High-field Dynamic Nuclear Polarization Research Articles

Solid effect in magic angle spinning dynamic nuclear polarization

For over five decades, the solid effect (SE) has been heavily utilized as a mechanism for performing dynamic nuclear polarization (DNP). Nevertheless, it has not found widespread application in contemporary, high magnetic field DNP experiments because SE enhancements display an ω(0)(-2) field dependence. In particular, for nominally forbidden zero and double quantum SE transitions to be partially allowed, it is necessary for mixing of adjacent nuclear spin states to occur, and this leads to the observed field dependence. However, recently we have improved our instrumentation and report here an enhancement of ε = 91 obtained with the organic radical trityl (OX063) in magic angle spinning experiments performed at 5 T and 80 K. This is a factor of 6-7 higher than previous values in the literature under similar conditions. Because the solid effect depends strongly on the microwave field strength, we attribute this large enhancement to larger microwave field strengths inside the sample volume, achieved with more efficient coupling of the gyrotron to the sample chamber. In addition, we develop a theoretical model to explain the dependence of the buildup rate of enhanced nuclear polarization and the steady-state enhancement on the microwave power. Buildup times and enhancements were measured as a function of (1)H concentration for both trityl and Gd-DOTA. Comparison of the results indicates that for trityl the initial polarization step is the slower, rate-determining step. However, for Gd-DOTA the spread of nuclear polarization via homonuclear (1)H spin diffusion is rate-limiting. Finally, we discuss the applicability of the solid effect at fields > 5 T and the requirements to address the unfavorable field dependence of the solid effect.

Solvent-Free High-Field Dynamic Nuclear Polarization of Mesoporous Silica Functionalized with TEMPO

We report high-field magic-angle spinning dynamic nuclear polarization (MAS DNP) of mesoporous silica functionalized with nitroxide radicals. These results demonstrate that co-condensation can be employed to incorporate DNP polarizing agents into inorganic materials and that solvent-free DNP is feasible for porous materials. For the investigated material, the direct MAS DNP enhances the 29Si nuclear magnetic resonance (NMR) spectra, whereas the indirect MAS DNP via protons is inapplicable owing to the inefficiency of $${}^{1}\hbox{H}\rightarrow{}^{29}\hbox{Si}$$ cross polarization transfer. Furthermore, the 29Si signals in direct experiments build up in a few seconds at 100 K. This fast polarization buildup improves the NMR sensitivity and will be useful for the investigation of direct DNP below 100 K.

High-field dynamic nuclear polarization with high-spin transition metal ions.

We report the dynamic nuclear polarization of (1)H spins in magic-angle-spinning spectra recorded at 5 T and 84 K via the solid effect using Mn(2+) and Gd(3+) complexes as polarizing agents. We show that the magnitude of the enhancements can be directly related to the effective line width of the central (m(S) = -1/2 → +1/2) EPR transition. Using a Gd(3+) complex with a narrow central transition EPR line width of 29 MHz, we observed a maximum enhancement of ∼13, which is comparable to previous results on the narrow-line-width trityl radical.

In situ High‐Field Dynamic Nuclear Polarization—Direct and Indirect Polarization of 13C nuclei

In situ High-Field Dynamic Nuclear Polarization: Direct and indirect polarization of 13C nuclei by DNP is investigated (see graphic). The field-dependent enhancement profile for both processes are investigated and the bulk polarization build-up time constants τBC and τBH for direct and indirect 13C polarization are compared.

Liquid state DNP using a 260 GHz high power gyrotron

Dynamic nuclear polarization (DNP) at high magnetic fields (9.2 T, 400 MHz (1)H NMR frequency) requires high microwave power sources to achieve saturation of the EPR transitions. Here we describe the first high-field liquid-state DNP results using a high-power gyrotron microwave source (20 W at 260 GHz). A DNP enhancement of -29 on water protons was obtained for an aqueous solution of Fremy's Salt; in comparison the previous highest value was -10 using a solid-state microwave power source (maximum power 45 mW). The increased enhancements are partly due to larger microwave saturation and elevated sample temperature. These experimentally observed DNP enhancements, which by far exceed the predicted values extrapolated from low-field DNP experiments, demonstrate experimentally that DNP is possible in the liquid state also at high magnetic fields.

Dynamic nuclear polarization experiments at 14.1 T for solid-state NMR

Instrumentation for high-field dynamic nuclear polarization (DNP) at 14.1 T was developed to enhance the nuclear polarization for NMR of solids. The gyrotron generated 394.5 GHz submillimeter (sub-mm) wave with a power of 40 W in the second harmonic TE(0,6) mode. The sub-mm wave with a power of 0.5-3 W was transmitted to the sample in a low-temperature DNP-NMR probe with a smooth-wall circular waveguide system. The (1)H polarization enhancement factor of up to about 10 was observed for a (13)C-labeled compound with nitroxyl biradical TOTAPOL. The DNP enhancement was confirmed by the static magnetic field dependence of the NMR signal amplitude at 90 K. Improvements of the high-field DNP experiments are discussed.

A High-Conversion-Factor, Double-Resonance Structure for High-Field Dynamic Nuclear Polarization

This contribution presents a novel design of a double-resonance structure for high-field dynamic nuclear polarization operating at 95 GHz and 144 MHz, in which a miniaturized radiofrequency coil is integrated within a single-mode nonradiative dielectric resonator. After a detailed discussion of the design principles, the conversion factors of this system are determined by means of microwave and radiofrequency measurements. The obtained results, 1.68 mT/W1/2 for the microwave conversion factor and 0.8 mT/W1/2 for the radiofrequency conversion factor, represent the state-of-the-art among the double-resonance structures. Simultaneous electron paramagnetic resonance and liquid-state 1H nuclear magnetic resonance experiments are performed on samples of nitroxide radical 2,2,6,6-tetramethylpiperidine-1-oxyl dissolved in a mixture of water and dioxane. A maximum dynamic nuclear polarization enhancement of about −16 is obtained at a microwave power of 70 mW with a radical concentration of 10 mM in nanoliter-sized sample volumes. These results are discussed in view of further improvements and applications of the proposed double-resonance structure.

