//B3LYP/6-311G(d,p) method for the involved conformations. The results show that the reaction pathways for both reactions consist of two ways: (1) the reactants can yield bent products (P1; P4) by syn-isomers; (2) the reactants can also yield three-membered products (P2; P5) by anti-isomers, which then further react with oxirane and thiirane to form the ultimate products (P3-1, P3-2; P6). Furthermore, a comparison with alkylidenecarbene, oxirane, and thiirane was done.     

Photocatalytic degradation of methylene blue on Fe3+-doped TiO2 nanoparticles under visible light irradiation

Fe³⁺-doped TiO₂ composite nanoparticles with different doping amounts were successfully synthesized using sol-gel method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and ultravioletvisible spectroscopy (UV-Vis) diffuse reflectance spectra (DRS). The photocatalytic degradation of methylene blue was used as a model reaction to evaluate the photocatalytic activity of Fe³⁺/TiO₂ nanoparticles under visible light irradiation. The influence of doping amount of Fe³⁺ (ω: 0.00%–3.00%) on photocatalytic activities of TiO₂ was investigated. Results show that the size of Fe³⁺/TiO₂ particles decreases with the increase of the amount of Fe³⁺ and their absorption spectra are broaden and absorption intensities are also increased. Doping Fe³⁺ can control the conversion of TiO₂ from anatase to rutile. The doping amount of Fe³⁺ remarkably affects the activity of the catalyst, and the optimum efficiency occurs at about the doping amount of 0.3%. The appropriate doping of Fe³⁺ can markedly increase the catalytic activity of TiO₂ under visible light irradiation. __________ Translated from Journal of Northwest Normal University (Natural Science), 2006, 42(6): 55–56 [译自: 西北师范大学学报(自然科学版)]     

Theoretical study of the reaction of Cu with OCS

The reactivity of Cu⁺ with OCS on both singlet and triplet potential energy surfaces (PES) has been investigated at the UB3LYP/6-311+G(d) level. The object of this investigation was the elucidation of the reaction mechanism. The calculated results indicated that both the C–S and C–O bond activations proceed via an insertion–elimination mechanism. Intersystem crossing between the singlet and triplet surfaces may occur along both the C–S and C–O bond activation branches. The ground states of CuS⁺ and CuO⁺ were found to be triplets, whereas CuCO⁺ and CuCS⁺ have singlet ground states. The C–S bond activation is energetically much more favorable than the C–O bond activation. All theoretical results are in line with early experiments.     

Structure, spin reorientation and M?ssbauer effect studies of Tb0.3Dy0.7(Fe1?xAlx)1.95 alloys

The effect of Al substitution for Fe on crystal structure, magnetostriction and spontaneous magnetostriction, anisotropy and spin reorientation of a series of polycrystalline Tb_0.3Dy_0.7(Fe_1−x Al_x)_1.95 alloys (x = 0, 0.05, 0.1, 0.15, 0.20, 0.25, 0.30, 0.35) at room temperature and 77 K was investigated systematically. It was found that the primary phase of Tb_0.3Dy_0.7(Fe_1−x Al_x)_1.95 is the MgCu₂-type cubic Laves phase structure when x < 0.4 and the lattice constant a of Tb_0.3Dy_0.7(Fe_1−x Al_x)_1.95 increases approximately and monotonically with the increase of x. The substitution of Al leads to the fact that the magnetostriction λ inceases slightly in a low magnetic field (H ⩽ 40 kA/m), but decreases sharply and is easily close to saturation in a high applied field as x increases, showing that a small amount of Al substitution is beneficial to a decrease in the magnetocrystalline anisotropy. It was also found that the spontaneous magnetostriction λ ₁₁₁ decreases greatly with x increasing. The analysis of the M?ssbauer spectra indicated that the easy magnetization direction in the {110} plane deviates slightly from the main axis of symmetry with the changes of composition and temperature, namely spin reorientation. A small amount of non-magnetic phase exists for x = 0.15 in Tb_0.3Dy_0.7(Fe_1−x Al_x)_1.95 alloys and the alloys become paramagnetic for x > 0.15 at room temperature, but at 77 K the alloys still remain magnetic phase even for x = 0.2. At room temperature and 77 K, the hyperfine field decreases and the isomer shifts increase with Al concentration increasing.