水溶性聚对芳撑乙炔在传感中的荧光猝灭

具有较高荧光量子产率,并且在水溶液中聚集很弱的阳离子型水溶性聚对芳撑乙炔（P1）是一种潜在的高灵敏荧光传感材料。通过比较研究多价无机抗衡离子和具有表面活性剂性质的抗衡离子对P1聚集态的影响,以及P1与3个具有相似结构的有机小分子猝灭剂之间的荧光猝灭效应,深入探讨了水溶性共轭聚合物荧光猝灭传感的猝灭剂构效关系。     

共轭聚合物中载流子迁移率的变温飞行时间检测

载流子迁移率是标定共轭聚合物光电器件性能的重要参数,在数值上其大小远小于传统半导体材料,所以常常用飞行时间方法来测量。利用自行搭建的变温飞行时间检测系统,能够准确地测量聚合物中载流子的迁移率。从原理和实践上,讨论了影响检测结果的限制因素和关键参数,其中包括光生载流子数量、薄膜样品厚度、激发光脉冲宽度、检测外电路的响应时间、载流子在电介质中的弛豫时间和对放大器探测器频率的限制等。只有选取恰当的实验参数才能够获得准确可靠的检测结果。     

共轭聚合物聚苯胺三阶非线性的研究进展

有机非线性光学材料因其优良的性能而引起广泛关注,共轭聚合物聚苯胺(PANI)的研究引起了人们的极大兴趣,文章综述了近年来聚苯胺及其衍生物三阶光学非线性的研究进展。     

共轭聚合物的光放大和激光发射

１　引言　　近来,共轭聚合物半导体已引起电子器件（如二极管、场效应晶体管）和光子器件,其中包括全息存储器、光调制器和发光二极管之类器件应用的注意,这些应用传统上都属无机半导体范畴。聚合物的结构灵活性、易于加工处理和低成本使聚合物器件具有竞争性。对光学应用的最有用特性之一是共轭聚合物的吸收和发射通过改变它们的化学结构而在整个可见光谱范围可调。最近已报导各种共轭聚合物光致发光（ＰＬ）谱线变窄和受激发射（ＳＥ）［１～６］。利用其半导体特性的小型电泵浦聚合物激光器的前景振奋人心。微腔结构中的光泵聚合物薄…     

π——共轭高分子光电性能及聚合物LED

π—共轭高分子光电性能及聚合物ＬＥＤ李文连（中国科学院长春物理研究所，长春１３００２１）（中国科学院激发态物理开放实验室，长春１３００２１）１引言自从Ｃ．Ｗ．Ｔａｎｇ［１］报道了由８—羟基喹啉铝与芳香二胺作为传输材料的积层型电致发光（ＥＬ）器件以来...     

共轭聚合物PFTQ/多孔硅复合膜的光致发光研究

为了实现硅基光电子集成,在多孔硅衬底上制备有机发光器件是一种很有优势的方法.采用匀胶机涂布法在多孔硅中嵌入了新型共轭有机聚合物聚(9,9-二辛基)-2,7-芴-co-N-(4-(2-苯基喹喔啉)苯)-4,4'-二苯胺(PFTQ),对比研究了多孔硅,PFTQ/多孔硅,PFTQ/硅以及PFTQ在甲苯溶液中的光致发光特性.实验结果表明:PFTQ/多孔硅复合膜光致发光强度是PFTQ/硅的2倍,而且相比在甲苯溶液中的PFTQ和PFTQ/硅,发光峰值有所红移,分析认为这是由于共轭聚合物在固态时有效共轭程度增加所致,并且与多孔硅中的激发载流子转移到聚合物分子上形成复合发光有关.     

低LUMO/HOMO共轭聚合物的制备及其电子传输性能

为了探究聚合物结构与性能的关系,获得电子传输型半导体材料。采用Stille交叉偶联反应,制备了基于噻吩-氰基乙烯-噻吩(TCNT)和2-氧吲哚-3-亚基-二氢吡咯吲哚-二酮(BDID)结构的一种新型的低能带隙给体-受体共轭聚合物PBDID-TCNT。采用热重分析仪、示差扫描量热仪、紫外-可见-近红外分光光度计、电化学工作站与原子力显微镜等测试手段对聚合物的热性能、光学性能、电化学性能以及微观结构进行了表征。结果表明:聚合物PBDID-TCNT具有优异的热稳定性,宽的吸收光谱,低的最低未占轨道/最高占有轨道能级(LUMO/HOMO)。首次制得了PBDID-TCNT型的聚合物,以聚合物为半导体层的有机薄膜晶体管器件展现出电子传输特性,电子迁移率达到0.11cm~2/(V·s),同时开关比超过10~5。     

全色非水溶性光致聚合物全息记录材料的研究

针对Ar+激光器、He-Ne激光器三基色波长,设计了一种有效的全色非水溶性光致聚合物体系;给出了该体系的研制流程.性能测试表明,该材料具有分辨率高、衍射效率高和感光光谱范围宽等优点,适合记录彩色反射全息图.     

