光敏性聚电解质重氮树脂及其自组装

二苯胺－4－重氮盐与甲醛的缩合产物是一种正离子性光敏性聚电解质重氮树脂，本文主要结合我们自己的研究工作，对重氮树脂的性质尤其是它的光、热反应，与阴离子表面活性剂所形成复合物性质，及基于这种带重氮基的光敏物质的各自组装进行了比较详细的介绍，并简要介绍了光敏性自组装超薄膜的应用。     

红外光谱法研究重氮树脂自组装膜的光化学反应

将具有导电功能的聚(4-羧酸钠苯基)乙炔阴离子(PCPA)与具有生物活性的DNA聚阴离子交替与重氮树脂聚阳离子(DR)进行自组装,可以得到层重复单元为DR／DNA／DR／PCPA的三夹层聚电解质自组装膜。重氮树脂聚阳离子在紫外光照射下可与聚阴离子发生光化学反应,使层与层之间的离子键连接转化为共价键连接,从而制备稳定的纳米级超薄膜。本文用红外光谱法对此类聚电解质自组装膜的光化学反应过程进行了研究。     

重氮树脂型聚电解质复合物与SDS相互作用研究

由于聚电解质与表面活性剂的相互作用具有很多特别的性质而倍受关注［１～１０］,但具有感光性的重氮树脂作为正离子聚电解质与表面活性剂相互作用尚未见报道．本文研究了重氮树脂（ＤＲ）与聚苯乙烯磺酸钠（ＰＳＳ）形成的聚电解复合物（ＤＲ－ＰＳＳ）与十二烷基硫酸钠...     

二苯胺型重氮盐的光、热分解及其树脂的复合物和自组装研究

本论文分为两部分,第一部分为二苯胺型重氮盐的光、热分解及其树脂复合物的研究.合成了4种二苯胺型重氮盐(咔唑-3-重氮盐,C-3-DS;N-乙基咔唑-3-重氮盐,NEC-3-DS;N-苄基咔唑-3-重氮盐,NBC3-DS;N-甲基-二苯胺-2-硝基-4-重氮盐,MNDDS)及其与甲醛缩合的树脂.研究了二苯胺型重氮盐的光、热分解,结果表明:在醇中,二苯胺型重氮盐的光解主要生成重氮基被乙氧基取代的产物;热解几乎生成唯一的重氮基被氢取代的产物.而硝基取代的二苯胺-4-重氮盐,在水中,无论是光解还是热解,其产物基本相同. 对重氮树脂作为聚正离子与磺酸基聚负离子间的相互作用进行了研究,结果表明重氮树脂与聚负离子在小于1:1时形成不溶性的聚电解质复合物沉淀,过量聚负离子的加入导致沉淀溶解.带大的疏水基团的聚电解质使溶解加快.初步阐明了聚电解质复合物溶解过程中疏水相互作用的贡献.2001年6月通过博士论文答辩     

重氮树脂—聚磷酸复合物

带有相反电荷 (通常在侧链 )的聚电解质 ,通过静电相互作用形成的复合物 ,称聚电解质复合物 (ＰＥＣ) .ＰＥＣ已有很多研究[1～ 3] ,也有一些应用的报道[4,5] .重氮树脂 (ＤＲ) ,一种由二苯胺 4 重氮盐与多聚甲醛在浓硫酸中缩合得到的缩聚物[6] ,因侧链带重氮基 ,所以是正离子聚电解质 .它能与各种负离子聚电解质生成感光性的ＰＥＣ ,并可用作光成像体系的感光剂[7,8] .ＤＲ与聚磷酸 (ＰＰＡ)生成重氮基为正离子 ,磷酸基为负离子的复合物 ,这种复合物文献上未有过报道 .本文初步研究了这种复合物的制备与性质 .1　重氮树脂 聚磷酸复合物 (…     

