Dataset Information

High-field 13C dynamic nuclear polarization with a radical mixture.

ABSTRACT: We report direct (13)C dynamic nuclear polarization at 5 T under magic-angle spinning (MAS) at 82 K using a mixture of monoradicals with narrow EPR linewidths. We show the importance of optimizing both EPR linewidth and electron relaxation times by studying direct DNP of (13)C using SA-BDPA and trityl radical, and achieve (13)C enhancements above 600. This new approach may be best suited for dissolution DNP and for studies of (1)H depleted biological and other nonprotonated solids.

SUBMITTER: Michaelis VK

PROVIDER: S-EPMC3605040 | biostudies-literature | 2013 Feb

REPOSITORIES: biostudies-literature

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High-field 13C dynamic nuclear polarization with a radical mixture.

Michaelis Vladimir K VK Smith Albert A AA Corzilius Björn B Haze Olesya O Swager Timothy M TM Griffin Robert G RG

Journal of the American Chemical Society 20130213 8

We report direct (13)C dynamic nuclear polarization at 5 T under magic-angle spinning (MAS) at 82 K using a mixture of monoradicals with narrow EPR linewidths. We show the importance of optimizing both EPR linewidth and electron relaxation times by studying direct DNP of (13)C using SA-BDPA and trityl radical, and achieve (13)C enhancements above 600. This new approach may be best suited for dissolution DNP and for studies of (1)H depleted biological and other nonprotonated solids. ...[more]

PMID: 23373472

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Project description:Solid-state dynamic nuclear polarization (DNP) using the cross-effect relies on radical pairs whose electron spin resonance (ESR) frequencies differ by the nuclear magnetic resonance (NMR) frequency. We measure the DNP provided by a new water-soluble verdazyl radical, verdazyl-ribose, under both magic-angle spinning (MAS) and static sample conditions at 9.4 T, and compare it to a nitroxide radical, 4-hydroxy-TEMPO. We find that verdazyl-ribose is an effective radical for cross-effect DNP, with the best relative results for a non-spinning sample. Under non-spinning conditions, verdazyl-ribose provides roughly 2× larger 13C cross-polarized (CP) NMR signal than the nitroxide, with similar polarization buildup times, at both 29 K and 76 K. With MAS at 7 kHz and 1.5 W microwave power, the verdazyl-ribose does not provide as much DNP as the nitroxide, with the verdazyl providing less NMR signal and a longer polarization buildup time. When the microwave power is decreased to 30 mW with 5 kHz MAS, the two types of radical are comparable, with the verdazyl-doped sample having a larger NMR signal which compensates for its longer polarization buildup time. We also present electron spin relaxation measurements at Q-band (1.2 T) and ESR lineshapes at 1.2 and 9.4 T. Most notably, the verdazyl radical has a longer T1e than the nitroxide (9.9 ms and 1.3 ms, respectively, at 50 K and 1.2 T). The verdazyl electron spin lineshape is significantly affected by the hyperfine coupling to four 14N nuclei, even at 9.4 T. We also describe 3000-spin calculations to illustrate the DNP potential of possible radical pairs: verdazyl-verdazyl, verdazyl-nitroxide, or nitroxide-nitroxide pairs. These calculations suggest that the verdazyl radical at 9.4 T has a narrower linewidth than optimal for cross-effect DNP using verdazyl-verdazyl pairs. Because of the hyperfine coupling contribution to the electron spin linewidth, this implies that DNP using the verdazyl radical would improve at lower magnetic field. Another conclusion from the calculations is that a verdazyl-nitroxide bi-radical would be expected to be slightly better for cross-effect DNP than the nitroxide-nitroxide bi-radicals commonly used now, assuming the same spin-spin coupling constants.

Dataset Information

High-field 13C dynamic nuclear polarization with a radical mixture.

Publications

High-field 13C dynamic nuclear polarization with a radical mixture.

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