含氰基三联苯聚噻吩液晶共轭聚合物单体合成

通过Sszuki偶联和Mitsunobu酯化等反应,设计合成了一种新型含氰基三联苯聚噻吩类液晶共轭聚合物单体,利用核磁共振(1H NMR)、红外光谱(IR)等方法表征了单体的结构.利用示差扫描量热仪(DSC)、带热台的偏光显微镜(POM)、紫外光谱(UV)和荧光光谱(PL)研究了单体液晶性和光电性能.结果表明,该单体具有近晶A型液晶态扇形织构,同时,由于三联苯的存在赋予了单体很好的紫外吸收和光致发光性能,在320 nm紫外光激发下,可发射400 nm的蓝光.     

Dynamic Control of Full‐Colored Emission and Quenching of Photoresponsive Conjugated Polymers by Photostimuli

A series of photoresponsive and full‐colored fluorescent conjugated copolymers is synthesized by combining phenylene‐ and thienylene‐based main chains with photochromic dithienylethene (DE) side chains. Solutions and cast films of the polymers exhibit various colored fluorescence in visible wavelengths of 400?700 nm corresponding to emissions of the conjugated main chain. The fluorescence is reversibly photoswitched between emission and quenching through DE photoisomerization using external stimuli from ultraviolet and visible light irradiation. The reprecipitation method with ultrasonication enables the polymers to form spherical aggregates with diameters of 20?70 nm in water. After investigating and comparing the optical properties, the resulting nanosphere solutions are assumed to exist in an intermediate state between an isolated state (i.e., in solution) and an aggregated state in cast film. The majority of the nanosphere solutions also exhibit the same photoswitchable fluorescence behavior as those in the solutions and the cast films. The results demonstrate that the visible fluorescence of the conjugated copolymers is reversibly switchable between emission and quenching using the photoisomerizing DE side chain regardless of the fluorescent colors and the polymer chain aggregation.     

Room Temperature Fluorescent Conjugated Polymer Gums

High molecular weight poly(diphenylacetylene) [PDPA] derivatives are introduced as fluorescent, soft conjugated polymers that exist in the gum state at room temperature. The gum‐like behavior of the polymers is easily modified according to the side alkyl chain length and substitution position. Long alkyl chain‐coupled PDPA derivatives provide soft and sticky gums at room temperature. Manual kneading of gum polymers produce soft films with very smooth surfaces. The gum polymers show an endothermic transition due to the melting of long alkyl chains. The X‐ray diffraction of gum polymers reveals a new signal due to the molten aliphatic chains. The gum polymers show significant viscoelastic relaxation at the melting temperature of the alkyl side chains. The dynamic thermo‐mechanical analysis (DTMA) of gum polymers at room temperature suggest that the meta‐substituted polymer is softer and stickier than para‐polymer. Rheological analysis suggests that the meta‐polymer has less entanglement than para‐polymer. The fluorescence emission of gum polymer is quite intense in the film and solution. The gum polymer film is readily stretched to produce a uniaxually oriented film. Stretching and subsequent relaxation of elastomer‐supported gum polymer film generate buckles perpendicular to the axis of strain. The gum polymer film accommodates the large strain without cracking and delamination.     

Rational Design of Conjugated Polymer Supramolecules with Tunable Colorimetric Responses

Polydiacetylenes (PDAs), a family of highly π‐conjugated polymers, have unique characteristics associated with their ability to self‐assemble. Disruption of the extensively delocalized enyne backbones of molecularly ordered PDA sidechains induces a blue‐to‐red color change, which has been elegantly applied in the design of chemosensors. Recently, colorimetrically reversible PDAs have received significant attention, not only to gain a better understanding of the fundamentals of PDA chromism, but also to develop methodologies to overcome limitations associated with their colorimetrically irreversible counterparts. In this article, recent progress made in the field of colorimetrically tunable (reversible, stable, or sensitive) PDAs is described. Major emphasis is given to rational design strategies developed in our group. Relevant mechanistic investigations, a diagnostic method to test colorimetric reversibility, as well as future challenges in this area will be also discussed.     

Favorable Molecular Orientation Enhancement in Semiconducting Polymer Assisted by Conjugated Organic Small Molecules

A bimodal texturing effect of semiconducting polymers is investigated by incorporating conjugated small molecules to significantly improve the charge transport characteristics via formation of 3D transport pathways. Solution blending of the electron‐transporting polymer, poly{[N,N′‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} (P(NDI2OD‐T2)), with small molecular crystals of tetrathiafulvalene and tetracyanoquinodimethane is used, and the thin film microstructures are studied using a combination of atomic force microscopy, transmission electron microscopy, 2D grazing incidence X‐ray diffraction, and surface‐sensitive near‐edge X‐ray absorption fine structure. Blended thin films show edge‐on and face‐on bimodal texture with long‐range order and microstructure packing orientation preferable for electron transport through the channel in organic field‐effect transistors, which is confirmed by high electron mobility 1.91 cm² V^?1 s^?1, small contact resistance, and low energetic disorder according to temperature dependence of the field‐effect mobility. Structural changes suggest a 3D network charge transport model via lamella packing and bimodal orientation of the semiconducting polymers.     

