荧光共轭聚合物在生物大分子检测中的应用*

共轭聚合物因其具有π-电子体系及共轭离域结构,一般都具有优异的发光性能,其发光强度和发射波长会随被检测化合物结构的不同而发生特异性响应,特别是在与被检测物相互作用过程中所产生电荷和能量能够沿共轭分子链进行有效传递,成倍放大这种作用,从而有效提高了检测灵敏度,这比相应的小分子化合物更具有优越性。目前共轭聚合物已被用于开发新型化学、生物传感器,尤其是在生物分子检测方面的应用得到迅速的发展。本文总结了近年来荧光共轭聚合物在生物传感方面的研究进展,主要讨论共轭聚合物在蛋白质、核酸及毒素检测中的应用。     

Photodynamics of a PV Trimer in High‐Viscosity Solvents and in PMMA Films: A New Insight into Energy Transfer versus Conformational Relaxation in Conjugated Polymers

Non‐Stokes–Einstein relaxation : The rate constant of conformational relaxation of a phenylenevinylene trimer (see picture) in different solvents is proportional to η^?α, with α values decreasing from close to unity (low viscosity) to zero at sufficiently high solvent viscosity. This behaviour is attributed to the flexible methylbutyl side chains of the trimer, which partially screen the solvent friction.

     

Conjugated Molecules and Polymers in Secondary Batteries: A Perspective

Intrinsically conducting polymers constituting a subclass of macromolecules, as well as a still growing family of large, conjugated molecules, oligomers, and polymers, have attracted research interest for the recent decades. Closely corresponding to the fascination of these materials, combining typical properties of organic polymers and metallic materials, numerous applications have been suggested, explored, and sometimes transferred into products. In electrochemistry, they have been used in various functions beyond the initially proposed and obvious application as active masses in devices for electrochemical energy conversion and storage. This perspective contribution wraps up basic facts that are necessary to understand the behavior and properties of the oligo and polymers and their behavior in electrochemical cells for energy conversion by electrode reactions and associated energy storage. Representative examples are presented and discussed, and an overview of the state of research and development is provided. Particular attention is paid to stability and related aspects of practical importance. Future trends and perspectives are indicated.     

Nanostructured Conjugated Polymers for Energy‐Related Applications beyond Solar Cells

To meet the ever‐increasing requirements for the next generation of sustainable and versatile energy‐related devices, conjugated polymers, which have potential advantages over small molecules and inorganic materials, are among the most promising types of green candidates. The properties of conjugated polymers can be tuned through modification of the structure and incorporation of different functional moieties. In addition, superior performances can be achieved as a result of the advantages of nanostructures, such as their large surface areas and the shortened pathways for charge transfer. Therefore, nanostructured conjugated polymers with different properties can be obtained to be applied in different energy‐related organic devices. This review focuses on the application and performance of the recently reported nanostructured conjugated polymers for high‐performance devices, including rechargeable lithium batteries, microbial fuel cells (MFCs), thermoelectric generators, and photocatalytic systems. The design strategies, reaction mechanisms, advantages, and limitations of nanostructured conjugated polymers are further discussed in each section. Finally, possible routes to improve the performances of the current systems are also included in the conclusion.     

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。     

共轭聚合物离子荧光化学传感器

荧光传感器能够将分子识别的信息转换成荧光信号,荧光法在灵敏度、选择性和实时原位检测等方面优势突出,最近已引起了人们很大的兴趣。本文主要介绍以共轭聚合物为基础的离子荧光化学传感器的近期研究进展,重点综述了共轭聚合物的荧光化学传感器在阳离子识别检测中的分子设计、合成、作用机理和应用,并展望了该领域的发展方向。     

Synthesis of Water‐Soluble Dendritic Conjugated Polymers for Fluorescent DNA Assays

Summary: Cationic water‐soluble dendritic poly(fluorene)s with positively charged amines on the exterior (PFP‐G_0–2) can be prepared by a macromonomer (generation‐by‐generation) approach. The charge densities of PFP‐G_0–2 can control their distances to DNA by electrostatic interactions. The PFP‐G₂ with higher generation of dendritic side chains possesses a higher charge density, and gives rise to efficient fluorescence resonance energy transfer (FRET) to a signaling fluorescein labeled at the terminus of DNA. These new conjugated polymers form less aggregates and yield more efficient FRET in a tetrahydrofuran/H₂O mixed solvent as compared to in pure water. The sensitivity of the DNA sensor is improved by utilizing highly dendritic conjugated polymers.

Structure of the dendritic conjugated polymer PFP‐G₂.     

High Performance Phototransistors of a Planar Conjugated Copolymer

A planar conjugated copolymer named HXS‐1 was applied in thin film phototransistors. Similar to organic field‐effect transistors using V_G to control the source‐drain current, in phototransistors, the light is used to substitute V_G as an independent variable to control the output of the transistors to realize light detection and signal magnification in a single organic device. All devices exhibited high performance with an on/off ratio up to 4.6 × 10⁴ (the highest on/off ratio of organic or polymer phototransistors), which could be assigned to i) the wide absorption features of HXS‐1 in the whole UV‐vis range, ii) the ideal HOMO energy level of HXS‐1 (5.21 eV) to align with Au electrodes (5.2 eV) and iii) the high mobility of the polymer thin films (∼0.06 cm²/Vs). Moreover, the devices, both under continuous operation conditions and long term measurement conditions, exhibited excellent stability, indicating potential applications of the devices in polymer‐based optoelectronics.

