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

化学物质的结构和反应活性受电荷分布的影响很大。这一评价不仅适用于合成体系，也适用于金属生物分子。因此，电荷密度在这些体系中的转移将导致分子和原子水平上的结构变化，从而注定以一种特有的方式对金属蛋白和金属酶的反应行为产生影响。含铜酶的催化活性就是一个突出的例子，这是基于电荷转移原理的。这些分子不仅从科学角度吸引了相当大的兴趣，而且还因为它们作为工业应用的指南在技术上具有重要意义。在本研究单位的范围内，我们打算利用这种系统中的光激发电荷转移和相关的合成模型，以便深入了解诱导过程的年表。这种科学方法的重点是利用基于超现代脉冲光子源的新型泵浦/探测技术，对处于激发态的合适分子进行时间分辨研究。设想的实验基于来自大规模设施的光子，如闪光灯、Petra III、ESRF、SLS和Doris III，并结合基于激光的光子源。这种方法允许触发生化过程，并研究分子复合体在飞秒到皮秒的时间尺度上产生的作用。基于可见光到紫外光光子引起的电荷转移跃迁，连续使用真空紫外光和软X射线光子可以研究在具有原子和轨道选择性的泵浦-探测配置中随时间分辨的下列行为。研究股还作为新的光子源及其目前在物理学领域开发的独特光谱能力以及量子理论物理中的现代方法之间的接口，以便解决关于金属在现代生物化学中的作用的重要基本问题。有了我们的结果，我们打算提供必要的边界和知识，以改进定制的氧化催化剂，最终了解生物电荷转移过程，并了解铜如何影响蛋白质中的病理折叠过程。

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.