Synthesis and characterization of wholly aromatic poly(azomethine)s containing donor–acceptor triphenylamine moieties

N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine was synthesized from N‐(4‐nitrophenyl)‐diphenylamine by the Vilsmeier‐Haack reaction. Soluble aromatic poly(azomethine)s (PAMs) were prepared by the solution polycondensation of N‐(4‐nitrophenyl)‐4′,4″‐bisformyl‐diphenylamine and aromatic diamine in N‐methyl‐2‐pyrrolidone (NMP) at room temperature under reduced pressure. All the PAMs are highly soluble in various organic solvents, such as N,N‐dimethylacetamide (DMAc), chloroform (CHCl₃), and tetrahydrofuran (THF). Differential scanning calorimetry (DSC) indicated that these PAMs had glass‐transition temperatures (T_gs) in the range of 170–230 °C, and a 10% weight‐loss temperatures in excess of 490 °C with char yield at 800 °C in nitrogen higher than 60%. These PAMs in NMP solution showed UV‐Vis charge‐transfer (CT) absorption at 405–421 nm and photoluminescence peaks around 462–466 nm with fluorescence quantum efficiency (Φ_F) 0.10–0.99%. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels of these PAMs can be determined from cyclic voltammograms as 4.86–5.43 and 3.31–3.34 eV, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4921–4932, 2007     

Axisymmetric frictionless contact of functionally graded materials

The main interest of this study is a new method to solve the axisymmetric frictionless contact problem of functionally graded materials (FGMs). Based on the fact that an arbitrary curve can be approached by a series of continuous but piecewise linear curves, the FGM is divided into a series of sub-layers with shear modulus varying linearly in each sub-layer and continuous at the sub-interfaces. With this model, the axisymmetric frictionless contact problem of a functionally graded coated half-space is investigated. By using the transfer matrix method and Hankel integral transform technique, the problem is reduced to a Cauchy singular integral equation. The contact pressure, contact region and indentation are calculated for various indenters by solving the equations numerically. An erratum to this article can be found at     

稀土及杂质元素对ZA27合金晶间腐蚀的影响

为了从本质上了解杂质与稀土元素对锌铝合金晶间腐蚀的影响 ,探索抑制合金晶间腐蚀的有效途径 ,依据晶界的大角度重位点阵理论编制出相应计算机软件 ,建立含稀土、杂质及 η相颗粒的α相大角度晶界原子集团模型 ,采用递归法计算了α相晶界间的电荷转移 ,由此讨论了杂质 (Pb、Sn、Cd)及稀土元素 (La、Y)对Zn、Al电极电位的影响 .结果表明 ,杂质Pb、Sn、Cd增大原子间的电荷转移量 ,提高Zn、Al电极电位差 ,加速合金的腐蚀 ,稀土元素减小原子间的电荷转移量 ,降低Zn、Al电极电位差 ,具有抑制晶间腐蚀的作用 .     

ClONO2异构化反应和分解反应的理论研究

用B3LYP/6 31+G(d)和MP2 (Full) /6 31+G(d)优化ClONO2 及其分解反应和异构化反应的过渡态和产物的分子结构 .在B3LYP/6 31+G(d)水平上计算了相关分子的振动频率 .ClONO2 的几何结构、振动频率和红外强度与实验测量值符合得很好 .找到了未曾报道的立体异构体 .对这一立体异构体进行了高级别理论方法CCSD(T) /6 311G(d)和QCISD(T) /6 311G(d)的几何结构优化和振动频率计算 ,表明它是一个稳定的立体异构体 .在所研究的几种反应中 ,ClONO2 分解为NO2 +ClO是最容易进行的反应 .而ClONO2 异构为立体异构体的反应是最难进行的反应 .其所需克服的过渡态的能垒为 4 81.5 2kJ/mol,而反应吸收能量为 2 99.85kJ/mol.次难进行的是ClONO2 经TS1到反应中间体M1,再经TS12而分解为ClNO +O2 的反应 .这个反应通道所需克服过渡态的能垒为 4 2 1.5 5kJ/mol,反应吸收能量为 15 7.98kJ/mol.从以上分析可知 ,和ClO +NO2 反应生成ClONO2 比较 ,ClONO2 具有较好的稳定性 .     

