A quantum-chemical study on the Mannich reaction with polynitromethanes

According to the results of SCF-CNDO/2 computation, we propose employing the “ladder weighting summation” to define a G_e index which is used to measure the relative magnitude of the nucleophilicity of the relevant amine and pseudo acid components in a Mannich reaction. We also put forward an A_e index to measure the relative magnitude of the electrophilicity of methyleneamine cationic species in the same reaction. A combined use of both G_e and A_e indices is suggested to evaluate the feasibility of a Mannich reaction for the polynitromethanes and the stability of the products. These results are consistent with those conclusions drawn from “soft-hard acid-base theory”.     

Resonance problems for the p-Laplacian systems

Two existence theorems of the solutions are obtained for the p-Laplacian systems at resonance under a Landesman-Lazer-type condition by critical point theory.     

Reconsideration to the deactivation of TiO2 catalyst during simultaneous photocatalytic reduction of Cr(VI) and oxidation of salicylic acid

Photocatalytic reduction/oxidation and deactivation of TiO₂ photocatalyst was investigated in the systems composed of Cr(VI) and salicylic acid. The selection of analysis method of Cr(IV) was very important to the monitoring of the photocatalytic process. It was found that as previously reported, serious deactivation of TiO₂ catalyst in the simultaneous photo-reduction of Cr(VI) and oxidation of salicylic acid was incorrectly observed if the Cr(VI) level was analyzed by directly monitoring the absorbance at characteristic 348 nm band of Cr(VI), because it seriously suffers from the interferences of the intermediates generated from the degradation of salicylic acid. By using an appropriate method to determine the Cr(VI) concentration, it was observed that all the added Cr(VI) could be reduced, not showing marked deactivation of the photocatalyst. A long time photocatalytic reduction of Cr(VI) under UV illumination induced the deposition of Cr(III) species on the surface of TiO₂ particles, which could cause a mild deactivation of the photocatalyst. However, the accompanied oxidation of salicylic acid was demonstrated to depress the deactivation effect of the deposited Cr(III) species on the photocatalytic activity of the TiO₂ photocatalyst.     

Palladium-catalyzed regiocontrolled internal heteroarylation of electron-rich olefins with heteroaryl halides

A highly efficient palladium-catalyzed Heck coupling reaction of heteroaryl halides with electron-rich vinyl ether and hydroxyalkyl vinyl ethers is described. It was found that the choice of solvent, ligand, and reaction temperature had a fundamental influence on the regioselectivity and reactivity of the reaction, and the combination of Pd(OAc)₂ and DPPF in ethylene glycol led to the most effective catalytic system. Under these conditions, a variety of heteroaryl halides reacted very quickly with electron-rich olefins to afford exclusively the branched products in good to excellent yields without employing triflates, halide scavengers, or ionic liquids.     

Microdeformation behavior in nanotemplated epoxy thermosets: A study with in situ tensile deformation technique in transmission electron microscopy

Microdeformation behavior in nanostructured block copolymer‐toughened epoxy resins, or templated epoxy thermosets, was studied using an in situ tensile deformation technique performed directly in a transmission electron microscope. The observed microdeformation modes were found to correlate well with the macroscopic mechanical properties of the materials. In the order of decreasing macroscopic fracture toughness, the microdeformation modes were observed to change from large uniform plastic deformation over an extensive area, to localized plastic deformation bands, to little plastic deformation observed in the most brittle material. A similar trend was also observed when samples of the same material were tested at different temperatures, reflecting changes in the deformation mechanism as a function of temperature. Structural defects were observed in nanotoughening phases when plastic deformation was observed. The implication of the observed microdeformation modes to the macroscopic toughening mechanisms is discussed in the context of the micromorphology of the nanometer sized toughening phases and parameters of the epoxy matrix chemistry such as bromination, molecular weight, and interfacial miscibility. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 393–406, 2009     

软X射线条纹相机用于激光等离子体辐射温度的测量方法

本文提出了软X射线条纹相机与吸收膜相耦合测量等离子体温度的实验原理与方法,编制了数值计算程序SCC,给出了平面金靶在1.06μm激光(LF—II~=激光装置)作用下,靶面功率密度约10~(14)W/cm~2的辐射温度。并对温度处理中存在的误差,以及把此方法推广到能谱的时间分辨和温度的空间分辨测量中的可能性进行了讨论。     

两两正交拉丁方最大数目的新上界

记D（x）是使得TD（x，n）存在的最小的数．本文给出D（x）的一个上界．     

^3D4（q）群与射影平面

本文证明若^3D4（q）△G≤Aut（^3D4（q）），这里q是素数方幂，则G不能点传递作用在一个射影平面上.