【作者】 毛燕妮；

【导师】 马建国；

【作者基本信息】 东华理工大学 ， 应用化学， 2012， 硕士

【摘要】 电化学测定方法是将化学物质的变化归结为电化学反应，即以体系中的电位、电流或电量作为发生化学反应的量度进行测定的方法，具有简单易行、灵敏度高和实时性好等特点。β-环糊精/碳纳米材料体系具有很好的导电性、稳定性和生物相容性。在不需要添加交联剂的情况下就可以很好的固定各种物质。目前，这样复合体系主要用来设计各种各样的生物电化学装置，以改善这些装置的生物活性和光电等性能。本文主要是通过利用特定的方法对碳纳米管、石墨烯和β-环糊精进行改性和修饰，以改善碳纳米管、石墨烯和β-环糊精的溶解性和分散性，同时也进一步提高了这几种物质的的电化学性能。将这些改性碳纳米管、石墨烯、β-环糊精复合后，再用于电极的修饰，修饰后的电极用于一些生物大分子的电化学性能以及电化学行为的研究，并进一步应用于生物大分子含量的测定，探索效果良好的分离方法和测试手段。论文主要包括以下内容：1.研究了多巴胺(DA)和抗坏血酸(AA)在氨基-β-环糊精/石墨烯/二茂铁修饰电极的电催化行为。制备氨基-β-环糊精/石墨烯复合物，二茂铁作为客体进入氨基-β-环糊精内腔中，形成比较稳定的超分子化合物。然后采用滴涂法对玻碳电极进行修饰后，对多巴胺(DA)和抗坏血酸(AA)进行测定。结果表明，复合物氨基-β-环糊精/石墨烯/二茂铁修饰后的玻碳电极能够有效促进这两种生物大分子在电极表面的电子传递速率，对这两种共同存在于人体内的生物大分子的氧化还原行为具有很好的电催化作用，且能将两种物质共存条件下检测出来。2.对单壁碳纳米管进行羧化处理，然后将羧化的碳纳米管(CNTs)分散在氨基-β-环糊精/二茂铁形成混合溶液，并通过滴涂法将该混合溶液用于制备修饰电极，用循环伏安法研究多巴胺在不同条件下的电化学行为。结果表明，氨基-β-环糊精/羧化单壁碳纳米管/二茂铁修饰后的玻碳电极能够有效促进多巴胺在电极表面的电子传递速率，对多巴胺具有很好的催化氧化作用。3.利用羧基-β-环糊精/石墨烯/二茂铁修饰玻碳电极对尼古丁和儿茶酚进行了电化学测定，利用化学方法将羧基-β-环糊精和石墨烯复合在一起，增强了石墨烯在电极上的稳定性，将上述复合物与二茂铁结合后制备的修饰电极通过循环伏安法探讨尼古丁和儿茶酚在不同条件下的电化学行为。结果表明该修饰电极对尼古丁和儿茶酚的电催化性能好，而且稳定性好、灵敏度高。4.将石墨烯进行改性，得到带有磁性的石墨烯，从而进一步增强了石墨烯体系的电化学性能。羧基-β-环糊精/磁性石墨烯复合膜修饰电极测定多巴胺，电催化作用较为明显，稳定性好，电极寿命较长，可以在实际中应用。5.利用Au-SH键稳定性高、导电性能好等特点，对β-环糊精进行改性，得到溶解性良好的巯基-β-环糊精。将其与石墨烯复合后对金电极进行修饰，修饰后所得巯基-β-环糊精/石墨烯复合膜修饰金电极对多巴胺和抗坏血酸的电化学测定效果良好，相对于玻碳电极灵敏度更好。更多还原

【Abstract】 Electrochemical analysis method is attributed chemical changes to electrochemicalreactions. Usually, the potential, current or electric quality of the reaction system is used asmeasurement of the reaction in this method. And the method has some advantages such assimple, high sensitivity and good real-time. The mixture of β-cyclodextrin (β-CD) and nanocarbon materials has good conductivity, stability and biocompatibility. It can be well fixedinto various substances without adding any crosslinking agent. At present, such complexsystem is mainly used to design various biological electrochemical sensors and improvebiological activity and optoelectronics properties of some devices. In this thesis, some specificmethods were used to modify CNTs、graphene and β-cyclodextrins in order to improve theirsolubility and dispersion, as well as improve the electrochemical properties of CNTs、graphene and β-cyclodextrins. The functionalized CNTs、graphene and β-cyclodextrins areapplied to the electrochemical performance determination of some biomacromolecules. Theelectrochemical behaviors of these biological macromolecules were investigated and thecontent of these biological macromolecules were determined. More effective methods forseparation and testing were explored. The mainly contents of the thesis are as follows:1. The electrocatalytic behaviors of dopamine (DA) and ascorbic acid (AA) inamino-β-cyclodextrin (β-CD-NH2)/graphene/ferrocene modified electrode were studied.Firstly, the amino-β-cyclodextrins/graphene composite was prepared and the inclusioncomplex of amino-β-cyclodextrins and ferrocene(Fc) was combined with graphene. Then theywere used drop-coated method to prepare modified electrode for determination of DA and AA.Results showed that the electrode modified with amino-β-cyclodextrin/graphene/ferrocenecan effectively promote electron transfer rate of these two biological macromolecules in theelectrode surface and perform excellent electrocatalysis in the redox behaviors of the twobiomacromolecules in bodies, the DA and AA in coexistence conditions were separated and detected.2. Carboxyl groups were grafted to the surface of single-walled carbon nanotubes(SWCNTs), then carboxylic SWCNTs were scattered in amino-β-cyclodextrin/ferrocenesolution by sonication. Subsequently, the modified electrode was prepared with drop-coatedmethod, the electrochemical behaviors of DA were studied in different conditions utilizing themodified electrode via cyclic voltammetry method. The results indicated that theβ-CD-NH2/SWCNTs-COOH/Fc modified electrode can effectively promote electronstransfer rate of DA in the electrode surface and perform excellent electrocatalysis in the redoxbehaviors of DA.3. The electrochemical behaiors of nicotine and catechol on the carboxylicβ-cyclodextrin/graphene/ferrocene modified glassy carbon electrode has been investigated.The stability of graphene in the electrodes was reinforced by carboxyl-β-cyclodextrins/graphene complexes via chemical method. Furthermore, the modified glassy carbon electrodewas applied to the electrochemical behaviors reserch of nicotine and catechol in differentconditions utilizing cyclic voltammetry method. The results showed that the modifiedelectrode indicated excellent catalytic properties and the method indicated good stability, highsensitivity in the electrochemical determination of nicotine and catechol.4. Aim to improve the electrochemical properties of electrode, the magnetic grapheneswere prepared and used to modify the naked glass carbon elecreode. Finally, theelectrocatalytic property of carboxyl-β-cyclodextrins/graphene-Fe3O4composite filmmodified electrode was investigated. It is showed that obvious catalytic properties, goodstability, the electrode has a long lifetime, it can be applied in real-detection.5. Firstly, the sulphur-β-cyclodextrins was synthesized for improving the solubilities ofβ-cyclodextrins. Then, the functionlized β-cyclodextrins was combined with graphene andused to modify gold electrode. Ultimately, the modified electrode was applied to determinethe electrochemical behaviors of DA and AA. The results showed that the modified goldelectrode illustrated higher sensitivity than modified glass carbon electrode. Moreover, themodified gold electrode illustrated good electrocatalystical properties.更多还原