论共轭聚合物的合成方法及其应用

π共轭聚合物因具有独特的光、电性能而引起了科学界的广泛关注。由富电子单元和缺电子单元构成的给一受电子模型聚合物由于其在太阳能电池、发光二极管、传感器等领域有着诱人的应用前景而受到科学界和商业界的青睐。本论文介绍共轭聚合物的特性及其合成方法,论述共轭聚合物在太阳能电池和发光材料中的应用。     

基于水溶性共轭聚合物的蛋白质荧光传感器

化学和生物传感器研究领域对新传感材料的开发越来越依赖.探讨了基于荧光信号放大共轭聚合物的蛋白质传感器的最新进展;共轭聚合物可作为高效电子/能量传递载体这一特性是其高灵敏度检测/信号放大的根源;详细介绍了数种传感策略.     

含二茂铁基团的芴-苯共轭化合物的合成及其性能研究

通过Suzuki偶联反应合成了二茂铁基团存在于侧链、主链和端基的苯-芴共轭化合物6、7和8,并通过 NMR和MS等表征手段对其结构进行了确认.共轭化合物中的二茂铁基团通过分子内的光致电子转移过程使6、7和8在溶液状态下的荧光猝灭.当向其溶液中加入氧化剂KMnO₄后,溶液的荧光强度显著增强,最大可增至75倍.荧光增强的幅度、对氧化剂的响应时间等性质受二茂铁在共轭化合物中的位置以及个数的影响.实验结果表明, 分子中含有一个二茂铁基团其荧光增强是线型增长的,响应时间也较短;当共轭分子中含有两个二茂铁基团时,其荧光强度的增长成二次函数关系,且其响应时间也较长.      

Synthesis and Characterization of Fluorene-based Polymers Containing Electron-withdrawing Thiazolo Thiazole Unit

1 Results Low bandgap polymers can be used for pure red light emitting materials or solar cell materials.To make low bandgap polymers,we designed conjugated polymers with alternating sequences of the appropriate donor/acceptor units in the main chain.3-hexyl thiophene was used as a electron donating unit.For the electron accepting unit,we selected thiazolothiazole and bithiazole units having electron withdrawing property.Polyfluorene(PF) is the preferred conjugated polymer in light-emitting applications...     

取代基影响邻菲罗啉衍生物-铕能量传递和荧光性能研究

配体结构调控是提高稀土配合物发光强度的有效手段,根据稀土配合物发光原理,理想配体应具备较高的光捕获能力并且能有效地向稀土离子传递能量。研究表明,增加配体的共轭程度可使配体的光吸收能力增强,而不同电子给予特性基团的引入则会改变配体与稀土离子间的能级匹配程度,从而影响配体向稀土离子的有效能量传递,提高配合物的发光效率。本文以引入不同特性(共轭特性、电子给予特性)取代基的邻菲罗啉为配体合成6种铕的配合物,通过分析配合物的吸收光谱、红外光谱、荧光光谱和X射线光电子能谱等发现,供电子基团和共轭基团能够提高配体的电子云密度,增大配体的摩尔吸收系数,同时有利于配体与稀土离子间形成配位键,能够明显提高配合物分子内能量传递,并使配合物发光性能增强。     

无机介孔材料在第三代电化学生物传感器中的应用研究

无机介孔材料是一种孔直径在2,50nm的多孔材料。这种材料具有结构规则,机械性能高、化学和热能稳定性好等特点。近年来,随着材料合成技术的提高,不断有新型高负载能力和生物相容性好的介孔材料被开发出来。同时,实验表明,无机介孔材料是固载生物大分子的良好载体。利用无机介孔材料固载氧化还原蛋白质并结合其的直接电子转移,为我们提供了一种新的构建第三代生物传感器的方法。基于无机介孔材料的特点及氧化还原蛋白质的直接电子转移,所构建的第三代电化学生物传感器有望具有较传统电化学传感器更好的性能。将介孔材料分为二氧化硅基和非二氧化硅基2大类,描述了无机介孔材料在第三代电化学生物传感器中的应用。     

导电聚合物的电化学性质

综述了几种有代表性的导电聚合物——聚吡咯、聚苯胺、聚噻吩等的电化学特性及其电化学掺杂／脱掺杂反应的机理,介绍了聚对苯撑乙烯(PPV)等光电活性共轭聚合物的循环伏安特性及其HOMO和LUMO能级的电化学表征方法;还对导电聚合物的电化学稳定性以及取代基对共轭聚合物电子结构的影响进行了讨论．     

