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The development of electroactive total internal reflection integrated optical waveguide and total internal reflection fluorescence devices for the characterization of metalloprotein films.

机译:电活性全内反射集成光波导和全内反射荧光器件的开发,用于表征金属蛋白膜。

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摘要

Orientation distributions of redox active films that correlate with an electron transfer behavior were reported for the first time using electroactive total internal reflection fluorescence spectroscopy (EA-TIRF) and electroactive integrated optical waveguide (EA-IOW) absorbance technology developed here. The mean tilt angle and the angular distribution about the mean were recovered using a Gaussian model. Previous anisotropy calculations were only possible using a theoretical approach (Hansen's model). In the work presented here, a novel method was developed that was based on experimental measurements. This method used Fresnel's equations and Snell's law to determine the relative polarized electric field intensity at the interface of the EA-TIRF substrate.; Optically transparent semiconductor surfaces of indium tin oxide (ITO) were used as the adlayer for EA-TIRF and EA-IOW devices. The ITO surface morphology, optical and conduction properties were characterized. The ITO was found to have adequate conduction, optical and surface morphology properties for molecular orientation distribution measurements. The results indicated the ITO morphology contributes a minimal degree of error to the calculated distribution.; Surface-bound films of model methylene blue were used to characterize the EA-TIRF and EA-IOW techniques prior to the investigation of horse heart cytochrome c. The studies demonstrated potential control of redox active adsorbed films. The mean tilt angle and the angular distribution about that mean were successfully determined. In addition, the studies of the methylene blue films indicated the possibility of orientation-dependent quenching (the loss of an electron from the excited state LUMO to the ITO semiconductor conduction band).; Studies of the cytochrome c films indicated anisotropic submonolayers electrostatically bound to the negative ITO surface. Cyclic voltammetry measurements showed the films to be electroactive, exhibiting quasi-reversible electrochemistry. An average tilt angle and the orientation distribution about the angle, as a function of potential, were reported for horse heart cytochrome c. This potential-dependent orientation distribution of submonolayer films is reported for the first time.
机译:首次报道了使用电活性全内反射荧光光谱(EA-TIRF)和此处开发的电活性集成光波导(EA-IOW)吸收技术与电子转移行为相关的氧化还原活性膜的取向分布。使用高斯模型恢复平均倾斜角度和关于平均角度的角度分布。以前的各向异性计算只能使用理论方法(Hansen模型)进行。在本文介绍的工作中,开发了一种基于实验测量的新颖方法。该方法使用菲涅尔方程和斯涅尔定律确定EA-TIRF基板界面处的相对极化电场强度。铟锡氧化物(ITO)的光学透明半导体表面用作EA-TIRF和EA-IOW器件的添加层。表征了ITO的表面形态,光学和导电性能。已发现ITO具有足够的导电,光学和表面形态特性,可用于分子取向分布测量。结果表明,ITO形态对计算的分布贡献最小的误差。在研究马心脏细胞色素c之前,使用亚甲基蓝模型的表面粘合膜表征EA-TIRF和EA-IOW技术。研究表明潜在控制氧化还原活性吸附膜。成功确定了平均倾斜角和关于该平均值的角度分布。另外,对亚甲基蓝膜的研究表明了取向依赖性猝灭的可能性(电子从激发态LUMO到ITO半导体导带的损失)。细胞色素C膜的研究表明,各向异性亚单层静电结合到负ITO表面。循环伏安法测量显示该膜是电活性的,表现出准可逆的电化学。据报道,马心脏细胞色素c的平均倾斜角和绕该角度的方向分布与电势有关。首次报道了亚单层膜的这种取决于电位的取向分布。

著录项

  • 作者

    Robertson, Rebecca Tinsley.;

  • 作者单位

    The University of Arizona.;

  • 授予单位 The University of Arizona.;
  • 学科 Chemistry Analytical.
  • 学位 Ph.D.
  • 年度 2002
  • 页码 289 p.
  • 总页数 289
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 化学;
  • 关键词

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