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High-Frequency Dynamic Nuclear Polarization in the Nuclear Rotating Frame

✍ Scribed by C.T Farrar; D.A Hall; G.J Gerfen; M Rosay; J.-H Ardenkjær-Larsen; R.G Griffin


Publisher
Elsevier Science
Year
2000
Tongue
English
Weight
94 KB
Volume
144
Category
Article
ISSN
1090-7807

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✦ Synopsis


A proton dynamic nuclear polarization (DNP) NMR signal enhancement (⑀) close to thermal equilibrium, ⑀ ‫؍‬ 0.89, has been obtained at high field (B 0 ‫؍‬ 5 T, epr ‫؍‬ 139.5 GHz) using 15 mM trityl radical in a 40:60 water/glycerol frozen solution at 11 K. The electron-nuclear polarization transfer is performed in the nuclear rotating frame with microwave irradiation during a nuclear spinlock pulse. The growth of the signal enhancement is governed by the rotating frame nuclear spin-lattice relaxation time (T 1 ), which is four orders of magnitude shorter than the nuclear spin-lattice relaxation time (T 1n ). Due to the rapid polarization transfer in the nuclear rotating frame the experiment can be recycled at a rate of 1/T 1 and is not limited by the much slower lab frame nuclear spin-lattice relaxation rate (1/T 1n ). The increased repetition rate allowed in the nuclear rotating frame provides an effective enhancement per unit time 1/2 of ⑀ t ‫؍‬ 197. The nuclear rotating frame-DNP experiment does not require high microwave power; significant signal enhancements were obtained with a low-power (20 mW) Gunn diode microwave source and no microwave resonant structure. The symmetric trityl radical used as the polarization source is water-soluble and has a narrow EPR linewidth of 10 G at 139.5 GHz making it an ideal polarization source for highfield DNP/NMR studies of biological systems.


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A high-frequency dynamic nuclear polarization (DNP)/electron copy to systems with nuclei that are few in number, have low paramagnetic resonance spectrometer operating at 211 MHz for gyromagnetic ratios, and/or have low natural abundance. 1 H and 140 GHz for g Å 2 paramagnetic centers (5 T static fi