水溶性含糖共轭聚合物的制备及应用

水溶性共轭聚合物具有优异的光学稳定性、高亮度、易于修饰和水溶性等特点,广泛应用于离子检测、蛋白检测和生物成像等领域。水溶性共轭聚合物主要通过在共轭聚合物的侧基或端基修饰水溶性的离子基团或水溶性聚合物实现其水溶性,水溶性共轭聚合物还可以通过引入功能性基团或聚合物使其具备不同的功能特性。糖化合物是天然存在的一类生物分子且大部分具有水溶性的特点,因此最近十几年来科研工作者将糖化合物引入共轭聚合物中以赋予共轭聚合物糖化合物的生物功能特性。本文总结了水溶性含糖共轭聚合物的制备方法、化学结构及其在凝集素、细菌检测和细胞荧光成像中的应用。最后总结了此类聚合物的特性、发展方向及目前所需解决的问题。     

共轭聚合物生物电子体系研究进展

共轭聚合物类的有机共轭分子由于其特殊的电子离域效应,具有优异的光电性能.另外该类材料骨架结构丰富、能带可调、易于修饰与制备,使得这类材料除了在发光二极管、场效应晶体管和光伏电池等方面有广泛的研究和应用之外,在生物成像、生物传感、疾病诊断和治疗中也发挥了重要作用.本文综述了近年来基于水溶性共轭聚合物的生物电子体系构建和应...     

水溶性共轭聚合物分子刷的研究进展

水溶性共轭聚合物研究属于国际前沿研究领域,因其具有水溶性和超级信号放大作用,在生物传感领域展现出良好的应用前景.但由于传统水溶性线型共轭高分子两亲性结构特点,其含有的憎水性刚性共轭链在水溶液中易聚集,水分子对共轭链激发态的影响导致其发光效率低(一般小于30%),严重制约了其应用与拓展.如何方便有效构筑高分子的高支化是获得高荧光效率的关键.在本篇综述中,我们综述了水溶性共轭聚合物分子刷的合成技术,分析了其结构与光学性质的关系,为水溶性共轭聚合物分子刷的设计和制备提供指导.另外,总结了水溶性共轭聚合物分子刷在化学生物传感、生物成像、药物运输、癌症治疗等领域的应用,最后对水溶性共轭聚合物分子刷存在的主要问题以及未来的热点方向进行了分析和展望!     

聚集诱导发光高分子在光学诊疗应用中的研究进展

高分子因其优异的光学特性、良好的生物相容性和分子结构易于调控等优势,在光学诊疗领域表现出巨大应用潜力.然而,传统荧光分子的聚集导致荧光淬灭现象限制了其生物应用.聚集诱导发光(AIE)分子因其聚集态高效发光的优势而备受关注.本文从AIE高分子的构建出发,重点介绍了D-A型共轭聚合物的构建策略、构-效关系以及相对于小分子的性能和应用优势,并从生物成像、肿瘤诊疗和抗菌三个方面总结了AIE高分子在光学诊疗领域的最新研究进展.生物成像方面主要总结了NIR-Ⅱ区AIE高分子在深部组织高分辨率荧光成像中的应用;肿瘤诊疗方面主要介绍了AIE高分子在光动力治疗、光热治疗及联合治疗中的应用;以及介绍了AIE高分子在细菌感染光动力治疗中的应用.最后对AIE高分子在光学诊疗领域的未来发展前景进行了展望.     

基于聚噻吩荧光化学敏感材料的设计及其应用

<正>水溶性共轭聚合物,由于其存在大量的重复性吸收单元,具有极强的光捕获能力,它与带电荷的生物分子之间强烈的静电相互作用和荧光信号自身的灵敏性,赋予了水溶性共轭聚合物在免标记生物成像及检测方面非常显著的优势.同时由于共轭链的"分子导线效应"使得其作为荧光探针分子的灵敏度相对于小分子大大提高.通过在共轭链骨架     