EPR Characterization of a Rigid Bis-TEMPO–Bis-Ketal for Dynamic Nuclear Polarization

We have characterized the rigid binitroxide radical bis-TEMPO-bis-Ketal (bTbK) by continuous-wave (CW) and pulsed electron paramagnetic resonance (EPR) spectroscopy performed at X-band (9 GHz) and G-band (180 GHz) frequencies. bTbK has been successfully used for dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SS-DNP) experiments based on the cross-effect, which involves two electrons and one nuclear spin, and gave very high signal enhancements. For a quantitative description of the polarization enhancements and their excitation frequency profile, a detailed information about the values and relative orientation of the magnetic hyperfine-, dipolar-, g-tensors and the exchange interaction of the two unpaired electron spins within the molecule is mandatory. We have determined these tensors and their relative orientation by CW-EPR spectra and pulsed electron double resonance experiments in frozen solution. The potential of using the cross-effect also for DNP in liquid solutions has been experimentally investigated by room-temperature high-field DNP experiments performed at 9.2 T.

High-Field Dynamic Nuclear Polarization for Solid and Solution Biological NMR

Dynamic nuclear polarization (DNP) results in a substantial nuclear polarization enhancement through a transfer of the magnetization from electrons to nuclei. Recent years have seen considerable progress in the development of DNP experiments directed towards enhancing sensitivity in biological nuclear magnetic resonance (NMR). This review covers the applications, hardware, polarizing agents, and theoretical descriptions that were developed at the Francis Bitter Magnet Laboratory at Massachusetts Institute of Technology for high-field DNP experiments. In frozen dielectrics, the enhanced nuclear polarization developed in the vicinity of the polarizing agent can be efficiently dispersed to the bulk of the sample via (1)H spin diffusion. This strategy has been proven effective in polarizing biologically interesting systems, such as nanocrystalline peptides and membrane proteins, without leading to paramagnetic broadening of the NMR signals. Gyrotrons have been used as a source of high-power (5-10 W) microwaves up to 460 GHz as required for the DNP experiments. Other hardware has also been developed allowing in situ microwave irradiation integrated with cryogenic magic-angle-spinning solid-state NMR. Advances in the quantum mechanical treatment are successful in describing the mechanism by which new biradical polarizing agents yield larger enhancements at higher magnetic fields. Finally, pulsed methods and solution experiments should play a prominent role in the future of DNP.

High-frequency dynamic nuclear polarization using mixtures of TEMPO and trityl radicals

In a previous communication [Hu et al., J. Am. Chem. Soc. 126, 10844 (2004)], an approach was demonstrated that improves the efficiency of the cross-effect polarization mechanism employed in high field dynamic nuclear polarization (DNP) experiments. Specifically, it was shown that tethering two TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) radicals increases the electron-electron dipole coupling from approximately 1 MHz in solutions of monomeric TEMPO to approximately 25 MHz in a tethered biradical. The larger coupling resulted in an increase in the DNP enhancements by a factor of approximately 3-4, from 45-50 to approximately 165. Here, a second approach to improving the efficiency of the polarization process is described that involves approximately satisfying the matching condition |omega(2e)-omega(1e)|=omega(n), where omega(2e) and omega(1e) are two frequencies in the electron paramagnetic resonance (EPR) spectrum and omega(n) is the Larmor frequency of the nuclear spins being polarized. Specifically, in a mixture of TEMPO and trityl [tris (8-carboxy-2,2,6,6-tetramethyl(-d3)-benzo[1,2d:4,5-d']bis(1,3)dithiol-4-yl) methyl] radicals, the intensity maxima in the EPR spectra of these two species are approximately separated by the (1)H NMR frequency. In this case the frequency difference between the g(yy) value of TEMPO and the narrow pseudo-isotropic g-value of trityl is approximately 224 MHz and the (1)H Larmor frequency is 211 MHz. The optimal magnetic field for DNP using the mixtures was found to coincide with the trityl EPR resonance. At 90 K and 5 T, a mixture of 20 mM TEMPO and 20 mM trityl enhanced the (1)H polarization by a factor of approximately 160, an improvement over the enhancement of approximately 50 with 40 mM TEMPO. The reasons for the improvement are discussed and evidence is presented suggesting that DNP enhancement can be improved further by tethering TEMPO and trityl or two similar radicals.

Conceptual Design Study of a Novel Gyrotron for NMR/DNP Spectroscopy

In this paper we present some initial results from a conceptual design study focused on the development of a novel frequency tunable gyrotron for nuclear magnetic resonance (NMR) spectroscopy with signal enhancement based on the utilization of high field radiation and dynamic nuclear polarization (DNP) technique. The first variants of both the electron optical system and the resonant cavity which have been designed aiming continuous frequency tunability in a broad frequency band are presented and discussed. The selected method for frequency tunability is based on the excitation of higher order axial modes and smooth transition between them. It was selected after a critical examination of the known theoretical and practical results related to the frequency control in gyrotrons. It is believed that the current conceptual design is an appropriate basis for development of the next (optimized) design which will include also a detailed design of other components (mode converter, output window etc.) and magnetic circuit (superconducting magnet and supplementary solenoids) as well as for the overall mechanical design and fabrication of the prospective gyrotron.