Metallo‐supramolecular micelles: Studies by analytical ultracentrifugation and electron microscopy

In aqueous solutions, amphiphilic block copolymers in which a polystyrene (PS) segment is connected to a poly(ethylene oxide) (PEO) block via a bis(2,2′:6′,2″‐ terpyridine ruthenium) complex can form micelles. Such micelles of the protomer type PS₂₀‐[Ru]‐PEO₇₀, according to the preparation procedure representing frozen micelles, were studied by sedimentation velocity and sedimentation equilibrium analysis in an analytical ultracentrifuge and by transmission electron microscopy, with different techniques applied for the sample preparation. The particles obtained were surprisingly multifarious in size. In ultracentrifugation experiments performed at relatively low salt concentrations, the distributions of the sedimentation coefficient s_20,w showed a pronounced peak at 9.6 S and a broad, only partly separated second peak around 14 S. The molar mass of the particles at the peak was around 430,000 g/mol, corresponding to an aggregation number of approximately 85. The average hydrodynamic diameter of the particles in the peak fraction was approximately 13 nm. In electron micrographs of negatively stained samples, spheres of diameters between 10 and 25 nm were the most abundant particles, but larger ones with a wide size range were also visible. The latter particles apparently were composed of smaller ones. The data from both sedimentation analysis and electron microscopy showed that (1) the studied compound formed primary micelles of diameters around 20 nm and (2) the primary micelles had a tendency toward aggregation. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3159–3168, 2003     

Na离子和Cl离子引起He原子直接多重电离过程的研究

利用2～8 MeV的Naq+、Clq+(q=2,3,4,5)轰击氦原子,对碰撞的直接多重电离过程进行研究.实验采用反冲离子-散射离子飞行时间符合技术,通过反冲离子飞行时间谱区分不同价态反冲离子;利用静电偏转和位置灵敏探测技术区分不同电荷态散射离子;结合CAMAC-PC多参数获取系统得到一定价态散射离子所对应的反冲离子电荷态分布谱;经分析该谱得到直接多重电离截面与直接单电离截面之比R21.讨论了R21随入射离子速度和电荷态的变化关系.     

27,28P+28Si总反应截面增强及可能相关的机制

测量了27,28P和相应同中子异位素在28Si靶上的中能反应截面.测得N=12和13同中子异位素的反应截面在Z=15处突然增大.对Z≤14同中子异位素和28P的实验数据结果可以用改进的光学极限近似的Glauber理论很好地描述.28P的反应截面能够用扩大核芯以改进的Glauber理论来解释.但是,用改进光学极限和少体近似的Glauber理论却低估了27P的实验数据.理论分析表明,扩大的核芯加质子晕可能是响应27P+28Si反应截面增强的机制. The reaction cross sections of~(27,28)P and the corresponding isotones on Si target were measured at intermediate energies. The measured reaction cross sections of the N=12 and 13 isotones show an abrupt increase at Z=15. The experimental results for the isotones with Z≤14 and~(28)P can be described well by the modified Glauber theory of the optical limit approach. The enhancement of the reaction cross section for~(28)P could be explained by the modified Glauber theory with an enlarged core. Theoretical ana...     

年龄相关的种群扩散系统的最优分布控制

本文讨论年龄相关的种群扩散系统的最优分布控制 ,证明了最优分布控制的存在性 ,得到了分布控制为最优的充分必要条件及确定最优控制的最优性组 .     

Stationary Intensity Distribution of Single-Mode Laser Driven by Additive and Multiplicative Colored Noises with Colored Cross-Correlation

Applying the approximate Fokker-Planck equation we derived, we obtain the analytic expression of thestationary laser intensity distribution Pst(Ⅰ) by studying the single-mode laser cubic model subject to colored cross-correlation additive and multiplicative noise, each of which is colored. Based on it, we discuss the effects on the stationarylaser intensity distribution Pst(Ⅰ) by cross-correlation between noises and “color“ of noises (non-Markovian effect) whenthe laser system is above the threshold. In detail, we analyze two cases: One is that the three correlation-times (i.e.the self-correlation and cross-correlation times of the additive and multiplicative noise) are chosen to be the same value(τ1 = τ2 = τ3 = τ). For this case, the effect of noise cross-correlation is investigated emphatically, and we detect thatonly when λ≠ 0 can the noise-induced transition occur in the Pst(Ⅰ) curve, and only when τ≠ 0 and λ≠ 0, can the“reentrant noise-induced transition“ occur. The other case is that the three correlation times are not the same value,τ1 ≠τ2 ≠τ3. For this case, we find that the noise-induced transition occurring in the Pst (Ⅰ) curve is entirely differentwhen the values of τ1, τ2, and τ3 are changed respectively. In particular, when τ2 (self-correlation time of additivenoise) is changing, the ratio of the two maximums of the Pst(Ⅰ) curve R exhibits an interesting phenomenon, “reentrantnoise-induced transition“, which demonstrates the effect of noise “color“ (non-Markovian effect).