Distance‐Dependence of Photo‐CIDNP in Biomimetic Tryptophan–Flavin Diads
Abstract
Abstract Nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) are essential tools in natural and life sciences, but their low sensitivity often hampers their applicability. Photochemically induced dynamic nuclear polarization (photo‐CIDNP) offers a versatile and mild method to overcome this limitation. Here, we report on structure‐photo‐CIDNP relationship studies in liquid‐state NMR utilizing a holistic approach. We synthesized biomimetic tryptophan–flavin diads with varying linker lengths composed of conformationally rigid oligoproline units. The predominant polyproline II (PPII) helical structure ensures consistent donor–acceptor distances. Photo‐CIDNP NMR experiments revealed significant hyperpolarization effects, particularly in diads with six proline units, mimicking the spatial arrangement found in natural photoactive proteins. Our findings highlight the potential of these biomimetic diads to enhance nuclear hyperpolarization in NMR spectroscopy. This work provides valuable insights into the design of diads for efficient photo‐CIDNP generation, paving the way for advanced studies in modern NMR and bio‐MRI.
Article Details
Authors (14)
Tobias Theiss
Department of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany
Guzel Musabirova
Department of Analytical Chemistry, Leipzig University, Linnéstr. 3, 04103 Leipzig, Germany
Luca Gerhards
Institute of Physics, Carl von Ossietzky Universität, Carl-von-Ossietzky-Street 9−11, 26129 Oldenburg, Germany
Irina S. Anisimova
Institute of Physics, Carl von Ossietzky Universität, Carl-von-Ossietzky-Street 9−11, 26129 Oldenburg, Germany
Ben G. E. Zoller
Organic Chemistry
Thi Ngoc Ha Nguyen
Department of Physics Chemnitz University of Technology Reichenhainer Str. 70 09126 Chemnitz Germany
Dmitry Denisov
Department of Analytical Chemistry Leipzig University Linnéstr. 3 04103 Leipzig Germany
Anton Schmidt
Institute of Physical Chemistry, University of Freiburg 1 , 79104 Freiburg,
Sabrina Panter
Institute of Physical Chemistry Albert‐Ludwigs‐Universität Freiburg Albertstr. 21 79104 Freiburg Germany
Stefan Weber
Institut für Physikalische Chemie
Christoph Tegenkamp
Department of Physics Chemnitz University of Technology Reichenhainer Str. 70 09126 Chemnitz Germany
Ilia A. Solov'yov
Institute of Physics Carl‐von‐Ossietzky‐University Carl‐von‐Ossietzky‐Str. 9–11 26129 Oldenburg Germany
Jörg Matysik
Department of Analytical Chemistry, Leipzig University, Linnéstr. 3, 04103 Leipzig, Germany
Tanja Gulder
Department of Organic Chemistry, Leipzig University, Johannisallee 29, 04103 Leipzig, Germany