Bis-Gadolinium Complexes for Solid Effect and Cross Effect Dynamic Nuclear Polarization
M. Sc. Monu Kaushik
Goethe-Universität Frankfurt am Main, Institut für Physikalische und Theoretische Chemie, Institut für Biophysikalische Chemie und Biomolekulares Magnetresonanzzentrum (BMRZ), Max-von-Laue-Strasse 7–9, 60438 Frankfurt am Main, Germany
Search for more papers by this authorDr. Mian Qi
Fakultät für Chemie und Centrum für Molekulare Materialien (CM2), Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Adelheid Godt
Fakultät für Chemie und Centrum für Molekulare Materialien (CM2), Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany
Search for more papers by this authorCorresponding Author
Dr.-Ing. Björn Corzilius
Goethe-Universität Frankfurt am Main, Institut für Physikalische und Theoretische Chemie, Institut für Biophysikalische Chemie und Biomolekulares Magnetresonanzzentrum (BMRZ), Max-von-Laue-Strasse 7–9, 60438 Frankfurt am Main, Germany
Search for more papers by this authorM. Sc. Monu Kaushik
Goethe-Universität Frankfurt am Main, Institut für Physikalische und Theoretische Chemie, Institut für Biophysikalische Chemie und Biomolekulares Magnetresonanzzentrum (BMRZ), Max-von-Laue-Strasse 7–9, 60438 Frankfurt am Main, Germany
Search for more papers by this authorDr. Mian Qi
Fakultät für Chemie und Centrum für Molekulare Materialien (CM2), Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany
Search for more papers by this authorCorresponding Author
Prof. Dr. Adelheid Godt
Fakultät für Chemie und Centrum für Molekulare Materialien (CM2), Universität Bielefeld, Universitätsstrasse 25, 33615 Bielefeld, Germany
Search for more papers by this authorCorresponding Author
Dr.-Ing. Björn Corzilius
Goethe-Universität Frankfurt am Main, Institut für Physikalische und Theoretische Chemie, Institut für Biophysikalische Chemie und Biomolekulares Magnetresonanzzentrum (BMRZ), Max-von-Laue-Strasse 7–9, 60438 Frankfurt am Main, Germany
Search for more papers by this authorAbstract
High-spin complexes act as polarizing agents (PAs) for dynamic nuclear polarization (DNP) in solid-state NMR spectroscopy and feature promising aspects towards biomolecular DNP. We present a study on bis(Gd-chelate)s which enable cross effect (CE) DNP owing to spatial confinement of two dipolar-coupled electron spins. Their well-defined Gd⋅⋅⋅Gd distances in the range of 1.2–3.4 nm allowed us to elucidate the Gd⋅⋅⋅Gd distance dependence of the DNP mechanism and NMR signal enhancement. We found that Gd⋅⋅⋅Gd distances above 2.1 nm result in solid effect DNP while distances between 1.2 and 2.1 nm enable CE for 1H, 13C, and 15N nuclear spins. We compare 263 GHz electron paramagnetic resonance (EPR) spectra with the obtained DNP field profiles and discuss possible CE matching conditions within the high-spin system and the influence of dipolar broadening of the EPR signal. Our findings foster the understanding of the CE mechanism and the design of high-spin PAs for specific applications of DNP.
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