水溶性共轭聚合物在生物传感中的应用

水溶性共轭聚合物在化学、医学、生命科学以及材料科学等领域中备受研究者们的关注,利用其独特的光化学和光物理性质,研究者们开展了一系列创新性研究并取得了重大的研究进展,进而拓展了聚合物的应用范围.共轭聚合物是一种由多个重复发光单元通过彼此间共轭而形成的高分子化合物,通过对其结构的精准调控,可以获得具有不同性能的功能性分子.其中,通过改变其主链结构,可以获得具有不同吸收和发射波长的荧光探针;通过对侧链结构修饰以水溶性基团和/或选择性识别分子,可以实现与特定靶标间的静电作用或者特异性结合,进而实现选择性识别的目的.本文综述了近年来水溶性共轭聚合物在生物传感中的应用,主要介绍了水溶性共轭聚合物在DNA检测、蛋白质检测、细胞和细菌的检测与区分以及细胞成像等方面的研究进展.     

含偶氮苯光学活性侧基聚合物研究进展

综述了含偶氮苯光学活性侧基聚合物近年来的发展概况 ,介绍了多种聚合体系的类型。由于偶氮苯光于活性侧基的存在 ,使得这些聚合物具有光致变色性、非线性光学活性、光学各向异性等光学性能 ,在光信息存储材料、非线性光学材料、液晶材料、光电子器件、生物分子活性光调控、纳米技术等诸多领域都有广泛的应用。     

水溶性共轭聚合物PFP/DNA/卟啉复合物光谱性质的研究

开发水溶性的、可双光子激发的且可选择性产生单态氧的系统在光生物与动力治疗等方面具有应用价值. 在本文中, 利用荧光共振能量转移的原理设计了一套光动力治疗系统, 其中带正电的水溶性共轭聚合物PFP作为能量给体, 在单双光子激发下均具有较高的光捕获能力. 带正电的卟啉作为能量受体, 具有极高的单态氧量子产率, 带负电的DNA是连接桥, 使水溶性共轭聚合物PFP与卟啉之间的能量转移得以实现. 通过研究这个体系的吸收、荧光光谱, 荧光寿命, 单态氧量子产率以及双光子吸收截面等性质, 我们发现具有不同DNA序列的系统能量转移效率和单态氧量子产率均不相同, 其中癌细胞中富含的四链DNA具有最高的选择性, 这使得该系统在光动力治疗上具有非常好的应用前景.     

基于共轭聚合物的核酸生物传感器的应用

共轭聚合物的π电子体系及共轭离域结构,使其具有良好的发光性能。聚合物链可充当“分子导线”,能够成倍放大光学信号,从而有效提高检测灵敏度。而核酸适体(aptamer)在特异性、与靶物质亲合力、信号传导方面比其他识别元件具有更大的优势,因此共轭聚合物的核酸生物传感器在生物检测方面得到了迅速发展。本文主要总结了近年来共轭聚合物的核酸生物传感器在生物检测方面的应用,并进一步对该类型传感器的发展趋势作出了展望。     

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。     

Efficient light harvesting in dye-endcapped conjugated polymers probed by single molecule spectroscopy

The development of sophisticated microscopic models of energy transfer in linear multichromophoric systems such as conjugated polymers is rarely matched by suitable experimental studies on the microscopic level. To assess the roles of structural, temporal, and energetic disorder in energy transfer, single molecule spectroscopic investigations of the elementary processes leading to energetic relaxation in conjugated polymers are desirable. We present a detailed study of energy transfer processes occurring in dye-endcapped conjugated polymer molecules on the single molecule level. These processes are mostly masked in ensemble investigations. Highly efficient intramolecular energy transfer along a single polyindenofluorene chain to a perylene endcap occurs in many instances and is resolved in real time. We further consider the spectral emission characteristics of the single molecule, the polarization anisotropy which reveals the chain conformation, the fluorescence intermittency, and the temperature dependence and conclude that the efficiency of energy transfer in the ensemble is controlled by the statistics of the individual molecules. The weak thermal activation of energy transfer indicates the involvement of vibrational modes in interchromophoric coupling. Whereas backbone-endcap coupling is strong, the rate-limiting step for intramolecular energy transfer is the migration along the backbone. The results are particularly relevant to understanding undesired exciton trapping on fluorenone defects in polyfluorenes.     

