新型聚二乙炔微米管敏感材料

Now continuous interest has been devoted to the fabrication of one-dimensional conjugated polymer microtube materials because of their high conductivity, ease of preparation and operation, good environmental stability, and a large variety of applications in molecular wires, chemical sensors, biosensors, and electronic devices. To data, the conjugated polymer microtube materials have been prepared by various methods including "the hard-templates method" by using zeolite channels, tract-etched polycarbonate and porous alumina membranes, "the soft-templates method" by using the micelle, surfactant, liquid crystal and inverse micro-emulsion, and "the self-assembly method". Moreover, the interfacial polymerization, oligomer-assisted and nanofiber seeding method have been also used to synthesize the conjugated polymer microtube materials. Polydiacetylene, classified as a one-dimensional conjugated polymer, possesses many interesting features in their electronical and optical properties. However, the design and synthesis of novel one-dimensional polydiacetylene microtube assembled from the nanometer-sized vesicle still remain a challenge. In this application, we will develop a novel facile and effective approach to fabricate polydiacetylene microtube based on the cooperation effect of the vesicles served as the basic self-assembling components and the non-covalent interaction (including van der Waals forces, hydrophobic interactions, hydrogen bonds and coordinate bonds) served as the main self-assembly driving forces. We will study the effect of the cooperation effect of the vesicles and the non-covalent interaction among the self-assembling components on the formation of one-dimensional polydiacetylene microtube structure, and explore the rule of the construction and variation of the polydiacetylene microtube structure. And we will also study the chromatic transition of the polydiacetylene microtube materials upon the external stimuli, and explore the effect of the composition, the diameters and the surface micro-structure of the designed polydiacetylene microtube on the responsive selectivity and sensitivity of the prepared materials, and reveal the relationship between the structure and function of the materials. Furthermore, by combining with the specific probe (or receptors) or the quantum dots, we will prepare novel one-dimensional polydiacetylene microtube composite materials with high selectivity of recognition and high sensitivity. The facile preparation procedures and their efficiency of response to the surrounding media, chemical and bio-analytes may render these novel microtube composite materials potential candidates for the applications in smart materials, chemical sensors and biosensors.

随着材料科学的飞速发展，设计和合成具有新型结构的聚合物材料，研究其独特的物理化学性质和功能已成为当今高分子领域研究的主要方向。特别是具有一维微米管状结构的共轭聚合物材料，由于其独特的结构-性能特征和广阔的应用前景而受到人们关注。本申请拟以纳米尺度的二乙炔囊泡为组装基元，配位键和氢键等非共价键相互作用为主要驱动力，通过自组装技术构筑聚二乙炔微米管；通过比较系统的研究找到二乙炔囊泡聚集、融合以及自发卷曲形成微米管状结构的临界条件，探索微米管组成、尺寸以及表面微结构等因素对聚二乙炔微米管材料敏感性能的影响，揭示聚二乙炔微米管材料多层次结构构筑和性能调控的规律；在此基础上，通过化学修饰和物理组装,将化学与生物分子探针、无机量子点等引入到聚二乙炔微米管体系中，制备一系列高选择性和响应灵敏度的聚二乙炔微米管复合材料，并进一步拓展其在智能材料、化学与生物传感器等领域的应用。

随着人类社会的高速发展，对信息量需求的不断增加，基于低维功能材料的各项研究受到广泛重视，将低维结构和共轭聚合物材料有机结合有望获取许多新的功能和应用。聚二乙炔主链构象对环境十分敏感，热、pH、溶剂、离子、应力和极性气体等外界刺激均能诱导聚二乙炔主链构象发生变化，从而发生肉眼可识别的颜色变化，甚至产生荧光，在光电子器件、高密度存储、化学和生物传感器等领域有重要潜在应用。我们在低维聚二乙炔功能材料的控制合成、表面修饰及功能调控等方面做了许多探索和尝试。在国家自然科学基金(51273186)的资助下，我们以聚二乙炔复合囊泡为基本组装单元，通过分级组装方法制备了聚二乙炔微米管：聚二乙炔复合囊泡先聚集融合形成片层结构，片层结构逐渐卷曲最终形成空心的微米管结构，配位键、氢键等非共价键相互作用在微米管的形成过程中起到了重要的作用。研究发现聚二乙炔微米管具有大的比表面积，良好的力学性能、化学稳定性和生物相容性，单分散性和可操作性好。红相聚二乙炔微米管表现出典型的光波导行为，通过外界环境刺激调节聚二乙炔微米管荧光强度即可对微米管光传输行为进行调控。我们通过物理组装或表面化学修饰等手段在微米管表面引入了不同的功能基团，制备了一系列功能化的聚二乙炔微米管，并探索了其在化学与生物传感器、智能光子学器件等领域的应用：1. 我们将化学与生物分子探针修饰到聚二乙炔微米管表面，构筑了一系列新型化学与生物荧光传感器，应用于高灵敏度和选择性地检测三硝基苯酚、miRNA等。2. 我们通过简单有机化学反应将螺吡喃、紫精等光、电响应基元修饰到聚二乙炔微米管表面，构筑了一系列新型光、电响应的智能光波导器件，并实现了一系列与门，或门和与非门等逻辑门操作。以上的研究工作有助于我们揭示聚二乙炔微米管形成机理，为构筑结构功能化和功能集成的聚二乙炔微米管器件提供理论基础和关键技术，并拓展其在化学和生物传感器、智能光子学器件等领域的应用。