1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU)-promoted efficient and versatile aza-Michael addition

A convenient and versatile method was developed for aza-Michael addition using a substoichiometric amount of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Various nitrogen nucleophiles were efficiently introduced to α,β-unsaturated carbonyl compounds employing 0.5 equiv of DBU. Furthermore, other heteroatomic nucleophiles could also be introduced successfully under the same reaction conditions.     

吖啶-多胺类缀合物的合成、 抗肿瘤活性及与DNA键合作用

设计合成了系列吖啶-多胺类衍生物(ACP1~ACP6), 并通过四甲基偶氮唑蓝(MTT)染色法研究了化合物对K562(人白血病细胞)、 A549(人肺癌细胞)和Hela(人宫颈癌细胞)细胞株的体外抗肿瘤活性. 结果显示, 化合物对肿瘤细胞具有一定的抑制作用, 尤其是化合物ACP2的抗肿瘤活性优于阳性对照顺铂. 通过UV-Vis光谱、 荧光光谱、 圆二色谱和热变性实验研究了合成化合物与小牛胸腺DNA(Ct-DNA)的键合作用. 结果表明, 三乙烯四胺修饰的化合物ACP2具有较好的抗肿瘤活性, 与DNA分子具有较强的结合能力.     

新型薄膜扩散梯度装置定量测量水环境中重金属形态

采用以纤维素透析膜为扩散相, 0.05 mol/L羧甲基纤维素钠(CMC)溶液为结合相的薄膜扩散梯度(DGT)装置(CMC-DGT)定量累积和测量水溶液中Cu²⁺, Cd²⁺和Pb²⁺的有效态; 考察了pH值和离子强度对CMC-DGT累积Cu²⁺, Cd²⁺和Pb²⁺的影响以及不同配体(乙二胺四乙酸二钠、 单宁酸和黄腐酸)对重金属有效态的影响; 测量了外加标的天然水和工业废水中重金属的有效态浓度; 并比较了不同结合相DGT装置对同一水体中重金属的有效态浓度. 实验结果表明, 0.05 mol/L CMC溶液对Cu²⁺, Cd²⁺和Pb²⁺累积容量分别为0.24, 0.11和0.45 mg/mL; 定量累积的最佳pH值范围分别为3.7～8.0, 4.7～9.0和4.7～8.0; 随着离子强度的增大, CMC-DGT对Cu²⁺, Cd²⁺和Pb²⁺的累积容量下降; CMC-DGT能够定量地累积配制水中的游离Cu²⁺, Cd²⁺和Pb²⁺, 回收率分别为92.1%, 100.6%和96.4%; 当有配体存在时, 随着配体浓度的增大, CMC-DGT测量的Cu²⁺, Cd²⁺和Pb²⁺有效态的浓度随之下降; 在过滤工业废水、 河水和湖水中, 不同结合相DGT装置对重金属有效态的测量值不同. 结果表明, CMC可作为DGT技术新的液态结合相.     

变几何域传热的表面热流反演方法

变几何域的表面热流反演是一类特殊的热传导逆问题,在再入飞行器烧蚀型防热材料的表面热流反演中具有工程实用价值.本文首先对变几何域传热的正问题计算方法进行了校核验证,然后建立了求解变几何域表面热流反演问题的顺序函数法和共轭梯度法;给出了这两种反演方法的基本思想和算法推导,并针对典型算例进行了仿真.结果表明:两种反演方法都能计算出较好的反演结果,并且算法受测量噪声的影响较小,具有较好的鲁棒性;反演算法能适应不同的几何域变化函数,但几何域变化量的测量误差在表面热流的反演结果中会有较为直接的反映.     

