纳米自组装聚电解质超薄多层膜

相反电荷的聚电解质在溶液中通过静电相互作用自组装形成超薄多层膜，这种膜的结构可实现分子水平上的控制。就其复合、结构及其影响因素、以及应用进行了概述。     

聚电解质多层有序膜电极的生成及其电化学特性

研究了在金电极表面硫醇自组装膜上聚电解质多层有序膜的形成过程及其电化学特性。用紫外光谱和电化学方法对多层有序膜进行了表征。结果表明，有序膜影响着离子在膜中的穿透性，离子型电活性物质如铁氰根离子和亚甲蓝等可嵌入有序膜中，研究了多层有序膜电极的电化学特性及膜中铁氰根离子的电化学行为。     

由聚电解质自组装多层膜制备微孔薄膜

带有相反电荷的聚电解质通过静电作用交替沉积可以得到自组装多层膜,由于这种技术可操作性强,用途广泛,近十几年来已有了大量的研究．聚电解质多层膜在一定条件下可以形成纳米孔和微米孔．Fu等研究了聚丙烯酸和聚乙烯基吡啶组成的氢键自组装多层膜在碱溶液中溶去其中的聚丙烯酸后,剩下的聚乙烯基吡啶重构形成微孔薄膜．Mendelsohn等发现将聚丙烯酸和聚烯丙基胺自组装而成的多层膜浸入pH=2．4左右的溶液中可制备微孔薄膜．但这些方法并不能使强聚电解质多层膜形成多孔结构。     

利用层层自组装技术制备聚电解质多层膜高效液相色谱固定相

以聚(乙烯-alt-马来酸)的苯乙胺衍生物与聚烯丙基胺盐酸盐为原料,通过层层自组装技术(LBL)在色谱硅胶表面交替沉积得到聚电解质多层膜高效液相色谱(HPLC)固定相;利用紫外光谱、红外光谱和元素分析研究了HPLC固定相的结构和组成.结果表明,聚电解质多层膜HPLC固定相被成功构筑在硅胶颗粒表面;制备的多层膜固定相可方便地用于6种芳香烃类及4种烷基苯类物质的分离分析.本文的研究结果说明LBL技术在制备HPLC固定相方面具有一定的应用价值.     

胶体颗粒在聚电解质多层膜表面的可控组装

利用原子力显微镜和扫描电子显微镜研究了磺化聚苯乙烯胶体颗粒在由聚二甲基二烯丙基氯化铵和聚苯乙烯磺酸钠层状自组装而成的多层膜表面的组装.该组装受表面性质影响,通过对多层膜的最外层的组装条件或利用盐溶液对多层膜进行后处理可以控制胶体颗粒在膜表面的组装密度.     

以聚电解质多层膜为纳米反应器制备Au@Pt核壳纳米粒子

以聚二烯丙基二甲基氯化铵和聚苯乙烯磺酸钠为构筑单元,通过静电层层自组装制备了多层膜,利用薄膜中存在的抗衡阴离子,选择AuCl-4和PtCl2-6作为Au和Pt的前驱体,通过连续的阴离子交换/还原,原位制备了Au-Pt双金属纳米粒子。 紫外-可见分光光度法、透射电子显微镜和能量色散X射线能谱数据表明,在聚电解质多层薄膜中成功地制备了具有核壳结构的Au@Pt双金属纳米粒子。 这种纳米粒子在电化学催化、燃料电池方面具有潜在的应用价值。     

层层自组装聚电解质多层膜的制备及在膜分离中的应用

扼要论述了聚电解质自组装膜制备过程中电荷密度、驱动力及增长方式等对膜厚和膜结构影响的基本规律,着重介绍了近年来聚电解质自组装渗透气化膜和离子分离膜研究概况.对聚电解质自组装分离膜今后的研究工作提出了建议.     

层层自组装聚电解质多层膜的制备及在膜分离中的应用

扼要论述了聚电解质自组装膜制备过程中电荷密度、驱动力及增长方式等对膜厚和膜结构影响的基本规律,着重介绍了近年来聚电解质自组装渗透气化膜和离子分离膜研究概况。对聚电解质自组装分离膜今后的研究工作提出了建议。     

层层自组装聚电解质膜光纤传感器的制备和应用

在过去几十年中,光纤的应用已经渗透到多个学科领域。光纤的抗电磁干扰、可远程监控、多重监测、体积小及质量轻等特点,使其在传感器研究领域备受关注。聚电解质层层自组装膜构建的光纤传感器自2000年诞生以来,已快速发展成为传感器领域新的研究热点。该类光纤传感器在微量物质的监测方面具有广泛的应用前景。本文从光纤和光纤传感器优点出发,总结了基于层层自组装多层膜的光纤传感器种类、性能、检测原理以及相应的光纤结构和自组装材料;进而结合作者已做的相关工作,论述了在光纤基底上的聚电解质层层自组装及基于自组装膜的光纤传感器的测试;重点综述了近十年层层自组装膜的光纤pH传感器、湿度传感器、气体传感器、生物传感器及其他类型的光纤传感器的制备与应用,并展望了今后聚电解质层层自组装多层膜光纤传感器的发展。     

