导电聚合物电致变色材料*

由于在电致变色、显示、军事等领域的广泛应用,电致变色材料受到了人们越来越多的关注。本文综述了聚苯胺(PANI)类、聚噻吩(PTh)类、聚吡咯(PPy)类及复合导电聚合物电致变色材料的性能及其研究进展,同时简单地叙述了这些材料作为电致变色材料的应用前景,指出具有丰富颜色变化、良好的稳定性及成膜性的共聚物及有机/无机复合导电聚合物材料是未来电致变色材料发展的方向。     

导电聚合物

导电聚合物是20世纪70年代发展起来的一个研究领域,因其诱人的应用前景受到广泛重视,本文介绍了导电聚合物的发展和发展历史,综述了导电聚合物的结构和掺杂特征,制造方法,电导和电化学特性及其本征态共轭聚合物的光电特性,对导电聚合物当前的研究热点和应用前景进行了讨论。     

导电聚合物LB膜

本文回顾了ＬＢ膜技术在导电聚合物体系中的利用，内容涉及共轭型导电聚合物（包括聚吡咯、聚噻吩、聚对亚苯基亚乙烯基、聚苯胺及其衍生物）ＬＢ膜的制备、结构表征、电导率与分子结构和分子堆砌之间的关系以及其他导电聚合物ＬＢ膜的研究现状。     

固态导电聚合物多色电致变色器件的制备

制备了基于聚3-甲基噻吩(P3MeT)和聚苯胺(PANI)的两种结构(侧面结构和垂直结构)固态导电聚合物多色电致变色器件(ECD). 采用电化学现场紫外-可见光谱法研究了侧面结构固态ECD的电致变色特性, P3MeT-ECD显示出蓝色和红色的可逆变化, PANI-ECD显示出墨绿色和黄绿色的可逆变化, 同时采用P3MeT和PANI作变色材料的P3MeT-PANI-ECD可以实现红、蓝、墨绿和草绿多色变化. 用激光雕刻微型化P3MeT-PANI变色层组装制得的侧面结构固态P3MeT-PANI-ECD控制合适电压也可多色变化. 另外, 用CeO₂-TiO₂作为P3MeT-PANI对电极的垂直结构固态P3MeT-PANI-ECD在实现红、蓝、墨绿和草绿多色变化的同时, 也可进行四色自由搭配选择.     

可溶性导电高分子的合成

本文以聚乙炔类导电高分子为重点简要地综述了可溶性导电高分子的合成与研究现状。     

Electrochemical Post‐Functionalization of Conducting Polymers

This article summarizes recent progress in the post‐functionalization of conjugated polymers by electrochemical methods. These electrochemical polymer reactions typically proceed via electrochemical doping of a conjugated polymer film, followed by chemical transformation. Examples include the quantitative oxidative fluorination of polyfluorenes and oxidative halogenation of polythiophenes, as well as the reductive hydrogenation of polyfluorenones. The degree of functionalization, otherwise known as the reaction ratio, can be controlled by varying the charge passed through the polymer, allowing the optoelectronic properties of the conjugated polymers to be tailored. Wireless bipolar electrodes with an in‐plane potential distribution are also useful with regard to the electrochemical doping and reaction of conjugated polymers and allow the synthesis of films exhibiting composition gradients. Such bipolar electrochemistry can induce multiple reaction sites during electrochemical polymer reactions.

     

L-Dopa Synthesis on Conducting Polymers

With regards to the synthesis of L-Dopa (l-3,4-dihydroxy phenylalanine) two types of biosensors were designed by immobilizing tyrosinase on conducting polymers; polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT). PPy and PEDOT were synthesized electrochemically and tyrosinase immobilized by entrapment during electropolymerization. The kinetic parameters of the designed biosensors, maximum reaction rate of the enzyme (V_max) and Michaelis Menten constant (K_m) were determined. V_max were found as 0.013 for PPy matrix and 0.041 μ mol/min.electrode for PEDOT matrix. K_m values were determined as 3.7 and 5.2mM for PPy and PEDOT matrices respectively. Calibration curves for enzyme activity vs. substrate concentration were drawn for the range of 0.8 to 2.5 mM L-Tyrosine. Optimum temperature and pH, operational and shelf life stabilities of immobilized enzyme were also examined.     

