Millen, Marthe, Nicholas Alaniva, Edward P. Saliba, Sarah A. Overall, Alexander Däpp, Ioannis Gr. Pagonakis, Snorri Th. Sigurdsson, Snædís Björgvinsdóttir, and Alexander B. Barnes. “Frequency-Chirped Magic Angle Spinning Dynamic Nuclear Polarization Combined with Electron Decoupling.” The Journal of Physical Chemistry Letters 15, no. 28 (July 18, 2024): 7228–35.
https://doi.org/10.1021/acs.jpclett.4c01075.
Magic angle spinning (MAS) dynamic nuclear polarization (DNP) increases the signal intensity of solid-state nuclear magnetic resonance. DNP typically uses continuous wave (CW) microwave irradiation close to the resonance frequency of unpaired electron spins. In this study, we demonstrate that frequency-chirped microwaves improve DNP performance under MAS. By modulating the gyrotron anode potential, we generate a train of microwave chirps with a maximum bandwidth of 310 MHz and a maximum incident power on the spinning sample of 18 W. We characterize the efficiency of chirped DNP using the following polarizing agents: TEMTriPol-1, AsymPolPOK, AMUPol, and Finland trityl. The effects of different chirp widths and periods are analyzed at different MAS frequencies and microwave powers. Furthermore, we show that chirped DNP can be combined with electron decoupling to improve signal intensity by 59%, compared to CW DNP without electron decoupling, using Finland trityl as a polarizing agent.