     

Porous Organic Polymer Films with Tunable Work Functions and Selective Hole and Electron Flows for Energy Conversions

Organic optoelectronics are promising technologies for energy conversion. However, the electrode interlayer, a key material between active layers and conducting electrodes that controls the transport of charge carriers in and out of devices, is still a chemical challenge. Herein, we report a class of porous organic polymers with tunable work function as hole‐ and electron‐selective electrode interlayers. The network with organoborane and carbazole units exhibits extremely low work‐function‐selective electron flow; while upon ionic ligation and electro‐oxidation, the network significantly increases the work function and turns into hole conduction. We demonstrate their outstanding functions as anode and cathode interlayers in energy‐converting solar cells and light‐emitting diodes.     

Single Base Pair Mismatch Detection Using Cationic Conjugated Polymers through Fluorescence Resonance Energy Transfer

A simple method using water‐soluble conjugated polymers and a DNA intercalator has been proposed for single base pair mismatch detection with enhanced detection efficiency. Fluorescence resonance energy transfer (FRET) was used as an indicator for unwinding of dsDNA due to base pair mismatch at elevated temperatures. The optical amplification effect of the CPs helps to achieve enhanced detection efficiency.

     

电磷光发光聚合物*

电致磷光材料可以同时利用单线态和三线态激子发光,具有较高的发光效率,受到人们广泛的关注。本文综述了近年来通过共价键将磷光配合物单元连接在高分子链上制备电磷光发光聚合物的研究进展。总结了主链型、侧链型以及超支化结构的电磷光发光聚合物的研究进展,评述了上述几类电磷光聚合物的发光性能与分子结构的关系。最后从电磷光发光聚合物的分子结构设计出发,在电磷光发光聚合物领域业已取得进展的基础上,分析了电磷光发光聚合物在电致发光领域应用中存在的一些问题,并展望了电磷光聚合物今后的发展方向。     

Metallacycle Transfer and its Link to Light‐Emitting Materials and Conjugated Polymers

Major advances in optoelectronic technologies (e. g., solar cells, organic light‐emitting diodes, etc…) are prefaced by the discovery of new synthetic methodologies. In this review, the key role of the Fagan‐Nugent reaction in enabling our team (and others) to gain access to new building blocks for luminescent materials and conjugated polymers bearing p‐block elements will be described. The Fagan‐Nugent reaction is extremely powerful as a synthetic tool since the efficient zirconium‐element atom exchange involved affords a wide range of unsaturated inorganic heterocycles of controllable composition and function.     

Conformation Control of Conjugated Polymers

In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π–π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization.     

Controlled Synthesis of Conjugated Microporous Polymer Films: Versatile Platforms for Highly Sensitive and Label‐Free Chemo‐ and Biosensing

Conjugated microporous polymers (CMPs), in which rigid building blocks form robust networks, are usually synthesized as insoluble and unprocessable powders. We developed a methodology using electropolymerization for the synthesis of thin CMP films. The thickness of these films is synthetically controllable, ranging from nanometers to micrometers, and they are obtained on substrates or as freestanding films. The CMP films combine a number of striking physical properties, including high porosity, extended π conjugation, facilitated exciton delocalization, and high‐rate electron transfer. We explored the CMP films as versatile platforms for highly sensitive and label‐free chemo‐ and biosensing of electron‐rich and electron‐poor arenes, metal ions, dopamine, and hypochloroic acid, featuring rapid response, excellent selectivity, and robust reusability.     

Conjugated Polymers Atypically Prepared in Water

Processability remains a fundamental issue for the implementation of conducting polymer technology. A simple synthetic route towards processable precursors to conducting polymers (main chain and side chain) was developed using commercially available materials. These soluble precursor systems were converted to conjugated polymers electrochemically in aqueous media, offering a cheaper and greener method of processing. Oxidative conversion in aqueous and organic media each produced equivalent electrochromics. The precursor method enhances the yield of the electrochromic polymer obtained over that of electrodeposition, and it relies on a less corruptible electrolyte bath. However, electrochemical conversion of the precursor polymers often relies on organic salts and solvents. The ability to achieve oxidative conversion in brine offers a less costly and a more environmentally friendly processing step. It is also beneficial for biological applications. The electrochromics obtained herein were evaluated for electronic, spectral, and morphological properties.     

树枝状共轭聚合物研究

本文介绍了树枝状共轭聚合物的最新发展,包括全共轭、部分共轭树枝状聚合物及树枝化共轭聚合物的特点及其在电致发光、电极、传感器以及光探测等领域的功能化应用;详细讨论了包括代数、支化单元、端基、核、金属离子的络合等结构因素以及溶剂和浓度等工艺因素对电荷传输的影响;并进一步提出该领域研究前景及有待于解决的问题.     

树枝状共轭聚合物研究

本文介绍了树枝状共轭聚合物的最新发展,包括全共轭、部分共轭树枝状聚合物及树枝化共轭聚合物的特点及其在电致发光、电极、传感器以及光探测等领域的功能化应用;详细讨论了包括代数、支化单元、端基、核、金属离子的络合等结构因素以及溶剂和浓度等工艺因素对电荷传输的影响;并进一步提出该领域研究前景及有待于解决的问题。     

发光性液晶共轭聚合物的研究进展发光性液晶共轭聚合物的研究进展

综述了可用做发光材料的液晶共轭聚合物（LCCPs)的种类及其制备,介绍了LCCPs在制备发光器件中的取向方法,并对其光学性能进行了评述。