类脂双层膜BLMs的镶嵌修饰与应用

报道了类脂双层膜BLMs在离子通道和电子跨膜传递、光电转换、膜与溶液中离子、分子的相互作用以及作为传感器检测离子、分子等方面的镶嵌修饰与应用。     

海洋环境现场监测手段的开发与应用

阐述了国际上化学传感器、化学分析器、生物传感器,以及基于这些传感器和分析器的多学科交叉现场观测系统等海洋环境现场监测手段的开发与应用概况,并略涉一些现场采样手段,重点列举了pCO2微电极、中性浮式沉积物采样器,以及用于研究海洋上层输出通量的锚式系统,可为我国引进和开发海洋观测高技术提供借鉴。     

低能离子与物质相互作用中电子能损微观机制的研究进展

深入了解离子与物质的相互作用是研究材料抗辐照性能以及应用离子束技术的基础和关键．离子的能量沉积是导致材料辐照损伤的根本原因,所以研究离子碰撞过程中的能损机制显得尤为重要．本文从离子与物质相互作用机制的研究背景和应用价值出发,阐述了有关载能离子在材料中的电子阻止本领的微观机制,总结了基于第一性原理分子动力学研究低速离子在材料中电子阻止本领的相关模型．回顾了国内外关于低能离子与物质相互作用中电子阻止本领及电子能损微观机制的理论和实验研究进展及发展趋势,论述了近几年北京师范大学在有关电子能损微观机制方面所取得的研究成果．阐述了电荷转移、化学键状态以及内层电子激发等因素对电子能损影响的微观机制,研究了在极低速度下电子阻止本领的阈值行为,为离子束技术的应用和材料抗辐照性能的评估提供了理论依据．对未来的研究进行建议展望．      

有机聚合物及小分子材料的电致发光器件

论述了有机聚合物及小分子材料的电致发光原理 ,发光二极管的结构及影响器件稳定性、寿命的原因 ,总结了目前该领域所取得的成果 ,展望了下世纪有机发光材料的应用前景和商业化可能性 .     

纳米纸在绿色电子器件中的研究进展

 纳米纸是由纳米纤维素自组装形成的二维薄膜材料,具有高透明性和极低的表面粗糙度,是一种理想的柔性电子器件基底材料。与合成高分子基底材料相比,纳米纸可以生物降解,为绿色电子器件的制备提供了条件。本文梳理了纳米纸的制备工艺、纳米纸的特点及纳米纸在柔性绿色电子器件,尤其是场效应晶体管、能源器件和发光器件等方面的应用。针对纳米纸在大规模低成本制备、在柔性绿色电子器件中存在的问题进行了分析,并对纳米纸在生物传感中的应用进行了展望。     

Control of conformational and interpolymer effects in conjugated polymers.

The role of conjugated polymers in emerging electronic, sensor and display technologies is rapidly expanding. In spite of extensive investigations, the intrinsic spectroscopic properties of conjugated polymers in precise conformational and spatial arrangements have remained elusive. The difficulties of obtaining such information are endemic to polymers, which often resist assembly into single crystals or organized structures owing to entropic and polydispersity considerations. Here we show that the conformation of individual polymers and interpolymer interactions in conjugated polymers can be controlled through the use of designed surfactant poly(p-phenylene-ethynylene) Langmuir films. We show that by mechanically inducing reversible conformational changes of these Langmuir monolayers, we can obtain the precise interrelationship of the intrinsic optical properties of a conjugated polymer and a single chain's conformation and/or interpolymer interactions. This method for controlling the structure of conjugated polymers and establishing their intrinsic spectroscopic properties should permit a more comprehensive understanding of fluorescent conjugated materials.     

