新型共轭聚合物的设计合成及其在场效应晶体管的应用

近年来,有机场效应晶体管(OFETs)由于在柔性器件和可穿戴电子学中的潜在应用受到了学术界和工业界的普遍关注,尤其是以聚合物半导体材料构筑的晶体管性能得到了快速的发展.如何设计合成用于OFETs的高性能聚合物半导体材料,一直是我们的追求目标.然而,分子结构对迁移率的影响仍缺少系统的比较.本文综述了近年来国内外新型聚合物材料的最新进展.我们按照材料的种类以及载流子的传输类型进行了分类,对高性能聚合物材料的发展过程、材料的设计思路以及相应的FETs性能进行了系统地归纳总结.通过研究分子及分子聚集态结构与器件性能之间的关系,希望为以后设计合成新型的高性能的聚合物材料提供有益的借鉴和指导.     

苯并噻吩类稠环化合物的合成及其在有机场效应晶体管中研究的进展

总结了苯并噻吩类稠环化合物半导体材料的最新研究进展,对其合成方法及结构与性能进行了归纳,介绍了它们在有机场效应晶体管中的应用,并对其研究和应用前景进行了展望。     

3-Methylcyclohexanone Processed n-Channel Organic Thin-Film Transistors Based on A Conjugated Polymer Synthesized by Direct Arylation Polycondensation

The solubility of a direct arylation polycondensation(DArP) synthesized conjugated polymer,i.e.,poly(3,6-bis(furan-2-yl)-2,5-bis(4-tetradecyloctadecyl)-pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione-alt-1,2-bis(3,4-d ifl uorothien-2-yl)ethene)(PFuD PP-4FTVT),in variou s organic solvents was studied.The polymer is soluble in 3-methylcyclohexanone(3-MC),a green solvent from peppermint oil,besides other solvents such as anisole,cyclopentyl methyl ether(CPME) and o-dichlorobenzene(o-DCB),etc.Based on the Ha...     

A Simple Method to Fabricate a Conductive Polymer Micropattern on an Organic Polymer Substrate

Summary: Under UV irradiation plus a photomask, a hydrophilic/hydrophobic hybrid polymer surface is created by sandwiching an ammonium persulfate solution between two polymer films. It is demonstrated that an effective conductive PANI micropattern can be fabricated on such a wettability patterned surface. For PET, a stable negative micropattern could be formed directly by the selective deposition of PANI onto the hydrophobic region. Alternatively, for PP or PI, direct deposition of PANI is non‐selective, however, the PANI layer remains preferentially on the hydrophilic region by peeling off the PANI layer on the hydrophobic region to form a positive micropattern.

Schematic illustration of the procedure used for the formation of a conducting polymer (PANI) micropattern on a wettability patterned polymer substrate.     

水/醇溶共轭聚合物界面材料及其在光电器件中的应用

相对于传统的无机半导体器件,以有机半导体(特别是聚合物半导体)材料为基础的有机光电器件,可采用与传统印刷技术(例如喷墨打印、卷对卷印刷等)相结合的溶液加工方式制备低成本、大面积、柔性光电器件,因而成为广泛关注的焦点,并得到了快速发展.实现溶液加工的高效有机光电器件的一个关键问题是界面问题——如何避免溶液加工时有机层间的互溶以及如何实现可印刷稳定金属电极的高效电子注入等.水/醇溶性共轭聚合物的迅速发展为解决溶液加工多层有机光电器件所面临的界面问题提供了有效手段.研究发现,水/醇溶共轭聚合物不但可以有效避免溶液加工多层器件中的界面互溶,而且还可与高功函数的稳定金属发生界面偶极相互作用而增强其电子注入,从而解决了高功函数稳定金属电子注入的难题,为实现全溶液加工的高效印刷有机光电器件提供了可行的方案.本文介绍了近年来本课题组在水/醇溶共轭聚合物阴极界面材料及器件应用方面的研究进展,并对水/醇溶共轭聚合物阴极界面材料在聚合物发光二极管和聚合物太阳电池中的工作机理进行了探讨.     

Recent Advances in Wide Bandgap Polymer Donors and Their Applications in Organic Solar Cells

Organic solar cells(OSCs)have attracted wide research interests in the past decades.In recent years,our group mainly focused on the new photovoltaic materials design and device engineering technologies for highly efficient OSCs.This account mainly summarizes our recent studies on the structural design of wide bandgap(WBG)polymers and their morphology control as well as applications in OSCs.Additionally,we introduce our work on binary and ternary blend devices and tandem solar cells containing these materials.     

