类水滑石纳米片/手性大分子电化学传感器的构建及分子识别研究

Chirality is one of the essential attribute of nature and has attracted a lot of attention from various areas. With the development of technology, chiral recognition has become the frontier and hot spots of research in the field of inorganic functional materials. Our research tends to combine nano-layer assembly technology with electrochemistry methods. At the meantime, making a combination of the advantages of the region selectivity of chiral macromolecules as well as chiral recognition and the characteristics of electrochemical sensors, such as simplicity, speed, sensitivity and high efficiency, etc. Based on the premise, we try to conduct the research on the construction of hydrotalcite-like nanosheets/chiral macromolecules electrochemical sensor as well as the study of molecule recognition. By functional design, the Mg2+ and Al3+ in the molecular structure of hydrotalcite will be replaced by the transition metal, whose charge is the same with Mg2+ and Al3+and radius are close with substituted elements. By this, we can require the precursor of multi-class hydrotalcite with perfect electrical activity. After that, to prepare the nanosheets of hydrotalcite with positive charge by the new type of stripping layer technology, and analyzing the structure and properties of as-prepared nanosheets with modern instruments. To assemble the preferred matching chiral macromolecules to the nanosheets with the help of multiple-class hydrotalcite-like nanosheets, which possess high-density charge, abundant hydrogen bonding sites and the acid-base activity, to obtain the inorganic/organic composite. To construct series of chiral electrochemical sensor device with excellent performance and stable structure to achieve the chiral recognition and high sensitive sensor of various types of antipodes on the electroactive substrate. The work is not only an innovation in sensor device, and has broad application prospect in chiral separation and detection.

手性是自然界的本质属性之一。手性识别已成为无机功能材料领域的研究前沿和热点。本项目拟将纳米片层组装技术与电化学方法相结合，将手性大分子的区域选择性及手性识别优势与电化学传感的简便快速、灵敏高效等优点相结合，开展水滑石纳米片/手性大分子新型电化学传感器的构建及分子识别研究。通过功能设计，采用电荷相同、半径相近的过渡金属离子同晶取代水滑石结构中Mg2+、A13+，制备电活性好的多元类水滑石前驱体；用新型剥层技术制备带有正电荷的水滑石纳米片，并借助现代仪器手段表征产物的结构和性能；利用多元类水滑石纳米片上高密度电荷、丰富的氢键位点及酸碱反应活性，将优选的匹配手性大分子组装到纳米片上，获得无机/有机手性复合材料；在电活性基底上构建出系列性能优异、结构稳定的手性电化学传感器件，以实现不同类型对映体的手性识别和高灵敏传感。该研究不仅具有传感器件上的创新，而且在手性分离和检测方面具有广阔的应用前景。

多元类水滑石纳米片上高密度电荷、丰富的氢键位点及酸碱反应活性，将优选的大分子组装到纳米片上，可获得无机/有机复合修饰材料，可构建出系列性能优异、结构稳定的手性电化学传感器件，以实现不同类型高灵敏传感。本项目通过尿素分解—均匀共沉淀法制备了NiAl水滑石（LDHs）六边形的纳米片胶状液并与铬黑T交替组装到电极上，构筑了检测水杨酸的电化学传感器；建立了合成镍铝水滑石纳米片-多壁碳纳米管复合材料的新方法，并构建了测定手性酪氨酸传感器和维生素B6、6-硫鸟嘌呤、维生素B2的系列电化学传感器。用电沉积法制备了氮掺杂的多壁碳纳米管表面生长NiAl/LDH纳米片的复合材料的修饰电极，构建对儿茶酚（CA）的电化学传感器；合成了Ni2+/MgFe水滑石纳米片的新材料，构建了基于葡萄糖酶生物传感器；合成了H-NiAl /LDHs纳米片状材料构建了用于检测的儿茶酚和对苯二酚传感器；用共沉淀法制备了一系列Ni2+/MgFe（LDH）新型三元复合纳米片材料，构建了检测对硝基苯酚等系列传感器；研究了对于L/D- 苯丙氨酸具有手性识别的传感体系；开展了L-半胱氨酸自组装纳米金修饰的碳糊电极对D,L-色氨酸的手性识别，并探讨其识别规律；制备了基于四氧化三钴-石墨烯纳米复合材料，构建了L-酪氨酸安培型传感器；研究了聚溴甲酚绿修饰电极（PBG/GCE）对尿酸、多巴胺和抗坏血酸的同时测定；制备了均匀有序的介孔ZnCo2O4纳米球，并用于修饰电极超灵敏电化学检测H2O2和葡萄糖燃料电池的研究；建立了静电纺丝法制备水滑石类金属氧化物新技术，总结了形成过程的一般规律；建立了电化学制备石墨烯-过渡金属氧化物纳米复合物的新技术，对扑热息痛和非那西汀进行了超灵敏测定；研究了电沉积氮化石墨烯-碳纳米管复合物作为增敏材料的咖啡因和香兰素电化学传感器；制备了石墨烯/β-环糊精纳米复合薄膜并用于检测槲皮素；用聚磺基水杨酸修饰的玻碳电极对罗红霉素和多巴胺进行了同时测定；基于电聚合分子印迹聚合物建立了复杂样品中目标物高灵敏度定量检测方法。为生命和环境体系的在线检测提供简便快速、灵敏高效的新手段。