【作者】 周磊；

【导师】 吴守国；

【作者基本信息】 中国科学技术大学 ， 分析化学， 2014， 硕士

【摘要】 过氧化氢(H202)的检测在环境监测和医学治疗方面都是非常重要的课题,因为H202即是工业生产过程中的副产物,也是生命代谢过程的副产物。普鲁士蓝(PB),被人称为“人工过氧化氢酶”,被广泛运用于H202电化学传感器和基于H202检测的生物传感器。相较于贵金属电极(如Pt电极),PB可以在较低的应用电势下催化还原H202,从而避免电话性物质的干扰；相较于昂贵且难以储存的酶电极,PB价格便宜且性能优越。然而,在弱碱性环境下PB稳定性较差是其主要缺陷。目前,将PB和导电聚合物进行杂化是改善PB膜稳定性的重要方向。在协同作用下,杂化膜可能具有两者性质,并有可能克服彼此的缺陷,从而整体提升PB的性能。导电聚合物具有优良的导电性、机械性能和生物相容性,但是其在弱碱性环境下导电性大大降低,限制了导电聚合物的实际应用。大量有关导电聚合物与PB的杂化膜被广泛报道,尤其是聚苯胺与PB的杂化膜。然而有关聚苯胺衍生物与PB的杂化材料却很少有人报道,并大部分之报道均采用分层镀膜的方式,其他镀膜方式鲜有报道。论文的主要研究工作有：1首次提出在含有低浓度乙酰苯胺(10mM)和FeCl3-K3[Fe(CN)6]4的电镀液中,采用循环伏安法以共沉积方式镀膜,只需一步即可制备聚乙酰苯胺-普鲁士蓝(PNAANI-PB)杂化膜。考察了杂化膜的结构和电化学性能,并且探究了电镀液中乙酰苯胺浓度和镀膜圈数对杂化膜性能的影响。PNAANI-PB杂化膜对H202的响应十分快速,具有良好的重现性,尤其是在弱碱性环境中稳定性好以及高灵敏、超宽线性。随后我们通过滴涂葡萄糖氧化酶-壳聚糖溶液制备了基于PNAANI-PB杂化膜的葡萄糖传感器。实验表明,该传感器性能优异且具有优良的抗干扰能力。2一种新型的PB/PNAANI-PB杂化膜通过两步制备出来：第一步,利用循环伏法在玻碳电极表面沉积PB膜,使得电极表面带有负电性；第二步,在含有高浓度乙酰苯胺(30mM)和FeCl3-K3[Fe(CN)6]4的电镀液中,利用循环伏安法在PB膜表面共沉积PNAANI-PB杂化膜。考察了复合杂化膜的结构和电化学性能,并且探究了两次循环伏法镀膜圈数对杂化膜性能的影响。PB/PNAANI-PB杂化膜对H202的响应具有电流稳定、重现性良好,弱碱性稳定性好以及高灵敏、超宽线性等优点。3我们利用现场化学合成PNAANI-PB杂化复合材料。在含有低浓度乙酰苯胺(10mM)和FeCl3-K3[Fe(CN)6]4的混合溶液,在常温水相条件下,通过两者自发的氧化还原化学反应生成PNAANI-PB杂化复合材料。以乙酰苯胺做还原剂在FeCl3-K3[Fe(CN)6]4体系中生成PB,而乙酰苯胺则以FeCl3为氧化剂发生聚合反应。通过后续的酸洗、水洗处理,制备出PNAANI-PB杂化复合材料悬浊液,滴涂在玻碳电极表面,制备出PNAANI-PB杂化复合膜修饰电极。考察了PNAANI-PB复合杂化膜的结构和电化学性能,并且探究乙酰苯胺浓度对PNAANI-PB杂化复合膜修饰电极性能的影响。实验也表明,PNAANI-PB杂化复合膜修饰电极对H2O2的响应具有电流高度稳定、极高灵敏度、较宽线性以及非常好的重现性等优点。更多还原

【Abstract】 The detection of hydrogen peroxide (H2O2) is an important topic for environmental control and clinical diagnosis due to it is not only a product of industry but also a risk factor for some diseases. Prussian Blue (PB), known as an artificial peroxidase, has been extensively used for H2O2detection and been a fundamental material for possible mass production of biosensors, due to its excellent catalysis for H2O2reduction at low potentials compared to noble metal, and a relatively cheap and stable electro-catalyst compared to enzyme. However, the primary problem of using PB as catalyst for detection of H2O2is the poor operational stability at neutral and alkaline solutions.Recently, hybrid film, which based on integration of PB and conducting polymers, has both properties of the individual components with the synergistic effect. Conducting polymers has their unique electronic and mechanical properties, as well as biocompatibility. However, as pH of the media increased above4, the polymer would lose its electrochemical activity, the applications in bioelectrochemistry are limited in neutral aqueous solutions. By now, large kinds of conducting polymer/PB composite films, specially composites of PB and PANI have been wildly studied. However, conducting hybrid composites using PB and polyaniline derivations are seldom studied. On the other hand, many reports were focused on the avenue of step by step for deposition, but the procedure of co-deposition have rarely been reported on this field. The main aspects were as follows:1A novel conductive polymer poly(N-acetylaniline)-Prussian blue (PNAANI-PB) hybrid film was prepared by one step co-electrodeposition in electroplating bath simultaneously containing low concentration of N-acetylaniline (10mM) and FeCl3-K3[Fe(CN)6]4. The structure and electro-activity of the PNAANI-PB hybrid film were evaluated. The effects of potential scanning cycles and the concentration of N-acetylaniline on the formation of the hybrid composite film were investigated. The hybrid film demonstrated rapid response, good reproducibility, long-term stability and free of interference towards reduction of H2O2. A glucose biosensor was further fabricated by immobilization of glucose oxidase on the hybrid film and applied to detect glucose in human serum samples. 2A novel conductive polymer PB/PNAANI-PB hybrid film was prepared by two steps. Firstly, the pure PB was electrodeposited on the GCE to form the negative charges of the surface of the electrode. Secondly, the PNAANI-PB hybrid film was co-electrodeposited on the pure PB film, by one step in electroplating bath simultaneously containing high concentration of N-acetylaniline(30mM) and FeCl3-K3[Fe(CN)6]4. The structure and electro-activity of the PB/PNAANI-PB hybrid film were investigated. The effects of potential scanning cycles in the both two steps were also investigated. The hybrid film demonstrated high current sensitivity, good reproducibility, and long-term stability towards reduction of H2O2.3In this work, a new methods for "in situ" chemically synthesized PB was proposed, and a novel route for fabrication PNAANI-PB hybrid composites is proposed by the spontaneous redox reaction in the FeCl3-K3[Fe(CN)6] and the N-acetylaniline solution. PB was easily synthesized from the FeCl3-K.3[Fe(CN)6] solution by using N-acetylaniline as reducer and chemical oxidation polymerization of N-acetylaniline simultaneously. With the existence of electrostatic interaction, the PNAANI-PB hybrid composites show synergistic augmentation of the response current for H2O2detection. The PNAANI-PB hybrid composites films exhibits high sensitivity, rapid response, good reproducibility, and long-term stability.更多还原