含共轭三键的聚合物的掺杂机理和导电特性的研究

以聚丁（对甲苯硫酸）－２,４－己炔－１,６－二醇酯（ＰＤＡ－ＴＳ）为例,探讨了含共轭三键的聚合物的掺杂和导电特性的研究,对其微观掺杂机制,在比较现有的掺杂模型的基础上,提出了新的掺杂模型。     

Magnetically assisted fluorescence ratiometric assays for adenosine deaminase using water-soluble conjugated polymers

A magnetically assisted fluorescence ratiometric technique has been developed for adenosine deaminase assays with high sensitivity using water-soluble cationic conjugated polymers (CCPs). The assay contains three elements: a biotin-labeled aptamer of adenosine (biotin-aptamer), a signaling probe single-stranded DNA-tagged fluorescein at terminus (ssDNA-Fl) and a CCP. The specific binding of adenosine to biotin-aptamer makes biotin-aptamer and ssDNA-Fl unhybridized, and the ssDNA-Fl is washed out after streptavidin-coated magnetic beads are added and separated from the assay solution under magnetic field. In this case, after the addition of CCP to the magnetic beads solution, the fluorescence resonance energy transfer (FRET) from CCP to fluorescein is inefficient. Upon adding adenosine deaminase, the adenosine is converted into inosine, and the biotin-aptamer is hybridized with ssDNA-Fl to form doubled stranded DNA (biotin-dsDNA-Fl). The ssDNA-Fl is attached to the magnetic beads at the separation step, and the addition of CCP to the magnetic beads solution leads to efficient FRET from CCP to fluorescein. Thus the adenosine deaminase activity can be monitored by fluorescence spectra in view of the intensity decrease of CCP emission or the increase of fluorescein emission in aqueous solutions. The assay integrates surface-functionalized magnetic particles with significant amplification of detection signal of water-soluble cationic conjugated polymers. Supported by the “100 Talents” Program of the Chinese Academy of Sciences, and the National Natural Science Foundation of China (Grant No. 20574073)     

检测汞的全细胞生物传感器构建

汞（Hg）是环境中主要的重金属污染物,暴露于环境中的汞对人体健康有严重危害。汞的精确检测对控制环境污染和减少对健康的危害有着重要意义。该实验是基于MerR蛋白调节的启动子对应答汞毒性基因的调控机理,首先通过试验确定红色荧光蛋白mCherry为报告基因。将MerR基因片段链接到质粒pUC57得到质粒pUC57-MerR,以其为模版得到质粒pUCRR,转入到E. coli DH5α中,得到工程菌株E. coli UCRR。为提高菌株的性能和灵敏度,通过易错PCR技术获得MerR基因突变体库,筛选出菌株V109E在培养4 h时,荧光信号强度远远高于其他菌株荧光信号,对Hg2＋有高度专一性,检测Hg2＋的最低浓度为0.5nM。     

螺旋聚合物的研究进展（综述）

对螺旋聚合物的种类、合成方法、表征手段等方面进行了概述,并对螺旋聚合物的发展历程和发展前景进行了综述。     

Collapse of stiff conjugated polymers with chemical defects into ordered, cylindrical conformations

The optical, electronic and mechanical properties of synthetic and biological materials consisting of polymer chains depend sensitively on the conformation adopted by these chains. The range of conformations available to such systems has accordingly been of intense fundamental as well as practical interest, and distinct conformational classes have been predicted, depending on the stiffness of the polymer chains and the strength of attractive interactions between segments within a chain. For example, flexible polymers should adopt highly disordered conformations resembling either a random coil or, in the presence of strong intrachain attractions, a so-called 'molten globule'. Stiff polymers with strong intrachain interactions, in contrast, are expected to collapse into conformations with long-range order, in the shape of toroids or rod-like structures. Here we use computer simulations to show that the anisotropy distribution obtained from polarization spectroscopy measurements on individual poly[2-methoxy-5-(2'-ethylhexyl)oxy-1,4-phenylenevinylene] polymer molecules is consistent with this prototypical stiff conjugated polymer adopting a highly ordered, collapsed conformation that cannot be correlated with ideal toroid or rod structures. We find that the presence of so-called 'tetrahedral chemical defects', where conjugated carbon-carbon links are replaced by tetrahedral links, divides the polymer chain into structurally identifiable quasi-straight segments that allow the molecule to adopt cylindrical conformations. Indeed, highly ordered, cylindrical conformations may be a critical factor in dictating the extraordinary photophysical properties of conjugated polymers, including highly efficient intramolecular energy transfer and significant local optical anisotropy in thin films.     

四噻吩与富勒烯(C60、C70、C84)间光致电子转移效率的研究

借助荧光猝灭可以观测和研究导电聚合物与富勒烯之间的电子转移效率及机理.文章通过对四噻吩/富勒烯相关原始数据的校正处理,排除了竞争吸收与重吸收对荧光谱值的影响,获得了能真实体现四噻吩与富勒烯(C60、C70、C84)之间荧光猝灭率的数据.