Direct Writing of Conducting Polymers

Described herein is a new printing method—direct writing of conducting polymers (CPs)—based on pipette‐tip localized continuous electrochemical growth. A single barrel micropipette containing a metal wire (Pt) is filled with a mixture of monomer, supporting electrolyte, and an appropriate solvent. A droplet at the tip of the pipette contacts the substrate, which becomes the working electrode of a micro‐electrochemical cell confined to the tip droplet and the pipette. The metallic wire in the pipette acts as both counter and reference electrode. Electropolymerization forms the CP on the working electrode in a pattern controlled by the movement of the pipette. In this study, various width poly(pyrrole) 2D and 3D structures are extruded and characterized in terms of microcyclic voltammetry, Raman spectroscopy, and scanning electron microscopy.

     

导电聚合物的结构和性能表征方法

综述了导电聚合物的结构与性能表征的几种经典和现代的仪器方法，指出了这些方法的特点及用途。     

离子液体在导电高分子中的应用

综述了离子液体作为介质，在导电高分子合成及其电化学性能测试，以及导电高分子电化学器件中（电化学电容、发光电化学池、驱动器、太阳能电池）的最新研究进展。在此基础上。展望了离子液体在导电高分子中的应用前景。     

Application of Conducting Polymers in Chemical Analysis

This paper presents recent achievements in the field of analytical application of conducting polymers, most of which were published in the last five years. Based on 171 references mainly to original papers in international scientific journals, the applications of conducting polymers in the design of electrochemical and optical sensors, enzymatic biosensors and immunosensors are reviewed together with applications in analytical preconcentration procedures and high-performance separation techniques.     

导电高聚物的分子设计问题

本文综述了导电高聚物分子设计的一些实验事实和必需考虑的因素。文章涉及的内容有分子性质与固体性质,共轭长度和链的取向与高电导的关系,对离子和离子交换,材料设计——溶解性、加工性和分子复合材料。     

导电聚合物超级电容器电极材料*

导电聚合物（聚苯胺,聚吡咯,聚噻吩）作为超级电容器电极材料的研究引起了人们广泛的兴趣,该类材料制备的超级电容器具有成本低、容量高、充放电时间短、环境友好和安全性高等优点。本文综述了近年来基于导电聚合物及其与无机材料（碳材料/金属氧化物材料）复合所得电极材料在超级电容器中的应用进展,指出具有纳米结构导电聚合物材料及导电聚合物与无机纳米材料的复合是超级电容器电极材料研究的重要发展方向。     

Proton‐Conducting Magnetic Coordination Polymers

Three isostructural lanthanide‐based two‐ dimensional coordination polymers (CPs) {[Ln₂(L)₃(H₂O)₂]_n ? 2n CH₃OH) ? 2n H₂O} (Ln=Gd³⁺ ( 1 ), Tb³⁺ ( 2 ), Dy³⁺ ( 3 ); H₂L=cyclobutane‐1,1‐dicarboxylic acid) were synthesized by using a low molecular weight dicarboxylate ligand and characterized. Single‐crystal structure analysis showed that in complexes 1 – 3 lanthanide centers are connected by μ₃‐bridging cyclobutanedicarboxylate ligands along the c axis to form a rod‐shaped infinite 1D coordination chain, which is further linked with nearby chains by μ₄‐connected cyclobutanedicarboxylate ligands to form 2D CPs in the bc plane. Viewing the packing of the complexes down the b axis reveals that the lattice methanol molecules are located in the interlayer space between the adjacent 2D layers and form H‐bonds with lattice and coordinated water molecules to form 1D chains. Magnetic properties of complexes 1 – 3 were thoroughly investigated. Complex 1 exhibits dominant ferromagnetic interaction between two nearby gadolinium centers and also acts as a cryogenic magnetic refrigerant having a significant magnetic entropy change of ?ΔS_m=32.8 J kg^?1 K^?1 for ΔH=7 T at 4 K (calculated from isothermal magnetization data). Complex 3 shows slow relaxation of magnetization below 10 K. Impedance analysis revealed that the complexes show humidity‐dependent proton conductivity (σ=1.5×10^?5 S cm^?1 for 1 , σ=2.07×10^?4 S cm^?1 for 2 , and σ=1.1×10^?3 S cm^?1 for 3 ) at elevated temperature (>75 °C). They retain the conductivity for up to 10 h at high temperature and high humidity. Furthermore, the proton conductivity results were correlated with the number of water molecules from the water‐vapor adsorption measurements. Water‐vapor adsorption studies showed hysteretic and two‐step water vapor adsorption (182000 μL g^?1 for 1 , 184000 μL g^?1 for 2 , and 1874000 μL g^?1 for 3 ) in the experimental pressure range. Simulation of water‐vapor adsorption by the Monte Carlo method (for 1 ) confirmed the high density of adsorbed water molecules, preferentially in the interlayer space between the 2D layers.     

