Measuring absolute spin polarization in dissolution-DNP by Spin PolarimetrY Magnetic Resonance (SPY-MR)
Dynamic nuclear polarization at 1.2 K and 6.7 T allows one to achieve spin temperatures on the order of a few millikelvin, so that the high-temperature approximation (Delta E < kT) is violated for the nuclear Zeeman interaction Delta E = gamma B(0)h/(2 pi) of most isotopes. Provided that, after rapid dissolution and transfer to an NMR or MRI system, the hyperpolarized molecules contain at least two nuclear spins I and S with a scalar coupling J(IS), the polarization of spin I (short for 'investigated') can be determined from the asymmetry A(S) of the multiplet of spin S (short for 'spy'), provided perturbations due to second-order (strong coupling) effects are properly taken into account. If spin S is suitably discreet and does not affect the relaxation of spin I, this provides an elegant way of measuring spin polarizations 'on the fly' in a broad range of molecules, thus obviating the need for laborious measurements of signal intensities at thermal equilibrium. The method, dubbed Spin PolarimetrY Magnetic Resonance (SPY-MR), is illustrated for various pairs of C-13 spins (I, S) in acetate and pyruvate. (C) 2015 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).