A density-functional study of Al-doped Ti clusters: TinAl (n=1-13)

Equilibrium geometries, stabilities, and electronic properties of TinAl (n=1-13) clusters have been studied by using density-functional theory with local spin density approximation and generalized gradient approximation. The ground-state structures of TinAl clusters have been obtained. The resulting geometries show that the aluminum atom remains on the surface of clusters for n<9, but is slowly getting trapped beyond n=9, meanwhile, the Al atom exhibits a valent transition from monovalent to trivalent. The geometric effects and electronic effects clearly demonstrate the Ti4Al cluster to be endowed with special stability. The studies on the bonds indicate the change from ionic to metalliclike. (C) 2004 American Institute of Physics.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

Electrochemical and in situ spectroelectrochemical behavior of 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and (Zn(II)OHTTAP)

The characterization of free base porphyrin 2,3,7,8,12,13,17,18-octakis(hexyl-thio) tetraazaporphyrin (H(2)OHTTAP) and its zinc(II) complexes [Zn(II)OHTTAP] containing eight thioether groups at the beta -pyrrole positions of the macrocycle was reported. Results obtained by cyclic voltammetry and differential pulse voltammetry indicated a five-electron reduction in five steps for each complex. They were oxidized in two single-electron-transfer steps to yield pi -cation radicals and dications and reduced in three single-electron-transfer steps to yield pi -anion radicals, dianions and trianions, respectively. The redox property of H(2)OHTTAP was unusual as compared to porphyrins (PPs) and phthalocyanines (Pcs). Each process was monitored by in situ thin-layer spectroelectrochemistry, which indicated that only the Ligand was electroactive. The existence of the eight hexylthio groups was responsible for the intrastack interactions and enhanced intracolumnar and intercolumnar electron motions, resulting in improved conductivity. Copyright (C) 2001 John Wiley & Sons, Ltd.

全同1，2－聚丁二烯的合成及用~(13)C-NMR方法研究1，2－聚丁二烯的序列结构

采用Cr／Al催化体系，成功地合成了全同1，2－聚丁二烯（PBD），并用DSC方法、X－射线衍射、红外光谱及~(13)C－NMR的方法进行结构与物性测定，得如下结果：全同1，2－PBD的熔点为124.3℃；三角晶系中，分子链成了螺旋，晶胞参数为a＝17.3A，c＝ 6.5A；在红外光谱中，其特征谱带出现在694.4 cm~(-1)处；在~(13)C－NMR谱中仅出现四条谱峰，其化学位移分别为142.51、111.56、39.26、37.43 ppm。全同1，2－PBD的~(13)C－NMR谱提供的实验数据表明，在~(13)C－NMR谱中1，2－PBD－CH二碳十个五元组谱峰的归属是有别于Elgert、Kumar已有的归属。它属于一种新的归属，与半经验方法所推演的结果相符。它恰巧同聚丙烯侧甲基五元组谱峰的归属一致。采用半经验方法研究了1，2－PBD的~(13)C－NMR增中CH二碳五元组、CH_2－碳四元组及六元组共振谱峰，同时讨论了模型链的链长、温度以及立构序列的排列对各立构序列键概率的影响，求得了相应的r值。同时采用经验方法对1，2－PBD的~(13)C－NMR谱中CH_2=碳、CH－碳五元组及CH_2－碳四元组谱峰做了归属。两种方法对CH_2－碳谱峰的归属得到了一致的结果。

二苯基-15-冠-5加速钠离子和钾离子在微米管支撑的微-水/1,2-二氯乙烷界面上的转移反应

玻璃微米管针尖可用于支撑微米级的水/1,2-二氯乙烷（W/DCE）界面,并用来研究二苯基-15-冠-5（DB15C5）加速钠离子和钾离子转移反应的机理和求算其络合物的稳定常数.在两种极限情况下,即水相中金属离子浓度远大于有机相中DB15C5的浓度（DB15C5扩散控制过程）和有机相中DB15C5的浓度远大于水相中金属离子浓度（金属离子扩散控制过程）,循环伏安研究表明,加速钠离子转移反应均发生1∶1（金属离子:载体）的界面络合转移过程,相应的一级络合常数分别为logβ1=8.97±0.05和logβ1=8.63±0.03.而对于加速钾离子转移反应,当 DB15C5扩散控制时发生的是一个1:2的界面络合转移过程,当钾离子扩散控制时,在电位窗内却观察到两个过程:一个较低电位的1∶2的界面络合转移过程和一个较高电位的1∶1界面络合转移过程.两种极限条件下所求算的钾离子和DB15C5的二级络合常数分别为logβ1=13.64±0.03和logβ2=11.34±0.24.

