Friday, April 18, 2014

Heteronuclear Cross-Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets

Donovan, K.J., A. Lupulescu, and L. Frydman, Heteronuclear Cross-Relaxation Effects in the NMR Spectroscopy of Hyperpolarized Targets. ChemPhysChem, 2014. 15(3): p. 436-443.

Dissolution dynamic nuclear polarization (DNP) enables high-sensitivity solution-phase NMR experiments on long-lived nuclear spin species such as (15)N and (13)C. This report explores certain features arising in solution-state (1)H NMR upon polarizing low-gamma nuclear species. Following solid-state hyperpolarization of both (13)C and (1)H, solution-phase (1)H NMR experiments on dissolved samples revealed transient effects, whereby peaks arising from protons bonded to the naturally occurring (13)C nuclei appeared larger than the typically dominant (12)C-bonded (1)H resonances. This enhancement of the satellite peaks was examined in detail with respect to a variety of mechanisms that could potentially explain this observation. Both two- and three-spin phenomena active in the solid state could lead to this kind of effect; still, experimental observations revealed that the enhancement originates from (13)C-->(1)H polarization-transfer processes active in the liquid state. Kinetic equations based on modified heteronuclear cross-relaxation models were examined, and found to well describe the distinct patterns of growth and decay shown by the (13)C-bound (1)H NMR satellite resonances. The dynamics of these novel cross-relaxation phenomena were determined, and their potential usefulness as tools for investigating hyperpolarized ensembles and for obtaining enhanced-sensitivity (1)H NMR traces was explored.