Design of flavoproteins for spin-hyperpolarization in NMR

最灵敏的光谱方法之一，荧光显微镜，依赖于特定的荧光剂作为绿色荧光蛋白（GFP），通过使用特定的表面标记物提供对比。磁共振成像（MRI）将受益于在照射时产生核自旋超极化并且还携带这种选择性表面标记的类似试剂。在这里，作为该路线的第一步，我们将使用固态光CIDNP（光化学诱导的动态核极化）效应作为发生在称为LOV结构域的小黄素蛋白中的核自旋超极化的来源。我们将通过改变电子供体和电子受体以及供体和受体之间的距离来修饰LOV结构域。此外，我们希望构建一个链的捐助者，因为它是已知的发生在较大的黄素蛋白作为光解酶。我们的目标是实证研究磁场的依赖性和最佳效率，旨在探索产生光致1H，13 C和15 N超极化的相关机制，以抑制不必要的副反应，并优化特定实验的条件。

One of the most sensitive spectroscopic methods, fluorescence microscopy, relies on specific fluorescent agents as the green fluorescent protein (GFP) providing contrast by using specific surface markers. Magnetic resonance imaging (MRI) would profit from analogous agents which produce nuclear spin-hyperpolarization upon illumination and also carry such selective surface markers. Here, as first step on that route, we will use the solid-state photo-CIDNP (photochemically induced dynamic nuclear polarization) effect as source of the nuclear spin-hyperpolarization occurring in small flavoproteins called LOV domains. We will modify the LOV domain by changing both electron donor and electron acceptor as well as the distance between donor and acceptor. Furthermore, we want to construct a chain of donors as it is known to occur in larger flavoproteins as photolyases. We aim for empirically study the magnetic-field dependence and the optimum efficiency aiming to explore the relevant mechanisms producing light-induced 1H, 13C and 15N hyperpolarization, to suppress unwanted side-reactions, and to optimize conditions for specific experiments.