Design of flavoproteins for spin-hyperpolarization in NMR

荧光显微镜是最灵敏的光谱方法之一，它依靠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来提供对比度。磁共振成像(MRI)将受益于类似的试剂，这些试剂在照射时会产生核自旋超极化，并携带这种选择性的表面标记。在这里，作为这条路线的第一步，我们将使用固态光CIDNP(光化学诱导动态核极化)效应作为核自旋超极化的来源，该自旋超极化发生在称为LOV结构域的小黄素蛋白中。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改LOV结构域。此外，我们希望构建一条供体链，因为众所周知，它存在于更大的黄素蛋白中，如光解酶。我们的目标是通过实验研究光致1H、13C和15N超极化产生的磁场依赖性和最佳效率，以探索产生1H、13C和15N超极化的相关机制，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.