聚(对乙烯基苯酚)的合成及其与重氮树脂的氢键自组装研究

带相反电荷的聚电解质,交替沉积在基片,形成超薄有序膜,通常称为静电自组装,自1991年由Decher首次阐明以来,静电自组装技术引起了广泛重视,利用氢键相互作用的氢键自组装1997年才有报道,沈家骢、张希等从聚丙烯酸和聚乙烯基吡啶通过氢键组装了有序超薄膜。和乙烯基吡啶通过氢键组装超薄膜的制备。由于静电力和氢键均很弱,此类膜对极性溶剂不稳定,如在DMF中会离解而遭破坏,我们曾报道重氮树脂（DR）与酚醛树脂间通过氢键的自组装,本文报道聚（对乙烯基苯酚）（PVPh）的制备及春与重氮树脂（DR）间的氢键相经作用,并结合光照,制备了对极性溶剂稳定的超薄膜。     

酚醛型重氮树脂复合物及自组装超薄膜的制备与应用

不同的高分子链之间可通过次价键而聚集,形成高分子复合物(polymer-polymer omplex).其中,研究最为深入的是基于库仑力的聚电解质复合物(polyelectrolyer complex,PEC)近年来一种继L-B膜技术之后,被称为"层-层”自组装(1ayer-by-layer self-assembly)的技术受到了越来越多的关注自组装技术所组装的分子大多是聚电解质,通常是将带不同电荷的聚电解质分子在水溶剂中交替地组装到片基上,实际上就是在固液界面一层一层地形成聚电解质复合物通过其它弱相互作用如氢键、电荷转移等高分子的自组装基本类似.因此可以说,对高分子自组装的研究基本上是对高分子复合物研究的延伸本论文对重氮树脂-酚醛树脂的感光性复合物以及基于重氮树脂的"层-层”自组装多层膜进行了研究,主要结果如下: 2001年6月通过博士论文答辩     

表面印迹交替层状组装薄膜

在简要概述非常规交替层状组装这一进展后,重点总结了如何利用非常规交替层状组装以实现表面印迹膜的制备.模板分子与聚电解质在溶液中组装形成超分子复合物,然后以此超分子复合物为构筑基元,与感光性高分子,如重氮树脂,通过常规交替层状组装形成聚合物多层膜.利用聚合物多层膜之间的光化学反应形成稳定的多层膜,然后去除模板分子得到分子...     

感光性聚电解质复合物与十二烷基硫酸钠的相互作用及聚电解质复合物的自组装研究

论文的第一部分研究二苯胺-4-重氮树脂(DR)与十二烷基硫酸钠(SDS)的相互作用,发现重氮树脂(DR)水溶液中加入SDS后,体系先产生重氮树脂-SDS复合物沉淀,继续加入SDS,该沉淀又会重新溶解.SDS与重氮树脂间的疏水相互作用对这一现象作了解释.另外,还发现SDS水溶液可以溶解难溶的聚电解质复合物,并通过比较溶解前后重氮基的热分解温度及红外振动吸收来判定其所对应的反离子,从而确定了该溶解的过程是SDS先将聚电解质复合物拆开,再通过疏水相互作用将带有相反电荷的聚电解质溶解.用SDS水溶液溶解的含有感光性重氮树脂的聚电解质复合物可用于阴图PS版感光液的制备,得到一种稳定好,污染小,成本低的感光液.     

聚电解质复合物在表面活性剂水溶液中的溶解机理

聚电解质复合物 ( PEC)因其独特的物理化学性质而受到广泛关注 .对其研究主要集中在其结构及形成的影响因素 ,如聚电解质的分子量 [1,2 ] 、电荷密度、电荷强弱 [1,2 ] 及溶液离子强度 [3,4 ] ,而很少有关于聚电解质复合物溶解性的报道 [5,6 ] .一般认为组成 PEC的聚正离子 ( PC)和聚负离子 ( PA)之间 ,通过离子键形成网状交联结构而不溶于水及有机溶剂 .只有一种特殊的溶剂体系屏蔽溶剂可溶解此类复合物[7,8] .本文报道一类新的聚电解质复合物 :以二苯胺重氮树脂 DR为聚正离子 ,苯乙烯 -马来酸酐碱性水解物 ( PSMNa)为聚负离子的 P…     

Self-assembly of homopolymer and copolymers of N-4-hydroxyphenyl-acrylamide with diazoresin via H-bonding attraction

