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Dynamic Nuclear Polarization (DNP)

 

Nuclear Magnetic Resonance (NMR) is one of the most powerful, informative, versatile methods for the structural and functional characterization of complex systems, with applications ranging from pure science to medicine and engineering. 

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However, an inherent caveat of NMR is its limited sensitivity, resulting from the small thermal polarization of the nuclear spin in an external magnetic field. This obstacle becomes a bottleneck when the studied nuclei display a broad range of interactions with their environment, leading to a substantial broadening of their signal, such that the signal intensity decreases.

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The electron spin, however, presents a much larger polarization, due to its large magnetic moment (~660 time that of protons). This sets the stage for Dynamic Nuclear Polarization (DNP) – the signal enhancement in NMR by the transfer of the electron polarization to the nucleus. In this method, we excite unpaired electrons, serving as polarizing agents, using microwave (MW) irradiation, and the interaction between the electron spins and the nuclear spins results in enhancement of the NMR signal (see figure). The resulting sensitivity gain lends itself to NMR measurements of systems otherwise inaccessible to NMR.

​

Nuclear Magnetic Resonance (NMR) is one of the most powerful, informative, versatile methods for the structural and functional characterization of complex systems, with applications ranging from pure science to medicine and engineering. 

​

However, an inherent caveat of NMR is its limited sensitivity, resulting from the small thermal polarization of the nuclear spin in an external magnetic field. This obstacle becomes a bottleneck when the studied nuclei display a broad range of interactions with their environment, leading to a substantial broadening of their signal, such that the signal intensity decreases.

​

 

The electron spin, however, presents a much larger polarization, due to its large magnetic moment (~660 time that of protons). This sets the stage for Dynamic Nuclear Polarization (DNP) – the signal enhancement in NMR by the transfer of the electron polarization to the nucleus. In this method, we excite unpaired electrons, serving as polarizing agents, using microwave (MW) irradiation, and the interaction between the electron spins and the nuclear spins results in enhancement of the NMR signal (see figure). The resulting sensitivity gain lends itself to NMR measurements of systems otherwise inaccessible to NMR.

​

Nuclear Magnetic Resonance (NMR) is one of the most powerful, informative, versatile methods for the structural and functional characterization of complex systems, with applications ranging from pure science to medicine and engineering. 

​

However, an inherent caveat of NMR is its limited sensitivity, resulting from the small thermal polarization of the nuclear spin in an external magnetic field. This obstacle becomes a bottleneck when the studied nuclei display a broad range of interactions with their environment, leading to a substantial broadening of their signal, such that the signal intensity decreases.

​

The electron spin, however, presents a much larger polarization, due to its large magnetic moment (~660 time that of protons). This sets the stage for Dynamic Nuclear Polarization (DNP) – the signal enhancement in NMR by the transfer of the electron polarization to the nucleus. In this method, we excite unpaired electrons, serving as polarizing agents, using microwave (MW) irradiation, and the interaction between the electron spins and the nuclear spins results in enhancement of the NMR signal (see figure). The resulting sensitivity gain lends itself to NMR measurements of systems otherwise inaccessible to NMR.

​

  1. Overhauser, A. W. Polarization of nuclei in metals. Phys. Rev. 92, 411 (1953).

  2. Ardenkjaer-Larsen, J. H. et al. Increase in signal-to-noise ratio of >10,000 times in liquid-state NMR. Proc. Natl. Acad. Sci. 100, 10158–10163 (2003).

  3. Maly, T. et al. Dynamic nuclear polarization at high magnetic fields. J. Chem. Phys. 128, 052211 (2008).

  4. Atsarkin, V. A. Dynamic nuclear polarization: Yesterday, today, and tomorrow. J. Phys. Conf. Ser. 324, 012003 (2011).

  5. Lee, D., Hediger, S. & De Paëpe, G. Is solid-state NMR enhanced by dynamic nuclear polarization? Solid State Nucl. Magn. Reson. 66–67, 6–20 (2015).

  6. Lilly Thankamony, A. S., Wittmann, J. J., Kaushik, M. & Corzilius, B. Dynamic nuclear polarization for sensitivity enhancement in modern solid-state NMR. Prog. Nucl. Magn. Reson. Spectrosc. 102–103, 120–195 (2017).

  7. Kaminker, I. Recent Advances in Magic Angle Spinning‐Dynamic Nuclear Polarization Methodology. Isr. J. Chem. 59, 990–1000 (2019).

  8. Corzilius, B. High-Field Dynamic Nuclear Polarization. Annu. Rev. Phys. Chem. 71, 143–170 (2020).

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