BLUE LIGHT-EMITTING POLY（FLUORENE-CO-BENZENE） CONTAINING AN OXADIAZOLE MOIETY

A new kind of polyfluorene containing oxadiazole as the side chain was synthesized. The introduction of oxadiazole moiety as more bulky group prevents the aggregation and reduces the crystallinity of the polymers. Efficient intramolecular energy transfer from oxadiazole moiety to the conjugated backbone has been realized, leading to 70% improvement of photoluminescence quantum efficiency of the designed polymers. Compared with PAF, the PFOXD exhibits significant improvement in electroluminescence properties, with luminous efficiency of 0.8 cd/A and maximum luminance of 1800cd/m^2,     

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.     

Toward transparent molecular wires: electron and energy transfer in transition metal derivatized conducting polymers

A great deal of research has concentrated on long range electron and energy transport in transition metal-based systems, including molecular donor-acceptor assemblies, electron and energy transfer cascades, dendrimers, and derivatized polymer systems. In an effort to improve efficiencies for electron and energy transport over large distances, several groups have now turned to conjugated systems. Several challenges exist to incorporating conducting materials/polymers in the study of photoinduced electron and energy transfer: solubility and processibility of the materials, thermal stability and limitations on direct spectroscopic characterization due to band gap absorptions. We have prepared a new series of conducting materials that provides for direct incorporation of chromophores and electrophores within the backbone of a conducting polymer. Energy transfer dynamics between conducting polymer bridges and porphyrin or metal-to-ligand charge transfer (MLCT) chromophores can be controlled through intermolecular interactions in solid vs solution samples. We have also developed a methodology to incorporate transmissive benzothiophene-type polymers such as polyisothianaphthene (PITN) within a copolymer assembly. These new materials are now being used to investigate long range electronic coupling and have potential applications that range from artificial photosynthesis to light emitting diodes.     

Fluorescence Study of Energy Transfer in PMMA Polymers with Pendant Oligo‐Phenylene‐Ethynylenes

A spectroscopic characterization of polymers containing rigid π‐conjugated oligo(phenyleneethynylene) chromophores as well as oligo(phenyleneethynylene) and methyl methacrylate is presented. The polymers exhibit molar masses of up to 15 000 g mol^?1 and a degree of polymerization between 22 and 80. Emission measurements of the monomeric and polymeric species show that radiative as well as nonradiative rates are influenced by the degree of polymerization due to intramolecular interactions of chromophores pendant to the polymer backbone. Time‐resolved emission anisotropy measurements suggest that energy migrates within the polymers. Steady‐state emission anisotropy measurements also point to energy migration. Additionally, two oligo(phenyleneethynylene)s with different sizes of the conjugated system are copolymerized in order to enable energy trapping due to energy transfer. The shortened energy‐donor fluorescence lifetime within the donor–acceptor copolymers suggest energy transfer. Depending on the degree of polymerization, dispersion of the donor fluorescence lifetime is observed.     

基于共轭高分子材料的光学生物传感器*

以聚芴、聚噻吩、聚乙炔为典型代表的共轭导电高分子材料,是作为传感元件进行光、电信号传导的优异材料,目前已成为生物传感器领域研究的热点。基于不同类型,不同性质的共轭高分子所设计的传感策略特色各异,功能也不尽相同,例如,利用共轭高分子可以与某些电子/能量受体之间发生电子/能量转移的特点,可以使传感器的检测信号得到数百万倍的放大,从而极大地提高检测的灵敏度;利用共轭高分子的光学性质随构象变化而变化的特点,则可以实现对靶介导的生物分子的构象或结构转变的检测。本文对各种基于不同传感策略的共轭高分子光学生物传感器研究进行了综述,并对该领域的发展前景进行了展望。     

