导电高聚物的合成及酶传感器的研究

【作者】 潘献华；

【导师】 阚锦晴；

【作者基本信息】 扬州大学 ， 物理化学， 2005， 硕士

【摘要】 1.导电复合材料葡萄糖氧化酶传感器的研究 研究了由乙基纤维素和乙炔黑制得的导电聚合物复合材料作为载体制备葡萄糖氧化酶传感器的方法及其性质。传感器的制备过程为:首先将0.010 g乙基纤维素,0.004 g乙炔黑,0.2 mg葡萄糖氧化酶和0.002 g固体石腊用1.5 cm³ YD-1试剂调成糊状物,然后取其1/40均匀涂在3mm×3mm的铂电极上,待其干燥后用环己烷洗去其中的石蜡即可制得葡萄糖氧化酶传感器。讨论了多种因素对该传感器响应电流的影响。当葡萄糖的浓度低于11.5 mmol dm^-3时,该传感器的响应电流随葡萄糖浓度增加而增大。实验测得此传感器酶催化反应的活化能为40.3 kJmol^-1。原子力显微镜表明,用环己烷洗去石蜡的导电聚合物复合材料葡萄糖氧化酶传感器具有粒状结构,这有利于酶催化反应的进行。 2.聚苯胺尿酸酶传感器的研究 首次研究了“模板法”制备聚苯胺尿酸酶传感器。其制作过程如下:首先由“一步法”制得聚苯胺尿酸酶电极,将该电极在6.0 mol dm^-3的HC1溶液中回流24小时以除去其中的尿酸酶（这些酶可能在固定过程中受苯胺单体的影响而失去了活性）。最后,根据聚苯胺的掺杂原理将有活性的尿酸酶固定进聚苯胺膜中制得聚苯胺尿酸酶传感器。讨论了温度、pH、电位和底物浓度等多种因素对该生物传感器响应电流的影响。通过尿酸酶传感器稳定性的测定可知,“模板法”制备的酶传感器的响应电流在60天内仅下降了18%,而由“两步法”制备的酶传感器的响应电流在40小时内就下降了39%。“模板法”制备的尿酸酶传感器中尿酸酶与聚苯胺的结合点为其醌环上的氮原子。首次将紫外和红外等运用于传感器的表征。 3.聚苯胺葡萄糖氧化酶传感器的研究 研究了“模板法”制备聚苯胺葡萄糖氧化酶传感器。其制作过程如下:首先扬州大学硕士论文由“一步法”制得聚苯胺葡萄糖氧化酶电极,将该电极在6.0 moldm一3的Hcl溶液中回流24小时以除去其中的葡萄糖氧化酶（这些酶可能在固定过程中受苯胺单体的影响而失去了活性）。最后,根据聚苯胺的掺杂原理将有活性的葡萄糖氧化酶固定进聚苯胺膜中制得聚苯胺葡萄糖氧化酶传感器。讨论了多种因素对该生物传感器响应电流的影响,如温度、pH、电位和底物浓度。通过葡萄糖酶传感器稳定性的测定可知,“模板法”制备的酶传感器的响应电流在30天仅仅下降了4.6%,而“两步法”制备的传感器的响应电流下降了55.4%。由紫外、红外的表征可知“模板法”制备的葡萄糖氧化酶传感器中葡萄糖氧化酶与聚苯胺的结合点为其醒环上的氮原子。4.苯胺和邻氯苯胺的电化学共聚 研究了用循环伏安法实现苯胺和邻氯苯胺的共聚。苯胺和邻氯苯胺电化学共聚的增长速率、氧化还原电位和电荷传递机制与苯胺和邻氯苯胺单体聚合均不同。苯胺和邻氯苯胺共聚物在甲基毗咯烷酮（NMP）、二甲基甲酞胺（DMF）、二甲基亚矾（DMSO）或丙酮等溶剂中具有良好的溶解性。比较了聚苯胺、聚邻氯苯胺及其共聚物的红外光谱。扫描电镜形貌和溶解度实验结果表明,共聚物并不是聚苯胺和聚邻氯苯胺的简单混合物。共聚物所表现出来的电化学性质主要由聚苯胺决定,但较聚苯胺有更好的电化学可逆性和可溶解性。5.苯胺一邻氨基苯酚共聚物尿酸酶传感器的研究 首次研究了用一种新型的共聚物来制备尿酸酶传感器。其制作过程如下:首先由循环伏安法制得苯胺一邻氨基苯酚共聚物尿酸酶电极,将该电极在6.0 moldm一3的HCI溶液中回流24小时以除去其中尿酸酶（这些酶可能在共聚过程中受影响而失去了活性）,最后根据苯胺一邻氨基苯酚共聚物的掺杂原理将有活性的尿酸酶固定进共聚物膜中获得共聚物尿酸酶传感器。研究了温度、PH、电位和底物浓度等因素对响应电流的影响。实验结果表明“模板法”制备的共聚物尿酸酶传感器的更多还原