Conjugated Polymer Based Nanoparticles as Dual‐Modal Probes for Targeted In Vivo Fluorescence and Magnetic Resonance Imaging

A facile strategy is developed to synthesize dual‐modal fluorescent‐magnetic nanoparticles (NPs) with surface folic acid by co‐encapsulation of a far‐red/near‐infrared (FR/NIR)‐emissive conjugated polymer (PFVBT) and lipid‐coated iron oxides (IOs) into a mixture of poly(lactic‐co‐glycolic‐acid)‐poly(ethylene glycol)‐folate (PLGA‐PEG‐FOL) and PLGA. The obtained NPs exhibit superparamagnetic properties and high fluorescence, which indicates that the lipid coated on IOs is effective at separating the conjugated polymer from IOs to minimize fluorescence quenching. These NPs are spherical in shape with an average diameter of ≈180 nm in water, as determined by laser light scattering. In vitro studies reveal that these dual‐modal NPs can serve as an effective fluorescent probe to achieve targeted imaging of MCF‐7 breast cancer cells without obvious cytotoxicity. In vivo fluorescence and magnetic resonance imaging results suggest that the NPs are able to preferentially accumulate in tumor tissues to allow dual‐modal detection of tumors in a living body. This demonstrates the potential of conjugated polymer based dual‐modal nanoprobes for versatile in vitro and in vivo applications in future.     

Graphene‐Oxide‐Conjugated Polymer Hybrid Materials for Calmodulin Sensing by Using FRET Strategy

The conformation of calmodulin (CaM) changes from closed configuration to open one, converting to a claviform dumbbell‐shaped biomolecule upon Ca²⁺‐binding. A hybrid probe of graphene oxide (GO) cationic conjugated polymer for detection of the conformation transition of CaM by using FRET technique is demonstrated. The stronger hydrophobic interaction and weaker electrostatic repulsion leads to more CaM adsorption to the surface of GO upon binding with Ca²⁺ than that of CaM in the absence of Ca²⁺ (apoCaM), resulting in much farther proximity between poly[(9,9‐bis(6′‐N,N,N‐trimethy­lammonium)hexyl)‐fluorenylene phenylene dibromide] (PFP) and green fluorescent protein labeled at the N‐terminus of CaM and therefore much weaker FRET efficiency for PFP/Ca²⁺/CaM in comparison with that of PFP/apoCaM in the presence of GO. Notably, the assembly of CaM with GO is quantitatively and reversibly controlled by Ca²⁺ ions.     

新型处理药剂（EP-110）处理各种重金属离子的实验研究

各行各业生产过程中会产生大量废水,重金属离子污染物是其中的重要控制指标,传统的处理方法不能完全解 决这类污染。本文通过大量的实验数据,对新型的处理药剂(EP-110)处理各种重金属离子的性能做了全面的测试、分析,并 提出了使用方法。     

Capillary‐Bridge Mediated Assembly of Conjugated Polymer Arrays toward Organic Photodetectors

Large‐scale patterning of high‐quality organic semiconductors is crucial for the fabrication of optoelectronic devices with high efficiency and low cost. Yet, owing to the uncontrollable dewetting dynamics of organic liquid in conventional solution patterning techniques, large defect density of organic architectures is inevitable, which is detrimental to the device performance. To address this challenge, herein a capillary‐bridge‐mediated assembly technique is developed for regulating the dewetting process, yielding large‐scale 1D microstructure ordered arrays. The 1D arrays organic photodetectors exhibit a high optoelectronic performance of light on/off ratio exceeding 100, responsivity of 3.24 A W^?1, detectivity of 3.20 × 10¹¹ Jones and fast response speed, showing a great improvement compared with spin‐coated membrane devices. In addition, the significant enhancement of the device photodetection under the electronic field modulation is investigated by applying a back‐gate voltage and explained with the photocurrent predominating in the OFF state and the neglected thermocurrent and tunneling current promoting in the ON state of the phototransistor devices. The research offers a new insight for the facile fabrication of large‐scale integrated photodetectors and other organic devices based on patterned conjugated polymers.     

Controlled Crystallization of Conjugated Polymer Films from Solution and Solvent Vapor for Polymer Electronics

Over the years, solution‐processable conjugated oligomers and polymers have proven to be very promising for application in organic electronic devices. In addition to tuning the chemical structure of the materials, the role of morphology has been identified as a key parameter in determining device performance. Conjugated polymers are typically semicrystalline in nature consisting of both crystalline and amorphous domains giving rise to a wealth of superstructures. In comparison to classical non‐conjugated semicrystalline polymers, they bear the additional advantage of absorbing light. This makes UV‐vis absorption spectroscopy an excellent tool to monitor polymer aggregation and crystallization in‐situ both in solution and in films. With this feature article we point out the delicate interplay between solution processing and the obtained morphology in polythiophenes and low bandgap copolymers. Subtle changes in the preparation protocol lead to significant changes in textures and also give rise to polymorphism. Solvent vapor annealing and solution crystallization are highlighted as tools to control the nucleation and growth processes in semicrystalline polymer films. Structure‐function relationships between morphological, optical and electronic properties are demonstrated.