Article pubs.acs.org/JPCB
Cite This: J. Phys. Chem. B 2018, 122, 1898−1904
Magnetic-Field-Dependent Lifetimes of Hyperpolarized Cryogenic Temperature
13
C Spins at
Peter Niedbalski, Qing Wang, Christopher Parish, Fatemeh Khashami, Andhika Kiswandhi, and Lloyd Lumata* Department of Physics, The University of Texas at Dallas, 800 West Campbell Road, Richardson, Texas 75080, United States ABSTRACT: Using a home-built cryogen-free dynamic nuclear polarization (DNP) system with a variable magnetic field capability, 13C spin−lattice T1 relaxation times of hyperpolarized [1-13C] carboxylates (sodium acetate, glycine, sodium pyruvate, and pyruvic acid) doped with trityl OX063 free radical were systematically measured for the first time at different field strengths up to 9 T at T = 1.8 K. Our data reveal that the 13C T1 values of these frozen hyperpolarized 13C samples vary drastically with the applied magnetic field B according to an apparent empirical power-law dependence (13C T1 ∝ Bα, 2.3 < α < 3.1), with relaxation values ranging from a few hundred seconds at 1 T to over 200,000 s at fields close to 9 T. This low temperature relaxation behavior can be ascribed approximately to a model that accounts for the combined effect of 13C−1H intramolecular dipolar interaction and the relaxation contribution from the paramagnetic impurities present in the DNP sample. Since the lifetime or T1 storage of the hyperpolarized state is intimately linked to DNP efficiency, these 13C relaxation data at cryogenic temperature have important theoretical and experimental implications as the DNP of higher magnetic fields.
1. INTRODUCTION Dynamic nuclear polarization (DNP) has recently undergone a resurgence through a combination of technological advances in microwave-driven signal amplification in high resolution solidstate NMR via magic angle spinning (MAS) DNP and in the liquid state with the invention of dissolution DNP.1,2 Dissolution DNP in particular has revolutionized metabolic imaging, allowing for the production of highly polarized liquid samples with >10,000-fold NMR or imaging (MRI) signal enhancements of endogenous metabolic probes.3 In this technique, a sample with target nuclear spins is doped with free radical, placed in a relatively strong magnetic field at cryogenic temperature (3.35 T) leads to higher polarization enhancement when polarizing in the low temperature region (T ∼ 1−2 K).13,16,41,42 Our relaxation data appears to be in agreement with this trend of increasing DNP efficiency with magnetic field. When the magnetic field increases, nuclear spins relax toward thermal equilibrium progressively more slowly, increasing the polarization level at which the microwave-driven transfer of polarization from electrons to nuclei is in equilibrium with the relaxation of nuclei. These field-dependent relaxation data of 13C DNP samples also have a direct implication on our ability to store hyperpolarized state for transport of hyperpolarized 13C substrates.43 As dissolution DNP progresses toward higher magnetic fields, the methods and results described herein could be essential to our experimental and theoretical understanding of optimal DNP storage and efficiency.
Figure 5. Magnetic field dependence of 13C T1 for (a) sodium pyruvate, (b) pyruvic acid, (c) sodium acetate, and (d) glycine. Solid lines are power law fits, while dashed lines are a linear combination of dipolar and paramagnetic relaxation components. The top panel in each graph shows a measure of the goodness of fit ([T1measured − T1fit]/ [T1measured]) with filled symbols corresponding to the power law fittings and empty symbols denoting the linear combination fittings.
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AUTHOR INFORMATION
Corresponding Author
magnetic relaxation results in the observed B3 dependence. Of note is that pyruvic acid, being much more strongly concentrated than sodium pyruvate (14.4 M vs 1.4 M), has much greater interaction between 13C spins given the comparatively small distance between molecules. This allows for a greater rate of spin diffusion which in turn results in shortened T1. The contribution of dipolar relaxation is increased for acetate. The 13C label in acetate is only two bond lengths from the methyl 1H spins, making the strength of the interaction between the nuclei much greater than in the case of pyruvate. This brings the field dependence closer to the B2 dependence of the 1H−13C dipolar relaxation. Similarly, the
*E-mail:
[email protected]. ORCID
Lloyd Lumata: 0000-0002-3647-3753 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS This research work was supported by the UT Dallas startup research funding, the Welch Foundation grant number AT1877, and the U.S. Department of Defense grant number W81XWH-17-1-0303. The authors would like to thank Prof. 1902
DOI: 10.1021/acs.jpcb.8b00630 J. Phys. Chem. B 2018, 122, 1898−1904
Article
The Journal of Physical Chemistry B
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Mark Lee for access to the cryogen-free superconducting magnet at the UT Dallas Department of Physics.
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DOI: 10.1021/acs.jpcb.8b00630 J. Phys. Chem. B 2018, 122, 1898−1904