层层自组装聚电解质多层膜的制备及在膜分离中的应用

扼要论述了聚电解质自组装膜制备过程中电荷密度、驱动力及增长方式等对膜厚和膜结构影响的基本规律,着重介绍了近年来聚电解质自组装渗透气化膜和离子分离膜研究概况。对聚电解质自组装分离膜今后的研究工作提出了建议。     

Polyelectrolyte Multilayer Films Containing Ferrocene: Effects of Polyelectrolyte Type and Ferrocene Contents in the Film on the Redox Properties

Electrochemical properties of Fc‐PEM films have been studied by changing the chemical structure of the polymer chains and the content of Fc moiety in the film systematically. We have prepared a series of PEM films by a layer‐by‐layer deposition of polycations, Fc‐modified poly(allylamine) (Fc‐PAA) and poly(ethyleneimine) (Fc‐PEI), and polyanionic poly(vinyl sulfate) (PVS) on the surface of a gold electrode. The redox properties of the Fc‐PAA/PVS and Fc‐PEI/PVS films depended significantly on the content of Fc moiety in the polymer chains and on the polymer type. Fc‐ PAA and Fc‐PEI polymer chains can penetrate 3 or 4 PAA/PVS bilayers inserted between the redox polymers and electrode. The Fc‐PAA film‐modified electrode can be used for electrocatalytic oxidation of ascorbic acid.     

Ordered Polyelectrolyte Multilayers: Unidirectional FRET Cascade in Nanocompartmentalized Polyelectrolyte Multilayers

Multifunctional polyelectrolyte (or layer‐by‐layer, LbL) multilayers consisting of a set of nanocompartments separated by impermeable ultrathin barriers, whereby the thickness of the compartments is tuned in the range 1–10 nm, are synthesized. Each compartment contains a different dye, introduced by co‐adsorption during multilayer deposition. Different LbL barriers are tested for impermeability towards dye diffusion while simultaneously allowing energy transfer to occur between the compartmentalized dyes. Cross‐linked LbL multilayers based on poly(acrylic acid) and poly(allyl amine) are shown to provide the desired impermeability for thicknesses as small as about 2.5 nm. A proof‐of‐concept system is then realized involving a cascade of two FRET processes, whereby the light energy is collected in a first nanocompartment containing pyranine, sent to a second nanocompartment loaded with fluorescein, before finally being transferred to a third, Nile blue‐filled compartment located at the external surface of the film. This demonstrates the possibility to fabricate complex light‐harvesting antenna systems by LbL assembly while controlling the architecture of the antenna down to a few nanometers.     

Multilayer characterization by energy dispersive X-ray reflectivity technique

An experimental setup was developed to verify the feasibility of silicon drift detector to be used for the multilayer characterization by means of multilayer energy dispersive X-ray reflectivity. Such a detector allows high count rates up to 3 × 10⁵ cps and can be used in principle for the direct beam intensity measurement, which is to be done for the X-ray multilayer reflectivity patterns obtaining. A series of measurements were performed for Mo/B₄C multilayer sample. A quality of the experimentally obtained data turns out to be enough to perform a sample structure exploration using a numerical procedure of experimental data fitting. Due to low cost and short time, required for the measurements, an experimental technique proposed has a good perspective to be used for some practical applications in industry.     

Construction of glucose biosensor based on sorption of glucose oxidase onto multilayers of polyelectrolyte/nanoparticles

A new approach to constructing an enzyme-containing film on the surface of a gold electrode for use as a biosensor is described. A basic multilayer film (BMF) of (PDDA/GNPs) _n /PDDA was first constructed on the gold electrode by electrostatic layer-by-layer self-assembly of poly(diallyldimethylammonium chloride) (PDDA) and gold nanoparticles (GNPs). Glucose oxidase (GOx) was then sorbed into this BMF by dipping the BMF-modified electrode into a GOx solution. The assembly of the BMF was monitored and tested via UV-vis spectroscopy and cyclic voltammetry (CV). The ferrocenemethanol-mediated cyclic voltammograms obtained from the gold electrode modified with the (PDDA/GNPs) _n /PDDA/GOx indicated that the assembled GOx remained electrocatalytically active for the oxidation of glucose. Analysis of the voltammetric signals showed that the surface coverage of active enzyme was a linear function of the number of PDDA/GNPs bilayers. This result confirmed the penetration of GOx into the BMF and suggests that the BMF-based enzyme film forms in a uniform manner. Electrochemical impedance measurements revealed that the biosensor had a lower electron transfer resistance (R _et) than that of a sensor prepared by layer-by-layer assembly of PDDA and GOx, due to the presence of gold nanoparticles. The sensitivity of the biosensor for the determination of glucose, which could be controlled by adjusting the number of PDDA/GNPs bilayers, was investigated.     