Electrophosphorescent Heterobimetallic Oligometallaynes and Their Applications in Solution‐Processed Organic Light‐Emitting Devices

By combining the iridium(III) ppy‐type complex (Hppy=2‐phenylpyridine) with a square‐planar platinum(II) unit, some novel phosphorescent oligometallaynes bearing dual metal centers (viz. Ir^III and Pt^II) were developed by combining trans‐[Pt(PBu₃)₂Cl₂] with metalloligands of iridium possessing bifunctional pendant acetylene groups. Photophysical and computational studies indicated that the phosphorescent excited states arising from these oligometallaynes can be ascribed to the triplet emissive Ir^III ppy‐type chromophore, owing to the obvious trait (such as the longer phosphorescent lifetime at 77 K) also conferred by the Pt^II center. So, the two different metal centers show a synergistic effect in governing the photophysical behavior of these heterometallic oligometallaynes. The inherent nature of these amorphous materials renders the fabrication of simple solution‐processed doped phosphorescent organic light‐emitting diodes (PHOLEDs) feasible by effectively blocking the close‐packing of the host molecules. Saliently, such a synergistic effect is also important in affording decent device performance for the solution‐processed PHOLEDs. A maximum brightness of 3 356 cd m^?2 (or 2 708 cd m^?2), external quantum efficiency of 0.50 % (or 0.67 %), luminance efficiency of 1.59 cd A^?1 (or 1.55 cd A^?1), and power efficiency of 0.60 Lm W^?1 (or 0.55 Lm W^?1) for the yellow (or orange) phosphorescent PHOLEDs can be obtained. These results show the great potential of these bimetallic emitters for organic light‐emitting diodes.     

Dithienocyclopentathieno[3,2‐b]thiophene Hexacyclic Arene for Solution‐Processed Organic Field‐Effect Transistors and Photovoltaic Applications

We have developed a ladder‐type dithienocyclopentathieno[3,2‐b]thiophene ( DTCTT ) hexacyclic unit in which the central thieno[3,2‐b]thiophene ring was covalently fastened to two adjacent thiophene rings through carbon bridges, thereby forming two connected cyclopentadithiophene ( CPDT ) units in a hexacyclic coplanar structure. This stannylated Sn‐DTCTT building block was copolymerized with three electron‐deficient acceptors, dibromo‐thieno[3,4‐c]pyrrole‐4,6‐dione ( TPD ), dibromo‐benzothiadiazole ( BT ), and dibromo‐phenanthrenequinoxaline ( PQX ), by Stille polymerization, thereby furnishing a new class of alternating donor–acceptor copolymers: PDTCTTTPD , PDTCTTBT , and PDTCTTPQX , respectively. Field‐effect transistors based on PDTCTTPQX and PDTCTTBT yielded high hole mobilities of 0.017 and 0.053 cm² V^?1 s^?1, respectively, which are among the highest performances among amorphous donor–acceptor copolymers. A bulk heterojunction solar cell that incorporated PDTCTTTPD with the lower‐lying HOMO energy level delivered a higher V_oc value of 0.72 V and a power conversion efficiency (PCE) value of 2.59 %.     

A Facile and Highly Efficient Approach to Obtain a Fluorescent Chromogenic Porous Organic Polymer for Lymphatic Targeting Imaging

Porous organic polymers have an open architecture, excellent stability, and tunable structural components, revealing great application potential in the field of fluorescence imaging, but this part of the research is still in its infancy. In this study, we aimed to tailor the physical and chemical characteristics of indocyanine green using sulfonic acid groups and conjugated fragments, and prepared amino-grafted porous polymers. The resulting material had excellent solvent and thermal stability, and possessed a relatively large pore structure with a size of 3.4 nm. Based on the synergistic effect of electrostatic bonding and π–π interactions, the fluorescent chromogenic agent, indocyanine green, was tightly incorporated into the pore cavity of POP solids through a one-step immersion method. Accordingly, the fluorescent chromogenic POP demonstrated excellent imaging capabilities in biological experiments. This preparation of fluorescent chromogenic porous organic polymer illustrates a promising application of POP-based solids in both fluorescence imaging and biomedicine applications.     

有机分子在基底上的自组装及其在仿生材料合成中的应用

基底对有机分子的自组装有着重要的影响作用，有机分子不同的自组装方式在仿生材料合成，生物膜等方面有重要用途，本文综述了有机分子在不同基底上的自组装方式及其在仿生材料合成中的应用，并对有机分子的自组装方式的发展趋势及广阔应用前景作了进一步的展望。     

Synthesis and Modifications of Dendrimers on Polymer System Supported on Montmorillonite and Their Use in Organic Synthesis

ABSTRACT

Molecules with dendrimeric structure (cascade molecules) were attached to a polymer-montmorillonite system. The supported dendrimeric molecules were modified to produce ammonium and phosphonium salts. The catalytic phase-transfer activities of these systems have been investigated. The results from the catalytic activity studies showed that the dendrimeric system is highly activating the selected organic reactions. This was attributed to the dendrimeric structure of the system which consequently increase the weight efficiency. It is worth mentioning that this is the first report in the literature describing the formation of dendrimers on polymer-montmorillonite system and their use as phase-transfer catalysts.

