PHOTOELECTRON SPECTROSCOPY STUDY OF AMMONIA-INDUCED CHANGES IN ELECTROSTATICALLY-ASSEMBLED CONJUGATED POLYMER FILMS

ABSTRACT

Exposure of electrostatically assembled polyelectrolyte films comprised of the anionic carboxylic conjugated polymer poly[2-(3-thienyl)-ethanolhydroxycarbonylmethyl-urethane], hereafter referred to as H-PURET, and polycations such as poly(diallyldimethylammonium) chloride, here after referred to as PDADMAC, to aqueous ammonia vapor leads to dra matic changes in the ultraviolet-visible absorption spectrum. In the case of H-PURET/PDADMAC, a shift from 442 to 494 nm is observed upon overnight ammonia exposure. X-ray photoelectron spectroscopy has been used to investigate the mechanism of the changes in optical properties. The C1s, O1s and S2p core levels exhibit negligible ammonia-induced changes. Two N1s peaks are observed in virgin H-PURET/PDADMAC assemblies, and ammonia exposure causes the nitrogen peak corresponding to the H-PURET side chain to become more intense relative to that of the PDADMAC layer. This selective change in the N1s feature suggests that ammonia interacts with the polythiophene side-chain, presumably by deprotonating the fraction of carboxylic acid groups that remain in the H-PURET layer. This deprotonation apparently leads to structural or single chain conformational changes in the conjugated polymer layers that alter the electronic absorption spectrum.     

格林互易定理在求解均匀带电圆环的静电势分布中的应用

对于静电场,由普遍的格林互易定理得出特殊情形下的格林互易定理.应用该定理推导出均匀带电圆环的数种在形式上互不相同的静电势分布解式.     

Charged patch attraction in dispersion: effect of polystyrene sulphonate molecular weight or patch size

The molecular weight (Mw) effect of polystyrene sulphonate (PSS) on the yield stress of ZrO₂ dispersion was evaluated. Three “monodispersed” samples with Mw of 1430, 9960 and 130,000, and two broad distribution samples of Mw 70,000 and 1.0 million were investigated. Adsorbed PSS gave rise to charged patch attraction that enhanced the maximum yield stress, τ _{y max}, of dispersions at charge neutral condition [3]. As a PSS patch consists of only one molecule, the patch size should increase with increasing Mw. For PSS of Mw 1430 with just only seven repeating units the patch formed would be rectangular (linear) and small with a high charge density. For Mw of 9960 and higher, the patch would be irregular in shape with a smaller charge density. At a moderate surface coverage of ˜20%, the τ _{y max} increases quite sharply from Mw 9960 to 130,000 and very gradually from 130,000 to 1.0 million. From Mw 9960 to 130,000, the strength of the patch attraction increases quite strongly with increasing patch size. From Mw 130,000 to 1million, the small increase in τ _{y max} reflected a limiting patch size effect. At the limiting size, the attraction is at maximum strength. At the same coverage, PSS of Mw 1430 also displayed a strong charge patch attraction. This was attributed to a higher number of charged patch interactions at the closest point of separation and also to the high charge density of the PSS patch. The low surface coverage of 6% revealed no significant molecular weight effect on τ _{y max}. The network structure consisted of a mixture of charge patch and bare surface interactions. Received: 4 July 2000/Accepted: 18 July 2000     

氩等离子体射流冲击平板壁面处电子温度的测量

本文对空气环境中氩等离子体射流冲击平板条件下冷壁附近的电子温度，采用静电探针方法进行了测量．研究了等离子体温度、速度以及平板至发生器出口距离等参数的影响．实验结果表明，在冷壁面附近，电子温度总是明显高于相应的重粒子温度，从而证明在等离子体射流冲击平板条件下冷壁附近的边界层显著偏离局域热力学平衡（ＬＴＥ）状态．实验结果还表明，探针污染是影响测量结果可靠性的一个重要因素．     

Prey-predator systems with intertwined basins of attraction

In this article, we show the existence of intertwined basins of attraction for a class of prey-predator systems, which improves the extant results by deleting some crucial and hard testing conditions.     

高效液相色谱-四极杆/静电场轨道阱高分辨质谱测定奶粉中的低聚果糖

建立了高效液相色谱-四极杆/静电场轨道阱高分辨质谱法测定奶粉中低聚果糖的方法。奶粉样品用水溶解,加乙酸锌沉淀蛋白,经离心、0.22 μm粒径的微孔膜过滤后,采用Carbohydrate色谱柱(100 mm×2.1 mm, 2.6 μm)进行分离,以乙腈与0.1%乙酸水溶液为流动相进行梯度洗脱。质谱采用正离子Target-MS/MS模式,在分离窗口为m/z 4.0和碰撞能为30 eV的条件下,提取响应值较高且在待测样品中无干扰的目标子离子的精确质量数,此方法能够很好地排除样品中的基质干扰。在所建立的色谱-质谱条件下,蔗果三糖(GF₂)、蔗果四糖(GF₃)和蔗果五糖(GF₄)能够得到较好的分离,高分辨质谱提取的质量准确度小于5×10^-6(5 ppm),整个分析时间只需10 min。该方法对GF₂和GF₃的检出限可达100 μg/kg,对GF₄的检出限可达55 μg/kg。待测物质采用外标法定量,线性关系良好,相关系数均大于0.998。通过加标验证,在5、10和20 mg/kg 3个加标水平下,奶粉中GF₂、GF₃和GF₄的平均回收率在75.8%~107.3%范围内,相对标准偏差(RSD)在1.6%~8.3%范围内。该方法样品前处理过程简单,只需沉淀蛋白质,通过二级子离子的选择即可排除基质干扰,分析时间短,测定结果准确、可靠,适用于任何奶粉的高通量测定。     

Structure and Dynamics of Confined Polymer Melts from Attractive Interaction to Repulsive Interaction Between Polymer and Smooth Wall

We studied the static and dynamic properties of unentangled polymer chains which have a variable strength of interaction with the confining smooth walls by means of the lattice Monte Carlo simulation based on the bond-fluctuation model, that is, investigated the wall-polymer interactions which systematically vary from attraction to repulsion. A critical value of attractive potential(ε_wc) is found to be -0.6k_BT, and only below it can the adsorption layer of monomers be formed near the wall. At the critical point of attraction ε_wc, attractive interaction counterba- lances the wall-polymer excluded volume effect, which minimizes the confinement effects on both chain dimension and mobility. Influences on both chain dimension and mobility increase with the increasing of either attraction or repulsion imposed by the walls. Despite of the nature and strength of the wall-polymer interaction, with the decrease of film thickness, configurations more parallelly aligned and flattened are adopted by confined chains, and a systematic trend of deceleration is found. Variations of chain dynamics with both film thickness and wall-polymer interaction can be well explained by the corresponding changes in the confinement of the nearest-neighboring particles that surround the chains. Besides, the thickness of the interfacial layer inside polymer films, where chains adopt a flattened “pancake” shape, is about two times the bulk radius of gyration and independent of the wall-polymer interaction.