¹³C dynamic nuclear polarization using isotopically enriched 4‐oxo‐TEMPO free radicals

Abstract

The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of ¹⁵ N and/or ² H isotopic labeling of 4-oxo-TEMPO free radical on ¹³ C DNP of 3 M [1-¹³ C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for ¹³ C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO-¹⁵ N, 4-oxo-TEMPO-d₁₆ and 4-oxo-TEMPO-¹⁵ N,d₁₆ . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the ¹³ C DNP efficiency of these ¹⁵ N and/or ² H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with ¹³ C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the ¹³ C DNP signals of these samples all doubled in the same manner, and the ¹³ C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the ¹³ C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd.