Novel Non-Linear Spectroscopic Probes of the Primary Photoreactions of Photolyases and Cryptochromes

这个项目的目的是为最先进的时间分辨振动和光学光谱技术开发新的模拟算法。这两种技术都利用不同的观察窗口来提供超快、锥形相交介导的光反应的实时视图。所涉及的分子运动可以通过时间和频率分辨的红外或拉曼技术直接观察到。对于它们的模拟，将开发一系列算法，其中包括全量子模拟协议，作为引入半经典近似的基准，以便于模拟生物相关系统的特征振动特征。多维光学光谱技术监测发色团之间的能量流动和相互作用。基于费米子多激子共玻色化的新的模拟协议将允许预测创新的高阶信号，这些信号揭示了生色团聚集体中的多体关联，并使重要的UV光谱区域的输运现象变得可访问。算法的发展将被用来揭示光解酶/隐色素黄素蛋白超家族中复杂的初级光反应的机制。时间分辨振动技术将允许预测光致反转的实时分子探测器，以解决有争议的光产物修复的机制预测。预测的多维光学信号将被用来区分隐色素中的电荷转移路径，以开发信号转导主要步骤的通用模型。新颖的多维手性诱导信号有可能实时跟随光吸收的构象变化，以便提供信号转导所需的电子激发到机械运动的详细图像。因此，该项目的理论发展有可能通过将已知的蛋白质结构与光诱导的动力学联系起来，提供蛋白质功能的全面图像，从而揭示生物重要过程中最早的机械步骤的光谱特征。

The aim of this project is the development of novel simulation algorithms for state-of-the-art time resolved vibrational and optical spectroscopic techniques. Both techniques exploit different windows of observation to provide a real time view of ultrafast, conical intersection mediated photoreactions. The involved molecular motions can be directly observed by time- and frequency-resolved infrared or Raman techniques. For their simulation a hierarchy of algorithms will be developed which cover full quantum simulation protocols as benchmark for introduced semiclassical approximations to facilitate simulations of characteristic vibronic signatures of biological relevant systems. Multidimensional optical spectroscopic techniques monitor energy fluxes and interactions between chromophores. Novel simulation protocols based on a co-bosonization of fermionic multi-excitons will allow to predict innovative higher order signals which reveal many-body correlations in chromophore aggregates and make transport phenomena in the important UV spectral region accessible. The algorithmic developments will be used to uncover the mechanism of the complex primary photoreactions in the Photolyase/Cryptochrome flavoprotein superfamily. Time-resolved vibrational techniques will allow to predict real-time molecular probes of the photolesion reversion to resolve controversial mechanistic predictions of (6-4) photoproduct repair. Predicted multidimensional optical signals will be used to discriminate between the charge transfer pathways in Cryptochromes to develop a universal model of the primary steps of signal transduction. Novel multidimensional chirality induced signals have the potential to follow conformational changes upon light absorption in real time in order to provide a detailed picture of the conversion of electronic excitation into the mechanical motion required for signal transduction. The theoretical developments of the project have thus the potential to uncover spectroscopic signatures of the earliest mechanistic steps of biological important processes by relating the known protein structure to the light induced dynamics to provide a comprehensive picture of the protein function.