Effect of lanthanide ions on dynamic nuclear polarization enhancement and liquid-state T1 relaxation

In the dynamic nuclear polarization process, microwave irradiation facilitates exchange of polarization from a radical's unpaired electron to nuclear spins at cryogenic temperatures, increasing polarization by >10,000. Doping samples with Gd3+ ions further increases the achievable solid-state polarization. However, on dissolution, paramagnetic lanthanide metals can be potent relaxation agents, decreasing liquid-state polarization. Here, the effects of lanthanide metals on the solid and liquid-state magnetic properties of [1-C-13]pyruvate are studied. The results show that in addition to gadolinium, holmium increases not only the achievable polarization but also the rate of polarization. Liquid-state relaxation studies found that unlike gadolinium, holmium minimally affects T1. Additionally, results reveal that linear contrast agents dissociate in pyruvic acid, greatly reducing liquid-state T1. Although macrocyclic agents do not readily dissociate, they yield lower solid-state polarization. Results indicate that polarization with free lanthanides and subsequent chelation during dissolution produces the highest polarization enhancement while minimizing liquid-state relaxation. Magn Reson Med, 2012. (c) 2012 Wiley Periodicals, Inc.