【Abstract】 1.Immobilizing Enzyme Using Conducting Polymer CompositeMaterialThe preparation and properties of glucose oxidase biosensor using conducting polymer composite material consisted of ethyl cellulose and acetylene black is reported. The final biosensor is constructed by applied the mixture containing 0.010 g ethyl cellulose, 0.004 g acetylene black, a little paraffin wax and 0.2 mg glucose oxidase on a platinum electrode (3 mm×3 mm). Effect of various factors on the response current of the biosensor was discussed. The response current increases linearly with increasing glucose concentration under 11.5 mmol dm~-3. Its activation energies are 40.3 kJ mol~-1 in enzyme-catalyzed reaction. AFM shows that conducting polymer composite material-glucose oxidase electrode’s film presents uniform granular structure after paraffin wax is washed with cyclohexane, which is conducive to enzyme-catalyzed reaction.2.Polyaniline-Uricase Biosensor Prepared with Template ProcessPolyaniline (PANI) uricase biosensor prepared with template process is first reported in this paper. The fabrication process is as follows: PANI-uricase electrode is obtained using one-step process. Then the electrode is hydrolyzed in 6.0 mol dm~-3 hydrochloric acid solution to remove the uricase that may be affected by aniline monomer from PANI film. Finally, active uricase is immobilized into the PANI film again and PANI-uricase biosensor is obtained. Some factors that affect response current are studied, such as temperature, pH, potential and substrate concentration. The determination of biosensors indicates that the response current of the biosensor prepared by template process only decreases by about 18% for 60 days, but that prepared bytwo-step process decreases by approximately 39% for 40 hours. The uricase in PANI-uricase biosensor prepared by template process mainly interact with the nitrogen that link with quinoid ring. It is characterized with FTIR and UV-vis for the first time.3. Polyaniline glucose oxidase Biosensor Prepared with TemplateProcessA new method of preparing polyaniline (PANI) glucose oxidase sensor, which is called template process, is reported in this paper. The process is as follows: Firstly, PANI glucose oxidase electrode is obtained using one-step process. Then the electrode is hydrolyzed in 6.0 mol dm"3 hydrochloric acid solution to drop the glucose oxidase affected by aniline monomer out from PANI film. Finally, active glucose oxidase is immobilized into the PANI film again and PANI glucose oxidase sensor is obtained. Some factors that affect response current are studied, such as temperature, pH, potential and substrate concentration. The stability of biosensors indicate that the response current of the biosensor prepared by template process comes to a maximum at the first two days, then decrease only 4.6% for 30 days; but that prepared by two-steps process decreases approximately 55.4%. The experiment show the glucose oxidase in the biosensor prepared by template process mainly locates at the nitrogen of quinoid ring.4. Electrochemical Copolymerization of Aniline and 0-ChloroanilineThe electrochemical copolymerization of aniline and o-chloroaniline using cyclic voltammetry is reported. The copolymerization of aniline and o-chloroaniline was different from the monopolymerization of aniline or o-chloroaniline in growth rate, redox potentials, and the charge transport mechanisms. The copolymer possesses good solubility in common organic solvents, such as NPM, DMF, DMSO or acetone. FTIR spectra and SEM were used to determine the possible structure and the morphology forcopolymer, respectively. According to the image of SEM and the solubility, the copolymer isn’t the simple mixture of polyaniline and poly-o-chloroaniline. The electrochemical properties of the copolymer are mainly determined by PANI, but the copolymer has better electrochemical reversibility and solubility.5. Preparation and properties of an uricase biosensor based oncopolymer of o-aminophenol-anilineAn uricase biosensor prepared with a new copolyme更多还原