基于刺激响应调控的聚合物膜电位型传感器用于多组分检测

In this project, novel polymeric membrane potentiometric sensors for multianalyte analysis using stimuli-responsive controlled molecularly imprinted polymers (MIPs) as receptors will be systematically investigated. The multianalyte detection mechanism of the proposed sensors based on stimuli-responsive MIPs will be clarified. For the first time, a smart potentiometric sensor for detection of multianalytes will be developed. The high-affinity functional monomers with stimuli-responsive properties are synthesized and then the stimuli-responsive MIPs with high selectivities are prepared. The obtained receptors are used as the recognition elements in the polymeric sensing membrane. By using different stimuli such as light, temperature and pH, each MIP in the membrane can function as the recepetor sequentially. Thus, multianalytes can be detected by the potentiometric sensor based on the MIP. In order to improve recognition abilities of MIPs in organic sensing membrane, a soluble MIP technique is employed. To eliminate the ion flux of primary ion and ion-exchange effect which can affect the detection limit significantly, the proposed is conditioned by interfering ions instead of primary ions. In this case, the detection sensitivity is largely improved. After measurements, the membrane can be easily and fastly regenerated by using environmental stimuli. This study makes a great contribution to the achievement of potentiometric multianalyte analysis and the improvement of sensor sensitivity, selectivity and regeneration, which will significantly promote the application of ion-selective electrode in the field of analytical chemistry.

本研究将对聚合物膜电位型传感器检测多组分进行系统研究，深入探讨以刺激响应分子印迹聚合物作为可调控识别元件构建电位型传感器的新方法，阐明传感器刺激响应调控检测多组分机理，首次开发出一类可检测多组分的智能型电位型传感器。通过合成具有刺激响应特性的高特异性功能单体，进而合成出高选择性的刺激响应分子印迹聚合物，并将其作为电极敏感元件；利用光、温度或pH等刺激因素调控膜相中多种刺激响应印迹载体先后发挥识别作用，实现电极对多种待测组分的电位检测；结合膜溶性印迹技术，提高印迹载体在膜相中的分子识别能力；通过采用干扰离子活化电极法消除主离子通量和“离子交换效应”，显著提高电极检测灵敏度；利用印迹载体的刺激响应特性，实现敏感膜的快速、高效更新。本项目在实现单支电位型传感器对多种待测物的高特异性识别以及高灵敏、高可逆性检测等方面具有重要的理论和方法上的创新，将为离子选择性电极在分析化学领域中的应用做出贡献。

聚合物膜离子选择性电极具有操作简单、成本低廉以及选择性高等诸多优点，广泛应用于工业分析、临床化验、环境监测等领域。然而，对于此类电极来说，单支电极仅能检测一种离子，这使得此类电极难以满足分析化学领域多组分分析检测需求。.本研究对聚合物膜电位型传感器检测多组分进行系统研究，以刺激响应分子印迹聚合物修饰的纳米孔作为可调控识别元件构建电位型传感器，利用温度和pH等刺激因素调控多种刺激响应印迹聚合物先后发挥识别作用，实现单只电极对多种待测组分的电位检测。.项目利用异丙基丙烯酰胺作为温度刺激响应单体，苯硼酸基单体作为pH 刺激响应单体，在纳米孔内表面合成了兼具温度和pH 刺激响应的分子印迹聚合物，并构建了纳米孔修饰的电位型传感器。优化了计时电位检测条件，实现了单只电极对甲胎蛋白和前列腺特异性抗原的先后电位检测，电极对5-100 μg/L的AFP和PSA呈现线性响应，检出限分别可达0.17和0.42 μg/L；利用刺激响应印迹聚合物的特性，改善了传感器检测的可逆性和稳定性；在此基础上，研制了一系列选择性好、灵敏度高、噪音低、环境相容性良好的电位型传感器，丰富和发展了聚合物膜电位型传感器技术。.项目开发的刺激响应分子印迹聚合物修饰纳米孔，将显著提升基于纳米孔技术的光、电化学传感器响应性能；开发的电位多组分检测方法，将极大地提升电位型传感器检测效率，拓宽电位分析技术的应用空间。.共发表论文18篇，其中SCI期刊论文16篇，12篇发表在中科院一区Top SCI期刊上。4篇发表于《美国分析化学》杂志，2篇发表于《Trends in Analytical Chemistry》杂志；获得中国发明专利授权2项，申请中国发明专利4项；培养博士及硕士毕业生5名；项目负责人在国内外会议上做特邀/邀请/口头报告6次；项目负责人获得了中国科学院“青年创新促进会”优秀会员以及山东省泰山学者青年专家等荣誉。