     

共价有机框架的合成及其在肿瘤治疗中的应用研究进展

共价有机框架(covalentorganicframeworks,COFs)是近年来开发的一种由有机单元连接而成的高结晶性多孔聚合物,由于具有良好的孔隙率、模块性、结晶性和生物相容性等特点在肿瘤治疗中显示出了良好的应用前景.本综述总结了已报道的COFs制备方法,包括溶剂热合成法、机械化学合成法、微波合成法、离子热合成法、界面合成法、室温合成法和纳米尺度COFs的合成方法,并根据对肿瘤作用机理的差异,将用于肿瘤治疗的COFs纳米载药系统归纳为药物化疗、光热治疗、光动力学治疗和联合治疗.此外还讨论了COFs在肿瘤治疗领域所面临的主要挑战和发展趋势.     

A Facile and Universal Method to Prepare Hydrophilic Molecularly Imprinted Microspheres by Encapsulating a Polymer in Hollow Mesoporous Silica Microspheres

Hydrophilic molecularly imprinted microspheres (MIP@SiO₂) for the adsorption of water‐soluble molecules in real aqueous samples were successfully synthesized. In this strategy, a molecular imprinted polymer (MIP) was encapsulated in the hollow core of hollow mesoporous silica (HMS) particles via a ‘ship‐in‐a‐bottle’ process. As the HMS shell contains plenty of Si‐OH groups, the as‐prepared microspheres proved to be hydrophilic and could be well dispersed in water. On the other hand, the MIP encapsulated in the HMS could specifically recognize small molecules with good binding efficiency through the mesoporous silica shell. Binding experiments in real aqueous solutions showed that the MIP@SiO₂ composites have excellent recognition ability for specific molecules. Thus, MIP@SiO₂ are highly promising alternatives to biological receptors with great potential for many analytical applications, such as environmental, food, and clinical analyses and other areas.     

表面活性剂与聚合物相互作用的动力学模拟

用扩散颗粒动力学模拟方法（Dissipative Particle Dynamics，DPD）模拟了 中性聚合物与离子型表面活性剂的相互作用。在分子水平上研究了介于微观和宏观 上的一些性质，直观地用三维图形描绘了聚合物在表面活性剂溶液中的聚集形成， 并通过聚合物的末端的变化表征了聚集过程。结果发现：随着表面活性剂浓度的增 加，聚合物呈现自由伸缩→形成松散的棒状结构→再出现胶束状珍珠链结构→最终 在六角状和层状相中分布的过程。DPD模拟方法能够直观地得到聚合物在表面活性 剂溶液中的聚集形态。     

New Polymer Syntheses Part 60: A Facile Synthetic Route to Polyamides Based on Thieno[2,3-b]thiophene and Their Corrosion Inhibition Behavior

Polyamides containing thieno[2,3-b]thiophene moiety were prepared via a simple polycondensation reaction of the diaminothieno[2,3-b]thiophene monomer 1 a with different kinds of diacid chlorides(including oxalyl, adipoyl, sebacoyl, isophthaloyl,terephthaloyl, 4,4′-azodibenzoyl, 3,3′-azodibenzoyl, p-phenylene diacryloyl) in the presence of Li Cl and NMP as a solvent through lowtemperature solution polycondensation. The chemical structures of model compound and synthesized polyamides were confirmed by FTIR, nuclear magnetic resonance spectroscopy(including ~1H-NMR and ~(13)C-NMR) and elemental analysis. In addition, the thermal stability, crystallinity structure and surface morphology of synthesized polyamides were characterized via thermogravametric analysis(TGA), wide-angle X-ray diffraction analysis(WAXD) and scanning electron microscopy(SEM). Also, the corrosion inhibition behavior of selected examples of polyamides was investigated; the inhibitive effect of the investigated polymers for carbon steel in 1.0 mol·L~(-1) HCl was studied using potentiodynamic polarization(PDP) and electrochemical impedance spectroscopy(EIS) methods. PDP results displayed that the polyamides containing thieno[2,3-b]thiophene moiety can be as mixed-type inhibitors. The inhibition efficiency(P, %) was found to be in the range from 67.13% to 96.01%. There is an increase in P by the synthesized polymers in comparison to the starting monomer.The adsorption of these polymers was found to obey Langmuir adsorption isotherm.     