A kind of photoactive multilayer utrathin films has been fabricated via H-bonding attraction from hydroxyphenyl containing polymers as H-donor and diazoresin (DR) as H-acceptor by means of a self-assembly technique. The layer-by-layer deposition of two components is monitored spectrometrically and shows that the UV-VIS absorbance of the film increases linearly both at 250 nm (absorption of benzene nucleus) and at 383 nm (absorption of diazonium group), which indicates that the fabrication proceeds regularly. The nature of H-bonding between layers was verified by the determination of IR spectra of the film fabricated directly on a CaF₂ wafer. The stability of the films toward polar solvents increases dramatically after UV irradiation of the films. It was confirmed provisionally that the bond nature between the layers of the film changes from H-bonding to covalent bonding under UV irradiation. The photodecomposition of the -N₂⁺ groups of the film under UV light follows first order reaction kinetics and a mechanism of the photoreaction has been tentatively proposed.     

Stable thin films and hollow spheres composing chiral polyaniline composites

Chiral polyaniline composite (CPAC) thin films were fabricated by self-assembly using diazoresin (DR) and CPAC. The weak linkage between the DR and CPAC of the film will convert to covalent bonds under UV irradiation or heating, and the thin film becomes very stable toward polar solvents and electrolyte aqueous solutions. Core-shell particles with stable DR/CPAC shell and polystyrene (PS) core can be prepared by similar methods. After the PS core is removed by chemical etching, stable DR/CPAC hollow spheres were obtained. Circular dichroism spectra and cyclic voltammetry measurements show that the DR/CPAC thin films are chirally active and possess good electrochemical stability.     

聚4-重氮基苯乙烯与聚苯乙烯磺酸钠的自组装

1991年Ｄｅｃｈｅｒ等将带相反电荷的聚电解质 ,于水溶液中交替沉积在片基上 ,制备了多层超薄膜[1] ,这种制膜方法现称为静电自组装 .它操作简单 ,无需专用设备 ;一般在水体系进行 ,对环境友好 ;静电力比范德华力强 ,使它比ＬＢ膜稳定 ,所以近年来有很大发展[2 ] .现在自组装成膜驱动力已从静电力扩展到氢键力、电荷转移相互作用、疏水相互作用等 ,用于组装的组分也从聚电解质扩展到多官能团小分子、胶体粒子、无机纳米颗粒 ,ＤＮＡ、蛋白质等生物大分子等[3～ 11] .虽然自组装膜比ＬＢ膜稳定 ,但它也不耐极性溶剂、电解质水溶液等侵蚀 .如…     

Surface molecularly imprinted polydopamine films for recognition of immunoglobulin G

We have prepared a surface imprinted polymer (SIP) film for label-free recognition of immunoglobulin G (IgG). The IgG-SIPs were obtained by covalent immobilization of IgG via a cleavable covalent bond and a suitable spacer unit to a gold electrode, followed by electrodepostion of a nm-thin film of polydopamine (PDA). The IgG was then removed by destruction of the cleavable bond so that complementary binding sites were created on the surface of the film. IgG-SIPs with various thicknesses of the PDA films were compared with respect to their affinity to IgG using a quartz crystal microbalance combined with flow injection analysis. The films were also characterized by cyclic voltammetry and scanning electron microscopy. The IgG-SIPs with a film thickness of around 17 nm showed the most pronounced imprinting effect (IF 1.66) and a binding constant of 296 nM.

Covalent attachment and hybridization of DNA oligonucleotides on patterned single-walled carbon nanotube films

DNA oligonucleotides were covalently immobilized to prepatterned single-walled carbon nanotube (SWNT) multilayer films by amidation. SWNT multilayer films were constructed via consecutive condensation reactions creating stacks of functionalized SWNT layers linked together by 4,4'-oxydianiline. Aminated- or carboxylated-DNA oligonucleotides were covalently immobilized to the respective carboxylated or aminated SWNT multilayer films through amide bond formation using 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride. UV-vis-NIR spectroscopic analysis indicated that the SWNT film surface density increased uniformly according to the number of reaction cycles. Scanning electron microscopy and contact angle measurements of the SWNT multilayer film revealed a uniform coverage over the substrate surface. The covalent attachment of DNA oligonucleotides to the SWNT multilayer films and their subsequent hybridization with complementary oligonucleotides were verified using X-ray photoelectron spectroscopy and fluorescence-based measurements. This is the first report demonstrating that DNA oligonucleotides can be covalently attached to immobilized SWNT multilayer films. The anchored DNA oligonucleotides were shown to exhibit excellent specificity, realizing their potential in future biosensor applications.     

