A Divide and Conquer Approach to the Response Properties of Biomolecules: Electron Transfer Reactions, Raman Spectroscopy, and Spectroscopic Probes of Chirality

生物分子响应特性的分而治之的方法：电子转移反应、拉曼光谱和手性光谱探针

基本信息

批准号：
9727657
负责人：
David Beratan
金额：
$ 29.3万
依托单位：
University of Pittsburgh
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
1998
资助国家：
美国
起止时间：
1998-03-01 至 2001-10-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=9727657&HistoricalAwards=false
关键词：
Divide Conquer Approach Response Properties

项目摘要

David Beratan is supported by a grant from the Theoretical and Computational Chemistry Program to study response properties of biomolecules including electron transfer reactions and Raman spectroscopic probes of chirality. The goal of the proposed work is to develop a general new tool that will enable the theoretical exploration of biochemical structure-function and reactivity relations by exploiting the local nature of chemical interactions. An ab initio divide-and-conquer method is proposed, tailored to describe the electronic and vibronic response properties of macromolecules. The methods will be developed in such a way that they can be used to: 1) establish a link between 3D structure and electron transfer rates in proteins and DNA; 2) assist in relating molecular structure to chiroptical properties critical for drug discovery and protein structure determination, and 3) expand the structure-property interpretations of proteins available via Raman spectroscopy. The actual implementation of this strategy involves the use of an effective Hamiltonian, and Greens function theory to determine the relevant response function. A quantitative molecular-level description of biological function will arise from a detailed description of macromolecular electronic and vibronic structure. Yet, reliable electronic structure calculations are possible on systems of only modest size. Beratan's research program will enable the theoretical exploration of biochemical structure-function and reactivity relations at the molecular level for macromolecular systems of biological interest.

David Beratan 得到理论和计算化学计划的资助，用于研究生物分子的响应特性，包括电子转移反应和手性拉曼光谱探针。拟议工作的目标是开发一种通用的新工具，通过利用化学相互作用的局部性质，对生化结构功能和反应性关系进行理论探索。提出了一种从头开始的分而治之方法，专门用于描述大分子的电子和振动响应特性。这些方法将被开发用于：1）建立蛋白质和 DNA 中 3D 结构与电子转移速率之间的联系； 2) 协助将分子结构与对药物发现和蛋白质结构测定至关重要的手性光学特性联系起来，以及 3) 通过拉曼光谱扩展可用的蛋白质结构-特性解释。该策略的实际实施涉及使用有效的哈密顿量和格林函数理论来确定相关的响应函数。对生物功能的定量分子水平描述将源自对大分子电子和电子振动结构的详细描述。然而，在尺寸适中的系统上，可靠的电子结构计算是可能的。贝拉坦的研究计划将使具有生物意义的大分子系统在分子水平上对生化结构-功能和反应性关系进行理论探索。