J. Am. Chem. Soc., 2009, 131 (44), pp 16014–16015

Proton NMR of 15N-Choline Metabolites Enhanced by Dynamic Nuclear Polarization
Riddhiman Sarkar†, Arnaud Comment‡§, Paul R. Vasos†, Sami Jannin, Rolf Gruetter‡§, Geoffrey Bodenhausen†, Hlne Hall, Deniz Kirik# and Vladimir P. Denisov#

Abstract
Chemical shifts of protons can report on metabolic transformations such as the conversion of choline to phosphocholine. To follow such processes in vivo, magnetization can be enhanced by dynamic nuclear polarization (DNP). We have hyperpolarized in this manner nitrogen-15 spins in 15N-labeled choline up to 3.3% by irradiating the 94 GHz electron spin resonance of admixed TEMPO nitroxide radicals in a magnetic field of 3.35 T during ca. 3 h at 1.2 K. The sample was subsequently transferred to a high-resolution magnet, and the enhanced polarization was converted from 15N to methyl- and methylene protons, using the small 2,3J(1H,15N) couplings in choline. The room-temperature lifetime of nitrogen polarization in choline, T1(15N) ≈ 200 s, could be considerably increased by partial deuteration of the molecule. This procedure enables studies of choline metabolites in vitro and in vivo using DNP-enhanced proton NMR.