一种水体中有机污染物快速筛查与半定量的方法及其应用

采用液液萃取法富集水体中的有机污染物,以气相色谱-质谱和Compound composer软件进行筛查和半定量计算,同时以气相色谱-质谱法在选择离子模式下对Compound composer软件的半定量结果进行验证,结果表明除3-氨基苯酚、豆甾醇和β-谷甾醇外,其它物质的回收率在74％～102％之间,保留时间偏差为-0.158 ～0.049 min,对添加量为1.0μg目标物的水样半定量,结果偏差在-0.48～0.62 μg之间.在无标准样品的条件下,利用Compound composer软件及其自带含近千种化合物标准曲线的数据库,对江苏省南通、苏州和无锡三市的地表水环境样品进行监测,筛查其中主要的有机污染物,并进行半定量计算.三市地表水样中共检出47种有机污染物.2,6-二叔丁基-4-甲基苯酚为检出浓度最高的化合物,其浓度达140 μg·L-1,酞酸酯类和多环芳烃类物质普遍存在,其单体浓度范围分别为1.7～48μg·L-1和0.13 ～9.6 μg· L-1.依照GB3838-2002《地表水环境质量标准》,三市地表水体中酞酸酯类严重超标,水体中总有机物污染状况应引起关注.     

Polymer Nanocomposites in Sensor Applications: A Review on Present Trends and Future Scope

Polymers are crucial constituents of modern electronic devices. They can be used in their pristine, composite or nanocomposite forms for several domestic and industrial applications with innumerable unique possibilities. Polymer nanocomposites have gained wide theoretical interest and numerous practical applications in diverse fields of science and technology as they bestow the materials not only with virtuous processability but also with exceptional functionalities. It is evidenced that the electrical conductance of polymer nanocomposite is governed by the conductive filler networks within the polymer matrix. Hence, insignificant variation in the conductive networks can result in noteworthy variations in the output electric signal of polymer nanocomposite. Exploiting this stimuli-responsive performance of conductive networks to the physical parameters, polymer nanocomposites can be harnessed to fabricate novel sensitive sensors to detect vital physical parameters viz.strain/stress, pressure, temperature, solvent or vapor. Technical and phenomenological studies on polymer nanocomposites are still enduring.Advanced explanations are being sought but the mechanisms governing the formation of several polymer nanocomposites are still topics of debate in the material science community. Their in-depth investigation requires copious scientific work. This review analytically sketches the synthesis, microstructures, physiochemical properties and the underlying mechanisms for stimuli-responsiveness to the physical parameters of the polymer nanocomposites as well as their applications in various sensitive sensors and detectors. Thus, it became evocative for this review to focus on their processing methodologies, physiochemical physiognomies, classification and probable potentials of polymer nanocomposites.This review primarily presents the current literature survey on polymer composites and the gap areas in the study encourages the objective of the present review article. Finally, the status, perspectives and the advantages of specific polymer nanocomposites at present are summarized. The attention of this review is drawn to the present trends, challenges and future scope in this field of study. Finally, the vital concern and future challenge in utilizing the stimulus responsive behavior of polymer nanocomposites to design versatile sensors for real time applications are elaborately discussed.     

基于硫酸根自由基的先进氧化活化方法及其在有机污染物降解上的应用

基于硫酸根自由基(SO₄^.-)的先进(高级)氧化法(AOPs)因其对新型有机污染物的高降解能力和高适应性而受到越来越多的关注。相比羟基自由基(·OH),SO₄^.-的选择性更好、还原电位更高、半衰期更长、pH范围更宽且成本更低,因而能更有效的降解污染物。SO₄^.-可由过一硫酸盐(PMS)或过二硫酸盐(PDS)等过硫酸盐(PS)通过热、机械化学、过渡金属、碳质材料、碱、紫外(UV)或电化学等方法活化产生。本文分析了不同活化方法的优缺点及其应用于有机污染物降解上的研究进展,总结了SO₄^.-降解含不同官能团污染物的三种机理(加成作用、夺氢作用和直接电子转移),并综述了SO₄^.-降解持久性有机污染物(POPs)、“伪持久性有机污染物”——药物和个人护理品(PPCPs)及有机染料三大类有机污染物的降解途径、降解产物及其研究进展,最后展望了该技术未来的研究方向。     

二维平面细胞微图案化技术及其生物学应用

可以控制细胞粘附形状、大小的方法统称为细胞图案化技术.这些方法结合微纳米制备、表面化学、电化学和光化学等手段可以动态控制细胞的粘附、迁移、分化及其相互作用,为细胞生物学研究提供了一个新平台.本文介绍了二维平面细胞图案化的各种方法,并对其优缺点进行了总结,评述了细胞图案化技术在细胞生物学基础研究、组织工程以及基于细胞的生物传感器领域的应用.