Friday, July 13, 2018

Reversal of Paramagnetic Effects by Electron Spin Saturation #DNPNMR

Jain, Sheetal K., Ting A. Siaw, Asif Equbal, Christopher B. Wilson, Ilia Kaminker, and Songi Han. “Reversal of Paramagnetic Effects by Electron Spin Saturation.” The Journal of Physical Chemistry C 122, no. 10 (March 15, 2018): 5578–89.


We present a study in which both significant dynamic nuclear polarization (DNP) enhancement of 7Li NMR and reversal of the paramagnetic effects (PEs) are achieved by microwave (μw) irradiation-induced electron spin saturation of nitroxide radicals at liquid-helium temperatures. The reversal of the PE was manifested in significant narrowing of the 7Li NMR line and reversal of the paramagnetic chemical shift under DNP conditions. The extent of the PE was found to decrease with increased saturation of the electron paramagnetic resonance line, modulated as a function of microwave (μw) power, frequency, duration of irradiation, and gating time between μw irradiation and NMR detection. The defining observation was the shortening of the electron phase memory time, Tm, of the excited observer spins with increasing μw irradiation and concurrent electron spin saturation of the electron spin bath. This and a series of corroborating studies reveal the origin of the NMR line narrowing to be the reversal of paramagnetic relaxation enhancement (PRE), leading us to debut the term REversal of PRE by electron Spin SaturatION (REPRESSION). The shortening of electron Tm of any paramagnetic system as a function of electron spin saturation has not been reported to date, making REPRESSION a discovery of this study. The reversal of the paramagnetic dipolar shift is due to the decrease in electron spin order, also facilitated by electron spin saturation. This study offers new fundamental insights into PE under DNP conditions and a method to detect and identify NMR signal proximal to paramagnetic sites with reduced or minimal line broadening.