本文研究了肌红蛋白(Mb)与具有特殊结构的小分子磺化-β-环糊精(s-β-CD)层层组装薄膜电极的直接电化学和电化学催化行为，并对薄膜组装的驱动力做了初步的探讨。 用石英晶体微天平(QCM)、紫外可见吸收光谱(UV–vis)和循环伏安方法(CV)监测并证实了{s-β-CD/Mb}n薄膜的组装过程。随着吸附双层数n的增长，薄膜的生长是大体均匀的，但电活性的Mb在每个双层中Mb总量中的比例却逐渐减小，当n > 9时达到稳态，表明只有接近PG表面的几个双层中的Mb才具有电活性。紫外可见光谱结果表明，Mb在{s-β-CD/Mb}n薄膜中能很好地保持其原始结构。{s-β-CD/Mb}n薄膜电极具有良好的稳定性。对{s-β-CD/Mb}n薄膜电极的方波伏安实验数据进行非线性回归分析，估计了该体系的表观异相电子传递速率常数ks等电化学参数。Mb在此薄膜电极上成功实现了直接电子转移和对不同底物的电化学催化。初步研究了s-β-CD 和不同pH的Mb之间的作用力。结果表明，带有负电荷的s-β-CD不仅能和pH 5.0时带正电荷的Mb层层组装，而且还能与pH 9.0时带负电荷的Mb 进行层层组装。

In this thesis, the direct electrochemistry and the electrocatalysis of myoglobin (Mb) in Mb layer-by-layer films with small-molecular s-β-CD were investigated. The driving force of layer-by-layer assembly was explored. Quartz crystal microbalance (QCM),UV–vis spectroscopy and cyclic voltammetry (CV) were used to monitor and confirm the assembly process. While the growth of the {s-β-CD/Mb}n films were essentially uniform with the increase of the number of adsorption bilayers, the fraction of electroactive Mb among the total adsorbed Mb in each bilayer showed a trend of decrease. When n > 9, the surface concentration of electroactive Mb did not increase anymore, indicating that only those Mb molecules in the bilayers closest to the electrode surface are electrochemically addressable. UV–vis spectroscopy indicates that the Mb in {s-β-CD/Mb}n films retains its near native structure. {s-β-CD/Mb}n films demonstrated good stability. Square wave voltammograms of {s-β-CD/Mb}n films combined with nonlinear regression analysis were used to estimate the apparent heterogeneous electron transfer rate constant (ks) and other electrochemical parameters. The direct electron trasfer of Mb was realized in this new kind of films at pyrolytic graphte (PG) electrodes, and was used to electrocatalyze the reduction of various substrates. The interaction between s-β-CD and Mb under different pH conditions was also explored. Not only the oppositely charged s-β-CD and Mb at pH 5.0, but also the likely charged s-β-CD and Mb at pH 9.0, could be assembled into {s-β-CD/Mb}n films.