Category Archives: pulsed ODNP

Frequency-Swept Integrated and Stretched Solid Effect Dynamic Nuclear Polarization #DNPNMR

Can, T. V., J. E. McKay, R. T. Weber, C. Yang, T. Dubroca, J. van Tol, S. Hill, and R. G. Griffin. “Frequency-Swept Integrated and Stretched Solid Effect Dynamic Nuclear Polarization.” The Journal of Physical Chemistry Letters 9, no. 12 (June 21, 2018): 3187–92. 

https://doi.org/10.1021/acs.jpclett.8b01002

We investigate a new time domain approach to dynamic nuclear polarization (DNP), the frequency-swept integrated solid effect (FS-ISE), utilizing a high power, broadband 94 GHz (3.35 T) pulse EPR spectrometer. The bandwidth of the spectrometer enabled measurement of the DNP Zeeman frequency/field profile that revealed two dominant polarization mechanisms, the expected ISE, and a recently observed mechanism, the stretched solid effect (S2E). At 94 GHz, despite the limitations in the microwave chirp pulse length (10 μs) and the repetition rate (2 kHz), we obtained signal enhancements up to ∼70 for the S2E and ∼50 for the ISE. The results successfully demonstrate the viability of the FS-ISE and S2E DNP at a frequency 10 times higher than previous studies. Our results also suggest that these approaches are candidates for implementation at higher magnetic fields.

Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla #DNPNMR #ODNP

Schöps, Spindler Philipp, and Prisner Thomas, “Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla.”

https://doi.org/10.1515/zpch-2016-0844

Dynamic nuclear polarization (DNP) is a methodology to increase the sensitivity of nuclear magnetic resonance (NMR) spectroscopy. It relies on the transfer of the electron spin polarization from a radical to coupled nuclear spins, driven by microwave excitation resonant with the electron spin transitions. In this work we explore the potential of pulsed multi-frequency microwave excitation in liquids. Here, the relevant DNP mechanism is the Overhauser effect. The experiments were performed with TEMPOL radicals in aqueous solution at room temperature using a Q-band frequency (1.2 T) electron paramagnetic resonance (EPR) spectrometer combined with a Minispec NMR spectrometer. A fast arbitrary waveform generator (AWG) enabled the generation of multi-frequency pulses used to either sequentially or simultaneously excite all three 14N-hyperfine lines of the nitroxide radical. The multi-frequency excitation resulted in a doubling of the observed DNP enhancements compared to single-frequency microwave excitation. Q-band free induction decay (FID) signals of TEMPOL were measured as a function of the excitation pulse length allowing the efficiency of the electron spin manipulation by the microwave pulses to be extracted. Based on this knowledge we could quantitatively model our pulsed DNP enhancements at 1.2 T by numerical solution of the Bloch equations, including electron spin relaxation and experimental parameters. Our results are in good agreement with theoretical predictions. Whereas for a narrow and homogeneous single EPR line continuous wave excitation leads to more efficient DNP enhancements compared to pulsed excitation for the same amount of averaged microwave power. The situation is different for radicals with several hyperfine lines or in the presence of inhomogeneous line broadening. In such cases pulsed single/multi-frequency excitation can lead to larger DNP enhancements.

Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla

Schöps, P., E. Spindler Philipp, and F. Prisner Thomas, Multi-Frequency Pulsed Overhauser DNP at 1.2 Tesla, in Z. Phys. Chem. 2017. p. 561.

https://www.degruyter.com/view/j/zpch.2017.231.issue-3/zpch-2016-0844/zpch-2016-0844.xml

Dynamic nuclear polarization (DNP) is a methodology to increase the sensitivity of nuclear magnetic resonance (NMR) spectroscopy. It relies on the transfer of the electron spin polarization from a radical to coupled nuclear spins, driven by microwave excitation resonant with the electron spin transitions. In this work we explore the potential of pulsed multi-frequency microwave excitation in liquids. Here, the relevant DNP mechanism is the Overhauser effect. The experiments were performed with TEMPOL radicals in aqueous solution at room temperature using a Q-band frequency (1.2 T) electron paramagnetic resonance (EPR) spectrometer combined with a Minispec NMR spectrometer. A fast arbitrary waveform generator (AWG) enabled the generation of multi-frequency pulses used to either sequentially or simultaneously excite all three 14N-hyperfine lines of the nitroxide radical. The multi-frequency excitation resulted in a doubling of the observed DNP enhancements compared to single-frequency microwave excitation. Q-band free induction decay (FID) signals of TEMPOL were measured as a function of the excitation pulse length allowing the efficiency of the electron spin manipulation by the microwave pulses to be extracted. Based on this knowledge we could quantitatively model our pulsed DNP enhancements at 1.2 T by numerical solution of the Bloch equations, including electron spin relaxation and experimental parameters. Our results are in good agreement with theoretical predictions. Whereas for a narrow and homogeneous single EPR line continuous wave excitation leads to more efficient DNP enhancements compared to pulsed excitation for the same amount of averaged microwave power. The situation is different for radicals with several hyperfine lines or in the presence of inhomogeneous line broadening. In such cases pulsed single/multi-frequency excitation can lead to larger DNP enhancements.

Have a question?

If you have questions about our instrumentation or how we can help you, please contact us.