【作者】 李艳春；

【导师】 宋焱焱；

【作者基本信息】 东北大学 ， 分析化学， 2013， 硕士

【摘要】 葡萄糖生物传感器是利用葡萄糖氧化酶催化反应的高度专一性与电化学信号检测的高灵敏度的一种电化学生物传感器。通过引入纳米粒子,由于纳米材料比表面积大,生物相容性好,不仅可以增加葡萄糖氧化酶的吸附量和稳定性,还可以促进酶与电极之间的电子传递速率,进而提高酶的催化活性和电极的响应速度和检测灵敏度。第一章简要综述了普鲁士蓝(PB)的结构、制备方法、电化学性质及应用,纳米材料的制备方法、性质及应用,酶生物传感器中生物分子的固定方法及其在葡萄糖传感器中的应用。第二章研究了修饰PB的Ti02纳米管阵列电极在H202传感器中的应用。采用阳极氧化法制备了直立生长的高度有序的TINT阵列电极,并且通过表面修饰技术在TiNT表面组装了AuNPs,有效地改善了TiNT阵列电极的导电性能。通过光照法沉积一层PB,制备了PB-AuNPs/TiNT修饰电极。FT-IR、XPS、XRD和电化学研究结果表明：固定在AuNPs修饰的TINT阵列电极上的PB有良好的生物催化性能,对H202有很好的电化学传感响应,该PB-AuNPs/TiNT阵列电极对H202的浓度检测范围为1.1 μmol/L～6.7 mmol/L,检测限为0.1 μmol/L。第三章发展了双酶修饰的PB的Ti02纳米管阵列电极的葡糖糖安培传感。通过邻苯二胺的电化学聚合将葡萄糖氧化酶和辣根过氧化物酶固定在第二章中制备的PB-AuNPs/TiNT上,并通过FT-IR证实了邻苯二胺(OPD)和双酶的已经成功组装。通过电化学实验可以看出酶的活性中心与电极表面间发生了直接电子转移并且酶在电极上保持了良好的生物活性和电催化活性。通过对所构建的双酶体系的葡萄糖传感性能进行研究得出：GOD-HRP-OPD-PB-AuNPs/TiNT电极对Glucose的浓度检测范围为0.03～0.30 mmol/L,检出限为10 μmol/L (S/D=3),灵敏度为0.021·mA·L·cm-2·mmol-1;而当电聚合时加入AuNPs,得到的AuNPs-GOD-HRP-OPD-PB-AuNPs/TiNT电极对Glucose的浓度检测范围为0.03～0.50 mmol/L,检出限达到1.0μmol/L (S/D=3),灵敏度为0.15·mA·L·cm-2·mmol-1。可见,随着AuNPs的加入,使双酶体系具有更高的检测灵敏度和更低的检测限。此外,由于电聚合得到的聚邻苯二胺是非导电型聚合物,因此本体系对常见的电活性物质如：抗坏血酸、尿酸、对乙酰氨基酚等,具有非常好的抗干扰能力。更多还原

【Abstract】 As an electrochemical biosensor, glucose biosensor takes advantage of high-specificity of glucose oxidase enzymatic reaction and high-sensitivity of Electrochemical signal detection. Nanoparticles have large specific surface area and high biocompatibility, and nanoparticles can also promote electron transfer rate between enzyme and electrode. We introduced nanoparticles to increase adsorptive capacity and stability of glucose oxidase (GOD). With this method, catalytic activity of enzyme, response speed of electrode and detection sensitivity can be improved.In chapter 1, we give a review for the structure, preparation method, and application of Prussian blue and nanomaterials. In this chapter, we also described fixing method of biological molecules and their application in glucose sensorsIn chapter 2, the application of PB modified TiO2 nanotube arrays in H2O2 sensing was studied. First, highly ordered TINT arrays electrodes were prepared by anodization, and then AuNPs was assembled on TiNTs via surface modification. By this method, the electrical conductivity of the TiNT arrays electrodes was improved effectively. PB-AuNPs/TiNT modified electrodes were prepared by illuminating. The results of FT-IR, XPS, XRD and electrochemical measurement showed that the PB which is decorated on AuNPs/TiNT arrays electrodes. The resulting electrode showed good electrochemical sensing response to H2O2 with the detection linear range of 1.1μmol/L to 6.7 mmol/L and detection limit was 0.10 μmol/L.In chapter 3, Glucose amperometric biosenser was developed about double enzyme modification based on PB/TiO2 nanotube arrays electrode. Glucose oxidase and horseradish peroxidase were fixed on the PB-AuNPs/TiNT by electrochemical polymerization of o-phenylendiamineThe FT-IR results confirmed that o-phenylendiamine(OPD)and double enzyme were assembled successfully. Electrochemistry results showed that direct transfer of electrons take out between active center of enzyme and electrode surface. Simultaneously, enzymes molecules fixed on the electrode keep their biological activity and electrocatalytic activity. Based on the study of dual-enzyme glucose sensing, the resultant composite electrode exhibit the detection linear range of 0.03 mmol/L to 0.30 mmol/L for glucose sensing on GOD-HRP-OPD-PB-AuNPs/TiNT electrodes, with the detection limit of 10 μmol/L(S/D=3), and the sensitivity of 0.021·mA·L·cm-2·mmnol-1. When AuNPs were introduced to electrochemical polymerization, the detection linear range is from 0.03 mmol/L to 0.50 mmol/L for glucose sensing on AuNPs-GOD-HRP-OPD-PB-AuNPs/TiNT electrodes, with the detection limit of 1.0μmol/L, and the sensitivity of 0.15-mA-cm-2·mmol-1·L. It can be concluded that, with the introduction of AuNPs the dual-enzyme glucose sensor exhibit a higher sensitivity and lower grade detection limits. Moreover, as poly o-phenylendiamine is one of non-conductive polymers, this system has high anti-interference ability to common electroactive material such as ascorbic acid, uric acid and acetaminophen and so on.更多还原