FOR 1405: Dynamics of Electron Transfer Processes within Transition Metal Sites in Biological and Bioinorganic Systems

FOR 1405：生物和生物无机系统中过渡金属位点内电子转移过程的动力学

• 批准号: 159419156
• 金额: --
• 依托单位: Arbeitskreis Bioanorganische Chemie und moderne Komplexchemie
• 依托单位国家: 德国
• 项目类别: Research Units
• 财政年份: 2011
• 资助国家: 德国
• 起止时间: 2010-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/159419156?language=en
• 关键词: 1405; Dynamics; Electron; Transfer; Processes

Structures and reactivities of chemical substances are highly affected by charge distributions. This appraisal holds not only for synthetic systems but for metallobiomolecules as well. Hence, transfer of charge density within these systems should result in structural changes on a molecular as well as on an atomic level and thus is predestinated to exert influence on the reaction behaviour of metalloproteins and metalloenzymes in a characteristic manner. The catalytical activity of copper containing enzymes is a prominent example, which is based on this principle of charge transfer. These molecules attract considerable interest not only from a scientific point of view but also because of their technical importance as guides for industrial applications. Within the scope of this Research Unit, we intend to make use of the optically excited charge transfer in such systems and related synthetic models in order to gain insights into the chronologies of the processes induced. The scientific approach is focussed on time-resolved investigations of suitable molecules in their excited states employing novel pump/probe techniques based on ultramodern pulsed photon sources. The envisioned experiments are based on photons from large-scale facilities such as FLASH, PETRA III, ESRF, SLS and DORIS III in combination with laser-based photon sources. This approach allows to trigger biochemical processes and to study the resulting action of the molecular complex on a femto- to picosecond time scale. Based on charge-transfer transitions induced by visible to UV photons, the successive use of VUV and soft X-ray photons allows to study the following actions time resolved in a pump-probe configuration with atomic and orbital selectivity. The Research Unit also acts as an interface between novel photon sources and their unique spectroscopic capabilities being currently developed in the field of physics a well as modern approaches in quantum theoretical physics in order to tackle important fundamental problems on the role of metals in modern biochemistry. With our results we intend to deliver the necessary boundaries and knowledge to improve tailor made oxidation catalysts, to finally understand biological charge-transfer processes, and to learn how copper affects pathological folding processes in proteins.

化学物质的结构和反应活性受电荷分布的影响很大。这种评价不仅适用于合成系统，而且适用于金属生物分子。因此，在这些系统内的电荷密度的转移应导致在分子以及在原子水平上的结构变化，因此预定以特征性的方式对金属蛋白和金属酶的反应行为施加影响。含铜酶的催化活性是一个突出的例子，其基于电荷转移的原理。这些分子吸引了相当大的兴趣，不仅从科学的角度来看，但也因为它们的技术重要性，作为指导工业应用。在本研究单元的范围内，我们打算利用这种系统和相关的合成模型中的光激发电荷转移，以深入了解诱导过程的时序。科学方法的重点是在其激发态采用新的泵/探测技术的基础上超现代脉冲光子源的合适的分子的时间分辨调查。设想的实验是基于来自大规模设施的光子，如FLASH，PETRA III，ESRF，SLS和DORIS III与基于激光的光子源相结合。这种方法允许触发生化过程，并研究在飞秒至皮秒时间尺度上分子复合物的最终作用。基于由可见光到UV光子引起的电荷转移跃迁，连续使用VUV和软X射线光子允许研究以下动作时间分辨的泵浦-探测配置与原子和轨道选择性。该研究单位还充当新型光子源及其独特的光谱能力之间的接口，目前正在物理学领域开发，以及量子理论物理学的现代方法，以解决现代生物化学中金属作用的重要基本问题。通过我们的研究结果，我们打算提供必要的边界和知识，以改善定制的氧化催化剂，最终了解生物电荷转移过程，并了解铜如何影响蛋白质的病理折叠过程。