Time-resolved studies on the dynamics of electronic charge transfer processes in bioinorganic complexes - development of technological foundations

生物无机模型化合物中电荷转移过程的动力学和相关的催化活性需要在从亚皮秒到分钟的广泛时间范围内研究时间分辨光谱技术，如共振拉曼和x射线吸收光谱（XAS）。SP1为在冷却厌氧条件下提供样品和开发测量程序奠定了技术基础，这些程序将允许有效研究生物无机复合物，如酪氨酸酶，CuA和TypeZero模型复合物。在第一个资助期内，通过设计、建造和首次运行三个不同的腔室，可以提供三种不同的射流和气溶胶注入系统，向泵和探针束的实验相互作用区域提供样品。首先，XAS和拉曼测量显示了这些输送系统的突破性潜力，因为它们避免了样品辐射损伤，并使中间时间域的泵流探针实验成为可能。在第二个资助期，我们将利用我们的专业知识，在两个关键方面改进实验。首先，我们将实现一个冷却器和激振器系统，以提高样品在温度敏感系统上更长的测量时间的稳定性；其次，我们将升级实验条件，例如泵探XAS，以便通过测量x射线的散粒噪声来提高信噪比。结合我们的初步结果，我们期望实现我们的目标，即测量和理解生物无机模型化合物中基态和激发态的电荷转移动力学。此外，我们提供关键的实验测量技术，以支持子项目3、4和5中的结构和电子表征。

The dynamics of charge transfer processes and the connected catalytic activities in bioinorganic model compounds require studies of time-resolved spectroscopic techniques such as resonance Raman and X-ray absorption spectroscopy (XAS) in a wide range of time domains from sub picosecond time scales to minutes. SP1 lays the technological foundation to supply samples under cooled anaerobic conditions and to develop measurement procedures that will allow the effective study of bioinorganic complexes such as Tyrosinase, CuA, and TypeZero model complexes. The supply of samples to the experimental interaction region of pump and probe beams has been accomplished within the first funding period by the design, construction and first operation of three different chambers that can be supplied with three different jet and aerosol injection systems. First XAS and Raman measurements show the ground breaking potential of these delivery systems as they avoid sample radiation damage and enable pump-flow-probe experiments for intermediate time domains. In the second funding period we will build on our expertise to improve the experiments on two crucial aspects. Firstly, we will implement a cooler and shaker system to increase the sample stability for longer measurement times on temperature sensitive systems and secondly we will upgrade the experimental conditions for instance for pump-probe XAS in order to enhance the signal to noise by e.g. measuring the shot noise of the x-rays. Together with our initial results we expect to accomplish our goal to measure and understand the charge transfer dynamics of ground and excited states in bioinorganic model compounds. Furthermore, we supply crucial experimental measurement techniques to enable and support the structural and electronic characterization within the subprojects 3, 4, and 5.