原位被动采样技术*

本文介绍了近些年来环境监测中三种新的原位被动采样技术-透析装置（Dialysis peepers）法、薄膜扩散平衡 (DET) 技术和薄膜扩散梯度 (DGT) 技术。综述了三种技术的原理、装置和特点。着重论述了三种技术在环境中的应用研究,包括透析装置以及DET 技术和DGT联用技术测量水体和沉积物孔隙水中可溶性金属的浓度;DGT技术可以作为一种预测重金属生物可利用性的新方法。DGT技术与其他技术（如DET、高离子选择电极、配体交换法、HPLC-ICP-MS等）联用可以更好地测量环境中重金属的形态。最后展望了原位被动采样技术未来的发展。     

Ultra-lean hydrogen-enriched oscillating flames behind a heat conducting bluff-body: Anomalous and normal blow–off

This paper presents a numerical study of ultra-lean hydrogen-methane flames stabilized behind a rectangular, highly conducting metallic bluff body acting as a flame holder. Using high fidelity numerical simulations, we show that lean inverted steady flames exist below normal flammability limits. They have distinct stabilization mechanism from pure methane flames. These flames are blown-off for sufficiently small velocities, a phenomenon called anomalous blow-off. At even leaner conditions oscillating ultra–lean hydrogen-methane flames can be established. These oscillating flames exist within a rather small range of equivalence ratios and inflow velocities, and move to mean locations closer to the flame holder as the reactant flow is increased. We show that the oscillations are associated with the shedding of flame balls from the downstream end of a “residual flame” that remains attached. Unlike their steady counterparts, the oscillating flames exhibit blow-off at both low velocities (anomalous blow-off) and at sufficiently high inflow velocities (normal blow-off). We show that normal blow-off is linked to heat losses to the flame holder.     

共轭效应的本质及其在有机反应中的特殊性

共轭效应是有机化学中特别重要的电子效应之一,存在于共轭体系之中;大学有机化学教学目标要求学生掌握并能熟练应用共轭效应理论解决有机化学中的实际问题。由于共轭效应涉及微观认知,学生普遍感觉不易理解。但作为教学重点与难点,又必须掌握;同时也是学生大学毕业后继续深造学习所必须的基础理论知识,理解、掌握并能熟练应用该理论知识解决有机化学中的学习问题显得尤为重要。本文采用密度泛函理论方法计算并给出了3个二烯烃分子轨道中最高占据分子轨道(HOMO)、最低空分子轨道(LUMO)结构图,揭示了共轭体系内部因存在电荷转移现象而产生电子云的平均化本质,表现在键参数中的键长平均化变化。     

CFD modeling and experimental validation of heat and mass transfer in wood poles subjected to high temperatures: a conjugate approach

In this article, a coupling method is presented in the case of high thermal treatment of a wood pole and a three-dimensional numerical simulation is proposed. The conservation equations for the wood sample are obtained using diffusion equation with variables diffusion coefficients and the incompressible Reynolds averaged Navier–Stokes equations have been solved for the flow field. The connection between the two problems is achieved by expressing the continuity of the state variables and their respective fluxes through the interface. Turbulence closure is obtained by the use of the standard k–ɛ model with the usual wall function treatment. The model equations are solved numerically by the commercial package ANSYS-CFX10. The wood pole was subjected to high temperature treatment under different operating conditions. The model validation is carried out via a comparison between the predicted values with those obtained experimentally. The comparison of the numerical and experimental results shows good agreement, implying that the proposed numerical algorithm can be used as a useful tool in designing high-temperature wood treatment processes. A parametric study was also carried out to determine the effects of several parameters such as initial moisture content, wood aspect ratio and final gas temperature on temperature and moisture content distributions within the samples during heat treatment.     

A new analytical method for computing solvent-accessible surface area of macromolecules and its gradients

In the calculation of thermodynamic properties and three-dimensional structures of macromolecules, such as proteins, it is important to have an efficient algorithm for computing the solvent-accessible surface area of macromolecules. Here, we propose a new analytical method for this purpose. In the proposed algorithm we consider the transformation that maps the spherical circles formed by intersection of the atomic surfaces in three-dimensional space onto the circles on a two-dimensional plane, and the problem of computing the solvent-accessible surface area is reduced to the problem of computing the corresponding curve integrals on the plane. This allows to consider only the integrals along the circular trajectories on the plane. The algorithm is suitable for parallelization. Testings on many proteins as well as the comparison to the other analogous algorithms have shown that our method is accurate and efficient.