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

生物无机复合物中电子电荷转移过程动力学的时间分辨研究——技术基础的发展

• 批准号: 174999663
• 负责人: Professor Dr. Matthias Bauer
• 金额: --
• 依托单位: Deutsches Elektronen-Synchrotron (DESY)
• 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/174999663?language=en
• 关键词: Time; resolved; studies; dynamics; electronic

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.

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时间分辨光谱技术的研究，例如共振拉曼和X射线吸收光谱（XAS），其时间范围从亚皮秒时间尺度到分钟。SP1为在冷却厌氧条件下提供样品奠定了技术基础，并开发了测量程序，从而可以有效地研究生物无机复合物，如酪氨酸酶，CuA和TypeZero模型复合物。在第一个供资期内，通过设计、建造和首次运行三个不同的腔室，完成了向泵浦光束和探测光束的实验相互作用区域提供样品的工作，这些腔室可提供三种不同的射流和气溶胶喷射系统。首先XAS和拉曼测量显示了这些传输系统的突破性潜力，因为它们避免了样品辐射损伤，并使泵流探测实验的中间时间域。在第二个资助期内，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，我们将实施冷却器和振荡器系统，以提高样品的稳定性，从而延长温度敏感系统的测量时间;其次，我们将升级泵浦-探测XAS的实验条件，以通过测量X射线的散粒噪声来提高信噪比。结合我们的初步结果，我们希望能够实现我们的目标，测量和了解生物无机模型化合物的基态和激发态的电荷转移动力学。此外，我们还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。

项目成果

Implications of Guanidine Substitution on Copper Complexes as Entatic‐State Models

胍取代对铜配合物作为束缚态模型的影响

• DOI: 10.1002/ejic.201600655
• 发表时间: 2016
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: A. Hoffmann;J. Stanek;B. Dicke;L. Peters;B. Grimm-Lebsanft;A. Wetzel;A. Jesser;M. Bauer;M. Gnida;W. Meyer-Klaucke;M. Rübhausen;S. Herres-Pawlis
• 通讯作者: S. Herres-Pawlis

A cryostat for low temperature resonance Raman measurements on operando oxygenated bioinorganic model complexes

用于对操作含氧生物无机模型复合物进行低温共振拉曼测量的低温恒温器

• DOI: 10.1016/j.ica.2017.07.010
• 发表时间: 2017
• 期刊: Inorganica Chimica Acta
• 影响因子: 2.8
• 作者: B. Grimm-Lebsanft;C. Brett;F. Strassl;D. Rukser;M. Biednov;F. Biebl;M. Naumova;A. Hoffmann;L. Akinsinde;D. Brückner;S. Herres-Pawlis;M. Rübhausen
• 通讯作者: M. Rübhausen

Oxygen Activation by Copper Complexes with an Aromatic Bis(guanidine) Ligand

铜配合物与芳香族双（胍）配体的氧活化

• DOI: 10.1002/ejic.201700528
• 发表时间: 2017
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: F. Strassl;B. Grimm-Lebsanft;D. Rukser;F. Biebl;M. Biednov;C. Brett;R. Timmermann;F. Metz;A. Hoffmann;M. Rübhausen;S. Herres-Pawlis
• 通讯作者: S. Herres-Pawlis

Jet delivery system for Raman scattering on bio-inorganic compounds

用于生物无机化合物拉曼散射的喷射传输系统

• DOI: 10.1063/1.4967476
• 发表时间: 2016
• 期刊: Applied Physics Letters
• 影响因子: 4
• 作者: A. Wetzel;F. Biebl;K. R. Beyerlein;J. Stanek;L. Gumprecht;A. Hoffmann;S. Herres-Pawlis;S. Bajt;H. N. Chapman;B. Grimm-Lebsanft;D. Rukser;M. Rübhausen
• 通讯作者: M. Rübhausen

Catalytic phenol hydroxylation with dioxygen: extension of the tyrosinase mechanism beyond the protein matrix.

• DOI: 10.1002/anie.201301249
• 发表时间: 2013-05-10
• 期刊: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
• 影响因子: 16.6
• 作者: Hoffmann, Alexander;Citek, Cooper;Binder, Stephan;Goos, Arne;Ruebhausen, Michael;Troeppner, Oliver;Ivanovic-Burmazovic, Ivana;Wasinger, Erik C.;Stack, T. Daniel P.;Herres-Pawlis, Sonja
• 通讯作者: Herres-Pawlis, Sonja