Cooperation Research Unit

合作研究单位

• 批准号: 191833926
• 负责人: Professor Dr. Gerald Henkel
• 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/191833926?language=en
• 关键词: Cooperation; Research; Unit

The interdisciplinary research group FOR1405 focuses the efforts of physicists and chemists to utilize cutting edge photon sources for the dedicated research in the area of charge transfer processes in bioinorganic copper model systems that are relevant for catalytic and enzymatic reactions.The concerted approach merges advanced bioinorganic copper chemistry and sophisticated spectroscopy that makes use of the tremendous potential of pulsed laser, free-electron laser and 3rd-generation-synchrotron applications. At its most ambitious level - for which the FOR is the most important prerequisite -, it provides us with fundamental insights into charge transfer dynamics with a time resolution between femtoseconds to nanoseconds with large relevance for bioinorganic chemistry.The technical foundation for the use of soft and hard X-ray free-electron lasers in connection with high-end synchrotron sources such as PETRA III is complemented by the use of high-end lab-based laser sources to implement and validate new experimental techniques such as modern jet technologies. The full range of modern Raman spectroscopy (resonance and pump-probe Raman) as well as of X-ray absorption spectroscopy (XAS, HERFD, XES, pump-probe XAS) is herefore applied throughout.Charge transfer comprises multiple elementary steps: Firstly, an electron is removed from the metal to a ligand (inner-sphere process) leading to a charge separation over small distances. In a next step this electron can be transferred to an external oxidant during an outer-sphere process. Subsequently, the electron is transferred over longer distances to other redox partners (charge transport).In the first funding period, we focused on Tyrosinase and CuA models. In order to investigate more thoroughly the underlying inner-sphere electron transfer processes, we chose to complement these studies on bi- and polynuclear model complexes by studying mononuclear copper complexes as models for Type Zero copper proteins. All three types of models allow for investigating specific questions on electron transfer in a controlled environment with each subproject focusing on two basic charge/electron transfer phenomena. We will use our knowledge on the dynamics of the excited state to allow a detailed microscopic and quantum mechanical understanding of the involved charge transfer dynamics. On the computational side, methodological developments as well as theoretical spectroscopy are planned for the second funding period. In order to achieve a more realistic description of the molecular electronic structure we will extend our studies towards full relativistic calculations including non-collinear spin polarization. In conjunction with broken symmetry calculations we hope in particular to explore and rationalize the spin structure of the dicopper complexes.

1405跨学科研究小组侧重于物理学家和化学家在收费转移过程中使用尖端光子源用于生物无机铜模型系统的专门研究，这些系统与催化和酶促反应相关。自由电子激光器和第三代同步物应用。 At its most ambitious level - for which the FOR is the most important prerequisite -, it provides us with fundamental insights into charge transfer dynamics with a time resolution between femtoseconds to nanoseconds with large relevance for bioinorganic chemistry.The technical foundation for the use of soft and hard X-ray free-electron lasers in connection with high-end synchrotron sources such as PETRA III is complemented by the use of基于高端实验室的激光源来实施和验证新的实验技术，例如现代喷气技术。因此，全面应用了多个基本步骤：首先，将电子从金属转移到ign-nitiganty（内部范围），因此，全面应用了多个基本步骤：首先将电荷转移量。在下一步中，该电子可以在外球过程中将其转移到外部氧化剂中。随后，电子将在更长的距离转移到其他氧化还原伙伴（电荷运输）。在第一个资金期间，我们专注于酪氨酸酶和CUA模型。为了更彻底地研究潜在的内球电子转移过程，我们选择通过研究单核铜复合物作为零铜蛋白的模型来补充对双核模型复合物的这些研究。所有三种类型的模型都允许在受控环境中调查有关电子传输的特定问题，每个副本都集中在两个基本电荷/电子转移现象上。我们将利用有关激发态动力学的知识，以允许对所涉及的电荷传输动力学有详细的显微镜和量子机械理解。在计算方面，计划在第二个融资期间计划进行方法论发展以及理论光谱。为了实现对分子电子结构的更现实的描述，我们将扩展研究朝着完全相对论计算，包括非共线自旋极化。结合损坏的对称计算，我们特别希望探索和合理化DiCopper复合物的自旋结构。