麻疹疫苗诱发中国仓鼠卵巢细胞(CHO-K_(1))染色体畸变和基因突变的研 究

以中国仓鼠卵巢细胞(CHO)次黄嘌呤-乌嘌呤磷酸核糖转移酶位点突变检测系统(CHO/HGPRT)检测国产麻疹疫苗的诱变性。实验证明,麻疹病毒及其疫苗可诱发染色体畸变。接种的三个剂量, 对细胞存活率无显著影响(P>0.05),但能使HGPRT位点正向突变频率升高。2.8logTC1D_(50)/ml和3.1logTC1D_(50)/ml组的突变频率的升高与对照组相比有统计学意义。表明HGPRT~(-)突变频率的升高与接种疫苗有关。

Preparation, characterization and quantized capacitance of 3-mercapto-1,2-propanediol monolayer protected gold nanoparticles

Monolayer protected gold nanoparticles (MPCs) are the focus of recent research for their stability and are deemed as the building blocks of bottom-up strategies. In this Letter, 3-mercapto-1,2-propanediol monolayer protected gold nanoparticles (MPD-MPCs) were synthesized and characterized by transmission electron microscopy, UV/Vis spectroscopy, X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The value of quantized double-layer capacitance (1.13 aF) of MPD-MPCs in aqueous media was obtained by differential pulse voltammograms.

Viscosity, Surface Tension, and Atomization of Water-Methanol and Diesel Emulsions

This article is the result of experimental studies of the rheologv, viscosities, surface tensions, and atomization of water-methanol and diesel emulsions. The Span 80 and Tween 60 are employed to make three emulsifying agents, Y01, Y02, and Y03, with viscosity of 1.32-1.5 Pa s and HLB values of 5.36, 4.83, and 4.51, respectively. In the water-in-oil emulsions, the aqueous phase is between 10% and 50%; the agent concentration added is 0.8-8.0%. The viscosity of the emulsions is 0.003-0.02 Pa s, and the surface tens ion is 0.04-0.1 N/m. The types and concentrations of agents significantly influence the viscosity of the emulsions, and the higher concentration of the aqueous phase (<50%) in creases the viscosities of the emulsions, especially for higher agent concentration. Interfacial membrane and HLB values of the agents can explain all these phenomena. Higher aqueous phase concentration and agent viscosity results in larger Sauter mean diameter.

具有摩擦阻尼结点之结构动力分析

本文将增量谐波平衡法(Incremental Harmonic Balance Method, I. H. B Method)结合组抗方法用于分析具有摩擦结点之结构稳态动力响应。这方法之主要优点是能将线性结构与摩擦结点分开来考虑。当摩擦结点之自由度远小于线性结构之自由度时,计算是很经济的。发展了一个分析这种系统之计算程序可与一般有限元结构分析程序如SAPV或ADINA相连,作为后处理程序。

水煤浆燃烧技术用于造纸黑液处理的研究(英文)

对水煤浆燃烧技术用于造纸黑液处理进行了中试研究。多种不同组成的黑液煤浆在改造过的 6 .5 t/ h的链条炉上进行了燃烧试验。对黑液燃烧产物如烟气、烟尘及灰渣进行了成分测试 ,对锅炉混烧水煤浆前后的效率进行了分析比较。结果表明 ,黑液煤浆与层燃煤混烧提高了锅炉效率并降低了污染。水煤浆燃烧技术在该领域的成功应用为造纸黑液的处理提供了新的思路。

燃烧物理学基础

位相锁定来自同一侧面抽运Nd：YAG板条的两束激光

实验研究了腔内位相锁定来至一LAD侧面抽运的Nd：YAG板条的两束激光，输出镜面出现干涉条纹，获得1.13W的相干光，其组束效率达到64.9%，相干度约60%。实验中发现只需要一根作为滤波的金属丝放在离输出镜合适的位置都就能有效稳定干涉条纹，金属丝引起的损耗低于8%。