Electrodeposition of gold particles on aluminum substrates containing copper

Electrodeposition of adhesive metal films on aluminum is traditionally preceded by the zincate process, which activates the aluminum surface. This paper presents an alternative approach for activation of aluminum by using films containing 99.5% aluminum and 0.5% copper. Aluminum/copper films are made amenable for subsequent electrodeposition by anodization followed by chemical etching of aluminum oxide. The electrodeposition of gold is monitored with electrochemical impedance spectroscopy (EIS). Analysis of EIS data suggests that electrodeposition of gold increases the interfacial capacitance from values typical for electrodes with thin oxide layers to values typical for metal electrodes. Scanning electron microscopy examination of aluminum/copper films following gold electrodeposition shows the presence of gold particles with densities of 10(5)-10(7) particles cm(-2). The relative standard deviation of mean particle diameters is approximately 25%. Evaluation of the micrographs suggests that the electrodeposition occurs by instantaneous nucleation followed by growth of three-dimensional semispherical particles. The gold particles, which are electrically connected to the conductive aluminum/copper film, support a reversible faradaic process for a soluble redox couple. The deposited gold particles are suitable for subsequent metallization of aluminum and fabrication of particle-type films with interesting catalytic, electrical, and optical properties.     

Simple and rapid methods for the fabrication of polymeric and glass chips for using in analytical chemistry

This paper describes simple and rapid methods for the fabrication of glass and polymeric chips for routine analytical applications. The methods are easily interfaced to the general laboratory environment and do not require special clean room facilities or expensive instruments. Glass microchips were fabricated by etching with HF solution. Microfluidic channels were designed with CAD program and transferred onto a sheet of commercial polymeric self-adhesive (PSA) film by a cutter plotter. The PSA film was used as a mask for etching process. The etching rate was about 7 μm min⁻¹. A cover glass plate was sealed on the top of etched substrate by using polycellulose (cellophane). Polymeric microchips were fabricated by sawing with a jigsaw. Commercial polycarbonate (PC) was used as a substrate and two iron sheets were used as leader masks. While this restricts us to the fabrication of straight channels, it is however, much faster and less complicated than the other methods. The chip comprised three polymeric plates and the channels were created in the middle plate. Thermal bonding was used to bond three layers of the microfluidic chip. With this method, we could achieve simple channels with the width of about 200 μm. The channel depth depends on the polymeric plate thickness. Fabricated channels were accurate without any sinuosity or sideshow.     

Why is copper locally etched by scanning electrochemical microscopy?

The etching of thin copper films by scanning electrochemical microscopy (SECM) was investigated. It is not trivial that locally injected charge by an oxidized mediator will lead to dissolution of copper as the charge can easily be dissipated by lateral charge propagation. We studied the effect of different parameters, such as thickness of the Cu film and concentration of the mediator, on the efficiency of etching. The feedback current is the sum of three charge transfer contributions: diffusion of mediator species, chemical reaction on the surface and lateral charge propagation across the copper film. We have introduced an approach for isolating the lateral contribution and studied the parameters affecting the fate of the locally injected charge. We found that etching becomes effective once the lateral contribution cannot dissipate the locally injected charge. This occurs as the concentration of the etchant increases or the film thickness decreases. Measuring the steady-state current above Cu films with different thickness, allowed estimating the potential difference across the Cu area underneath the tip. We conclude that driving local processes, such as etching, depends on creating a mechanism which maintains the injected charge focused.     

智能响应与自修复的层层组装聚合物膜

具有刺激响应性和自修复功能的复合膜是重要的仿生功能膜材料.层层组装是一种基于物质交替沉积而制备复合膜的方法,可以实现膜的结构和组成的精确调控.通过结构与组成的精确调控,基于层层组装制备的微米厚度的聚电解质厚膜可以对外界刺激产生快速有效的响应,因而在制备智能仿生膜材料方面具有重要的价值.本文以作者的研究结果为基础,阐明了基于层层组装的聚电解质膜可以成功用于制备湿度和温度响应的双结构自支持膜和高效的促动器及行走机器,以及自修复超疏水和划痕修复聚电解质膜.