Unusual Internal Electron Transfer in Conjugated Radical Polymers

Nitroxide‐containing organic radical polymers (ORPs) have captured attention for their high power and fast redox kinetics. Yet a major challenge is the polymer's aliphatic backbone, resulting in a low electronic conductivity. Recent attempts that replace the aliphatic backbone with a conjugated one have not met with success. The reason for this is not understood until now. We examine a family of polythiophenes bearing nitroxide radical groups, showing that while both species are electrochemically active, there exists an internal electron transfer mechanism that interferes with stabilization of the polymer's fully oxidized form. This finding directs the future design of conjugated radical polymers in energy storage and electronics, where careful attention to the redox potential of the backbone relative to the organic radical species is needed.     

Optimization of the molecular orbital energies of conjugated polymers for optical amplification of fluorescent sensors

Cationic water-soluble poly(fluorene-co-phenylene)s with electron withdrawing or donating substituents on the conjugated backbone were designed and synthesized. Fluorescence resonance energy transfer (FRET) experiments between these conjugated polymers and dye-labeled single-stranded DNA (ssDNA-C*) reveal the importance of matching donor and acceptor orbital energy levels to improve the sensitization of C* emission. Quenching of polymer fluorescence with ssDNA-C* and differences in C* emission suggest involvement of photoinduced charge transfer (PCT) as an energy wasting mechanism. The HOMO and LUMO energy levels of the conjugated polymers and C serve as a preliminary basis to understand the competition between FRET and PCT. Dilution of C in polymer/ssDNA-C complexes by addition of ssDNA yields insight into C*...C self-quenching. Under optimized conditions, where there is no probe self-quenching and minimum PCT, efficient signal amplification is demonstrated despite poor spectral overlap between polymer and C.     

Synthesis and properties of electrophosphorescent chelating polymers with iridium complexes in the conjugated backbone

The synthesis of electrophosphorescent chelating polymers by Suzuki polycondensation of A-A- and B-B-type monomers is described, in which the fluorene-alt-carbazole (PFCz) segment is used as polymer backbone. By using alkyl-substituted ligands of iridium complex monomers, chelating copolymers with higher contents of iridium complex can be synthesized. Chemical and photophysical characterization confirm that the Ir complex is incorporated into the polymer backbone as one of the monomer repeat units by means of two 5-bromotolylpyridine ligands. Chelating polymers with Ir complexes in the conjugated polymer backbone show highly efficient energy transfer of excitons from the PFCz host segment to the Ir complex by an intramolecular trapping mechanism. The external quantum and luminous efficiencies of a device made with PFCzMppyIrhm4 copolymer reach 4.1 % ph/el (photons/electron) and 5.4 cd A(-1), respectively, at a current density of 32.2 mA cm(-2), an emission peak of 577 nm, and a luminance of 1730 cd cm(-2). Most important, the devices made from the chelating copolymers show no notable efficiency decay with increasing current density due to reduced concentration quenching and triplet-triplet (T-T) annihilation. This indicates that incorporation of the phosphorescent complex into the rigid conjugated polymer main chain is a new way to simultaneously realize high efficiency, long-term stability, and simple processing of phosphorescent polymer light-emitting diodes.     

Comparative study on polymer light-emitting devices based on blends of polyfluorene and 4,7-di-2-thienyl-2,1,3-benzothiadiazole with devices based on copolymer of the same composition

The small molecule 4,7-di-2-thienyl-2,1,3-benzothiadiazole (DBT) dye has been synthesized and blended into blue-emitting polyfluorene as a host. The photophysics of the blend films and electroluminescence device performance was compared with that from polyfluorene-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole (PFO-DBT) copolymer of the same molar composition, with DBT incorporated covalently into the polyfluorene backbone. The role of intra- and interpolymer chain interaction and energy transfer in the polymer light-emitting devices are discussed. On the basis of the direct comparison of blend and copolymer from the same molecular composition, we can draw the conclusion that, in conjugated polymers, intrachain energy transfer along the polymer backbone is more efficient than that via interchain interaction and plays a more important role in polymer light-emitting devices.