THEORETICAL STUDY OF BIOLOGICAL ELECTRON TRANSFER

描述：(改编自申请人的摘要)一份谅解 电子如何在蛋白质的有机介质中长距离穿行 对于描述许多生物过程至关重要，例如 如光合作用和呼吸作用。这是一个广泛的长期目标 提出的研究内容是开发详细的量子力学 复杂分子中的长距离电子转移反应图像 涉及蛋白质和DNA的系统。为了实现这一目标， 计算机模拟、与实验数据的比较和系统化 光致电子转移动力学的理论分析 将对各种新颖的复杂分子进行反应 最近进行了实验研究的系统。在这些 体系中的两种过渡金属络合物，给体和受体 反应，是由一个大的生物分子，如蛋白质 或DNA，它介导了光诱导的电子转移反应。 具体地说，非弹性隧穿的作用，对称性效应 施主和受主状态，以及结构和受主之间的相互作用 我们将研究生物隧道效应的动力学方面。 将被研究的系统包括修饰的细胞色素，例如 Ru(Bpy)2im(His X)-cyt-c、天青蛋白、肌红蛋白等 Ru络合物与基因工程结合的金属蛋白 蛋白质表面的组氨酸；类似的，可变长度的DNA 含有束缚Ru络合物的螺旋将从理论上进行研究。 配合物Will的pi轨道体系的电子转移性质 被调查。DNA和蛋白质复合体将用于研究 距离、结构和碱基对序列 分子内电荷转移速率的依赖关系。建议数 研究将提供一个定量的了解如何结构和 生物分子的动力学最多只能控制电荷转移 基本的量子力学水平。

DESCRIPTION: (Adapted from the applicant's abstract) An understanding of how electrons tunnel long distances through organic media of proteins is crucial for the characterization of many biological processes, such as photosynthesis and respiration. A broad long-range goal of the proposed research is the development of a detailed quantum mechanical picture of long-distance electron transfer reactions in complex molecular systems that involved proteins and DNA. In order to achieve this goal, computer simulations, comparison with experimental data, and systematic theoretical analysis of the dynamics of photoinduced electron transfer reactions will be carried out for a variety of novel complex molecular systems that recently have been studied experimentally. In these systems, two transition metal complexes, donor and acceptor in the reaction, are separated by a large biological molecule, such as protein or DNA, that mediates a photoinduced electron transfer reaction. Specifically, the role of inelastic tunneling, symmetry effects of the donor and acceptor states, and interplay between structural and dynamical aspects of the biological tunneling will be investigated. Systems that will be studied include modified cytochromes, such as Ru(bpy)2im(his X)-cyt-c, azurin, myoglobin, and some other metalloproteins in which a Ru complex is bound to genetically engineered histidines on the surface of the protein; similarly, variable-length DNA helices containing a bound Ru-complex will be studied theoretically. Electron transfer properties of the pi-orbital system of the complex will be investigated. The DNA and protein complexes will be used to study the distance, as well as the structure, and base pair sequence dependence of intramolecular charge transfer rates. The proposed research will provide a quantitative understanding of how structure and dynamics of biological molecules controls charge transfer at the most fundamental quantum mechanical level.