【作者】 王辉；

【导师】 孙涛垒； 张明曦；

【作者基本信息】 武汉理工大学 ， 材料学， 2015， 硕士

【摘要】 糖作为生命体的三大物质单元之一,在自然界中在广泛存在,在生命活动中起着至关重要的作用。其不仅作为能量物质为维持生命体的活动提供能量来源,还作为结构物质为细胞的构建提供骨架单元,而且它还有许多不为人所熟知的功能,如免疫反应、癌症的转移、细胞之间的沟通、病原体引起的传染病等。糖的检测和识别对研究生命体的生理过程以及疾病的产生与转移有着重要的意义。因此对生物体内各种糖的识别和检测已经成为生命科学领域的重要内容,开发对糖具有高选择性和高灵敏度的传感器有着重要的意义。受自然界中细胞膜上离子通道的启发,通过人工合成的方法之制备出具有选择性、响应性和可控性的传感器件,实现对糖的超灵敏性的检测,对生物、化学和材料学尤其是生物传感领域都有着十分重要的理论和实际意义。本论文以苯硼酸、二肽单元为识别单元、硫脲为协同单元、异丙基丙烯酰胺为功能单元,分别合成对糖具有响应性的二元和三元智能共聚物,将其修饰到多孔阳极氧化铝膜的内壁,并利用皮安计检测的方法,构建一种新型的智能纳米通道,用于多种糖的高灵敏性和高选择性识别。本论文的工作分为以下三个部分:第一章为综述部分。对近年来糖的传感器进行了梳理,分为硼酸类受体和非硼酸类受体的糖传感器。并对多孔阳极氧化铝膜在构建智能纳米通道中的应用做了简要的介绍,进一步介绍了本论文研究的目的和内容。第二章将3-丙烯酰硫脲基苯硼酸(ATPBA)与N-异丙基丙烯酰胺(NIPAAm)通过可逆加成-断裂链转移聚合(RAFT)合成的糖响应性聚合物PNIPAm-co-PATPBA修饰到PAA膜的内壁中,构建对糖具有响应性的智能纳米通道。并对修饰的后的PAA膜进行了扫描电子显微镜(SEM)、X射线光电子能谱(XPS)的表征。利用皮安计对构建的纳米通道对葡萄糖、甘露糖、阿拉伯糖和木糖的响应性进行了表征。结果表明我们构建的传感器对糖具有灵敏的响应性和选择性,当糖浓度为10-7 M时,阿拉伯糖、木糖、甘露糖和葡萄糖的电流变化率分别为50%、25%、60%和90%,从而实现对葡萄糖的高灵敏检测。第三章以具有手性识别作用功能性单元二肽分子(β-Asp-Phe)、响应性单元异丙基丙烯酰胺(PNIPAAm)和起调节作用的苯基硫脲单体合成的三元共聚物(PNI-β-MAP-diTFP)修饰多孔阳极氧化铝薄膜,构建对糖对映体具有不同响应性的智能纳米通道,通过皮安计的测量来苏糖对映体通过纳米通道时电流的变化,实现响应性的信号的传递和放大,用于糖对映体的检测和识别。更多还原

【Abstract】 As one of the three substantial units in living body, saccharide widely exists in nature and plays a vital role in life activities, Carbohydrates are well know not only as an energy source for providing energy for life-sustaining body activities, but also as a structural material to provide the backbone units for constructing the cell. In addition he also has many not well-known functions, such as immune response, fertilization, communication between the cells, and infections caused by pathogens and so on. The detection and recognition of sugar has an important significance to study physiological processes of living organisms and disease and transfer. Therefore it has become an important research in life sciences for the detection of saccharides and their concentrations, it is significant for the development of a high sensitivity method for the detection of saccharides. Inspired by the ion pumps and ion channels in cells, the design and preparation artificial ion channels with the properties of selective, responsiveness, and controllable by chemical synthesis methods realize ultra-sensitive detection of monosaccharides, this will have important theoretical and practical significance in the interdisciplinary fields of chemistry, physics, and materials science, especially for biosensing.Sugar-responsive copolymers was synthesized with recognition units(phenylboronic acid or dipeptide), mediating units(thiourea), and functional switching units(N-isopropylacrylamide) and be used to modified the inner surface of porous anodic alumina(PAA) membrane. We build a new type of smart nanochannel, which has high sensitivity and selectivity for the sugar recognition by picoammeter detection.The work of this paper includes the following three contents:Chapter 1. General introduction. We presents an overview about the recent development of saccharide sensors including boronic acid-based sensors and other sensers, and boronic acid-based sensors was described in detail. The porous anodic alumina membrane application in the building smart nanachannels was described and finally the purpose and significance of this research work was presented.Chapter 2. Poly(3-(acryloylthioureido)phenylboronic acid-co-N-isopropyl acrylamide) [P(ATPBA-co-NIPAAm)] was synthesized by reversible addition-fragmentation chain transfer(RAFT) polymerization and be used to modify PAA. The modified nanochannels were characterized by scanningelectron microscopy(SEM), X-ray photoelectron spectrometry(XPS), and contact angle measurements. This modified nanochannel was evaluated by saccharides. Results show that the sensor is high sensitive and selective to sugar, when the sugar concentration is 10-7 M, the current change ratios of arabinose, xylose, mannose and glucose were 50%, 25%, 60% and 90% respectively, so as to realize high sensitive detection of glucose.Chapter 3. Three-component copolymers(PNI-β-MAP-diTFP)with chiral responsiveness containing chiral recognition units(β-Asp-Phe), mediating units [bis(trifluoromethyl)-modified phenylthiourea(diTFP)], and functional switching units(PNIPAAm) was synthesized by RAFT polymerization. PAA membrane was modified with the three-component copolymers and characterized by SEM and XPS. This modified nanochannel has different response for sugar enantiomers,which can realize signal transmission and amplification, and used in the detection of sugar enantiomer.更多还原