Recent Advances in Electropolymerized Conducting Polymers in Amperometric Biosensors

Conducting electroactive polymers (CPs) are materials discovered just over 20 years ago which have aroused considerable interest on account of their electronic conducting properties and unique chemical and biochemical properties. Consequently, they have numerous (bio)analytical and technological applications. CPs are easily synthesized and deposited onto the conductive surface of a given substrate from monomer solutions by electrochemical polymerization with precise electrochemical control of their formation rate and thickness. Coating electrodes with CPs under mild conditions opens up enormous possibilities for the immobilization of biomolecules and bioaffinity or biorecognizing reagents, the improvement of their electrocatalytic properties, rapid electron transfer and direct communication to produce a range of analytical signals and new analytical applications. Co-immobilization of other molecules (enzymatic co-factors or charge-transfer mediators) by entrapment within electropolymerized films or by covalent binding on these films permits straightforward fabrication of reagentless biosensors. The characteristics of CPs and their uses, mainly in amperometric biosensors, are reviewed. The most recent applications and lines of research related to CP films are summarized in the different sections of the paper, and probable future trends are discussed.     

离子液体应用于电合成导电聚合物*

自20世纪70年代导电聚合物发现以来,聚吡咯、聚苯胺、聚噻吩、聚（3,4-乙撑二氧噻吩）、聚对苯及其衍生物等,以其特殊的电子、电化学、光学性质以及巨大应用潜力受到广泛关注。离子液体是一类在室温或接近室温时呈液态的离子化合物,作为一类环境友好的新型绿色溶剂,具有很多独特的物理化学性质。本文综述了离子液体作为反应介质、支持电解质、测试介质以及离子液体参与形成的聚集体,在导电聚合物的电化学合成以及电化学性质测试中的研究进展,并展望了发展趋势。     

Applications of Oligomers for Nanostructured Conducting Polymers

This Feature Article provides an overview of the distinctive nanostructures that aniline oligomers form and the applications of these oligomers for shaping the nanoscale morphologies and chirality of conducting polymers. We focus on the synthetic methods for achieving such goals and highlight the underlying mechanisms. The clear advantages of each method and their possible drawbacks are discussed. Assembly and applications of these novel organic (semi)conducting nanomaterials are also outlined. We conclude this article with our perspective on the main challenges, new opportunities, and future directions for this nascent yet vibrant field of research.

     

Chemical Biological Sensors Based on Advances in Conducting Electroactive Polymers

Advances in conducting electroactive polymers (CEPs) have driven the design of novel chemical and biochemical sensors. The redox properties of CEPs have been intensely studied for more than two decades with emphasis on their synthesis and characterization. Little attention has been paid to the importance of mechanism in sensor designs. However, in order to design robust and stable sensors, it is important to understand how the polymer structure, morphology, adhesion properties and microenvironment affect sensor performance. This work describes how chemical and biological sensors have been designed, fabricated, characterized and tested based on the fundamental understanding in CEPs. The use of photopolymerized conducting polymers in sensor designs is described. Four focus areas are presented in which the electronic properties of CEPs have enabled the design of novel sensors for organics, nucleic acids, biological molecules, vapors and metal ions.     

导电聚合物在药物可控释放领域的应用

导电聚合物(conducting polymers,CPs)是一类与金属具有相似的电、磁和光学特性的有机聚合物,电刺激会引起其氧化-还原状态的改变,从而导致CPs的电荷量、掺杂水平、导电性以及体积发生变化.利用CPs的这些特性,可将其用于药物、蛋白质以及基因等的传递和可控释放.通过对CPs基体进行化学物理修饰,可以扩大CPs基体的载药品种、提高载药量以及优化药物控释手段.本文简要介绍了CPs的性能和制备方法,对CPs基药物传递体系的药物担载和释放机理进行了详细的讨论,并归纳总结了近年来国内外以CPs为基体的药物传递体系的研究进展,最后对CPs基药物传递体系所面临的问题和未来发展进行了总结和展望.     

Thienylmethylene Oxindole Based Conjugated Polymers via Direct Arylation Polymerization and Their Electrochromic Properties

Direct arylation methods have been used to polymerize thienylmethylene oxindoles(TEIs) and 3,3-bis[[(2-ethylhexyl)oxy]methyl]-3,4-dihydro-2 H-thieno-[3,4-b][1,4]dioxepin(ProDOT) for new donor-acceptor conjugated polymers. The polymers exhibited blue hues in neutralstate with distinct color-to-transmissive reversible electrochromic switching under applied potentials from 0 V to +1.5 V, and showed high coloration efficiencies(436-438 cm~2·C~(-1)) in near-infrared regions with high switching speeds around 1-2 s under ambient conditions.