聚电解质PDDA/PSS层层自组装膜的渗透汽化性能

采用聚电解质层层自组装(LbL)技术, 在不同盐浓度下制备了聚(二烯丙基二甲基氯化铵)/聚苯乙烯磺酸钠(PDDA/PSS) 多层自组装膜, 并用于渗透汽化性能的研究. 重点考察了组装溶液中NaCl的浓度、组装层数及操作温度对自组装膜的异丙醇脱水性能的影响. 同时, 用扫描电镜观测了不同条件下制备膜的表面形貌. 结果表明, 在高NaCl含量的聚电解质溶液中只需组装几个双层的LbL膜, 即能获得较高的分离因子和较大的通量, 并解释了该LbL膜呈现反“trade-off”现象的原因.     

PET/PC共混体系的酯交换反应对其高压结晶行为的影响

利用转矩流变仪、DSC、SEM及WAXD等表征手段研究了PET/PC共混体系的酯交换反应对其高压结晶行为的影响.SEM观察表明,PET和PC熔混时的酯交换反应有利于PET/PC体系在高压结晶时生成厚度较大的伸直链晶体,且可以促进其高压下酯交换反应的发生.楔形伸直链晶体和弯曲伸直链晶体的存在证明链滑移扩散和酯交换反应两种机制对体系中聚酯伸直链晶体的增厚有贡献.拟合分峰法和War-ren-Averbach傅里叶分析法的计算结果表明,随PET/PC体系熔混时酯交换反应程度的增加,高压结晶共混物的结晶度降低,PET的平均微晶尺寸增大,点阵畸变平均值则减小,而微晶尺寸分布变宽.提出了在共聚物组分都具备结晶能力时,结晶诱导化学反应和化学反应诱导结晶两种过程在一定条件下可同时发生的观点.     

支化聚醚电解质的研究：Ⅰ支化聚氧化乙烯的合成及表征

采用Ｗｉｌｌｉａｍｓｏｎ反应成功地合成了支化聚氧乙烯，并用ＩＲ、＾１３ＣＮＭＲ、ＤＳＣ对其进行了表征。结果表明，＾１３ＣＮＭＲ可半定量地表征支化度，链的支化可以降低玻璃化温度和结晶度。     

Self‐Assembly of Gold Nanoparticles/Electroactive Polyelectrolyte Multilayer Films for Tunable Electrocatalysis

This study described fabrication, characterization, and application of multilayer films based on layer‐by‐layer assembly of ferrocene poly(ethylenimine) and gold nanoparticles. Assembly process of the multilayer film was investigated by atomic force microscopy, UV‐visible absorption spectroscopy and electrochemical impedance spectroscopy. The multilayer films exhibited a pair of well‐defined redox peaks as revealed by cyclic voltammetry, as well as bifunctional and fine‐tunable electrocatalysis for oxidation of ascorbic acid and reduction of oxygen. Both the outer layer and layer number had effect on the electrocatalytic response. Electrocatalytic activity of the films could be controlled with assemblies at the nanoscale level by simply adjusting deposition cycles or amount of component in the films.     

表层纳米氧化锆包覆硅球色谱载体的制备和表征

硅胶是目前应用最为广泛的色谱载体. 硅胶的比表面积及孔体积大, 渗透性好, 孔结构适宜于色谱分离, 但在pH＜2及pH＞8条件下不稳定, 对碱性化合物, 尤其是对生物样品产生不可逆吸附. 氧化锆化学性质非常稳定[1], 适宜碱性样品尤其是生物大分子的分离; 但是其比表面积和孔体积小[2～5], 孔结构对色谱分离不利[6], 可涂敷的固定相量较小, 渗透性差. 本文采用分子自组装方法[7～9]在微米硅球表面包覆多层纳米氧化锆制备了较为理想的色谱载体.     

IONIC SELF-ASSEMBLY AND HUMIDITY SENSITIVITY OF POLYELECTROLYTE MULTILAYERS

Multilayer thin films of alternately adsorbed layers of polyelectrolytes PDDA and PS-119 were formed on bothplanar silica substrates and optical fibers through the ionic self-assembly technique. Intrinsic Fabry-Perot cavities werefabricated by stepwise assembling the polyelectrolytes onto the ends of optical fibers for the purposes of fiber optical deviceand sensor development. Ionically assembled polyelectrolyte multilayer thin films, in which there are hydrophilic side groupswith strong affinity towards water molecules, are a category of humidity-sensitive functional materials. The polyelectrolytemultilayer thin film Fabry-Perot cavity-type fiber optical humidity sensor can work over a wide range from about 0% RH toabout 100% RH with a response time less than 1s.