Dynamic Nuclear Polarization System Research Articles

1H Hyperpolarization of Solutions by Overhauser Dynamic Nuclear Polarization with 13C–1H Polarization Transfer

Dynamic nuclear polarization (DNP) is a method that can significantly increase the sensitivity of nuclear magnetic resonance. The only effective DNP mechanism for in situ hyperpolarization in solution is Overhauser DNP, which is inefficient for 1H at high magnetic fields. Here we demonstrate the possibility of generating significant 1H hyperpolarization in solution at room temperature. To counter the poor direct 1H Overhauser DNP, we implement steady-state 13C Overhauser DNP in solutions and then transfer the 13C hyperpolarization to 1H via a reverse insensitive nuclei enhanced by polarization transfer scheme. We demonstrate this approach using a 400 MHz gyrotron-equipped 3.2 mm magic angle spinning DNP system to obtain 1H DNP enhancement factors of 48, 8, and 6 for chloroform, tetrachloroethane, and phenylacetylene, respectively, at room temperature.

Production of highly polarized [1-13 C]acetate by rapid decarboxylation of [2-13 C]pyruvate - application to hyperpolarized cardiac spectroscopy and imaging.

The objective of the present work was to develop and implement an efficient approach to hyperpolarize [1-13 C]acetate and apply it to in vivo cardiac spectroscopy and imaging. Rapid hydrogen peroxide induced decarboxylation was used to convert hyperpolarized [2-13 C]pyruvate into highly polarized [1-13 C]acetate employing an additional step following rapid dissolution of [2-13 C]pyruvate in a home-built multi-sample dissolution dynamic nuclear polarization system. Phantom dissolution experiments were conducted to determine optimal parameters of the decarboxylation reaction, retaining polarization and T1 of [1-13 C]acetate. In vivo feasibility of detecting [1-13 C]acetate metabolism is demonstrated using slice-selective spectroscopy and multi-echo imaging of [1-13 C]acetate and [1-13 C]acetylcarnitine in the healthy rat heart. The first in vivo signal was observed ~23 s after dissolution. At the corresponding time point in the phantom experiments, 97.9 ± 0.4% of [2-13 C]pyruvate were converted into [1-13 C]acetate by the decarboxylation reaction. T1 and polarization of [1-13 C]acetate was determined to be 29.7 ± 1.9% and a 47.7 ± 0.5 s. Polarization levels of [2-13 C]pyruvate and [1-13 C]acetate were not significantly different after transfer to the scanner. In vivo, [1-13 C]acetate and [1-13 C]acetylcarnitine could be detected using spectroscopy and imaging. Decarboxylation of hyperpolarized [2-13 C]pyruvate enables the efficient production of highly polarized [1-13 C]acetate that is applicable to study short-chain fatty acid metabolism in the in vivo heart.

An efficient liquid helium / gas-gap switch allowing rapidly servicing low-temperature dynamic nuclear polarization systems

The authors present a novel design for servicing inserts for Hyperpolarising or similar systems operating at temperatures below 4 K. Sample space sleeves that accommodate variable temperature inserts are usually deeply integrated in the cryostat structure and are impossible to remove or to warm up in case of service needs. We present experimental results that show the performance of a liquid helium / gas-gap switch that will be used together with a sample space insert which is in direct contact to a cold plate. This sample space sleeve can be serviced by thermally disconnecting the switch from the cold plate. Furthermore, the additively manufactured heat switch features a novel cold plate interposer for heat transfer that allows the physical separation of the sample sleeve tube from the cold plate enabling a room temperature warm up or complete sleeve removal, if required.

Assembly and performance of a 6.4T cryogen-free dynamic nuclear polarization system.

We report on the assembly and performance evaluation of a 180-GHz/6.4T dynamic nuclear polarization (DNP) system based on a cryogen-free superconducting magnet. The DNP system utilizes a variable-field superconducting magnet that can be ramped up to 9T and equipped with cryocoolers that can cool the sample space with the DNP assembly down to 1.8K via the Joule-Thomson effect. A homebuilt DNP probe insert with top-tuned nuclear magnetic resonance coil and microwave port was incorporated into the sample space in which the effective sample temperature is approximately 1.9K when a 180-GHz microwave source is on during DNP operation. 13 C DNP of [1-13 C] acetate samples doped with trityl OX063 and 4-oxo-TEMPO in this system have resulted in solid-state 13 C polarization levels of 58±3% and 18±2%, respectively. The relatively high 13 C polarization levels achieved in this work have demonstrated that the use of a cryogen-free superconducting magnet for 13 C DNP is feasible and in fact, relatively efficient-a major leap to offset the high cost of liquid helium consumption in DNP experiments.

Construction and 13 C hyperpolarization efficiency of a 180GHz dissolution dynamic nuclear polarization system.

Dynamic nuclear polarization (DNP) via the dissolution method has become one of the rapidly emerging techniques to alleviate the low signal sensitivity in nuclear magnetic resonance (NMR) spectroscopy and imaging. In this paper, we report on the development and 13 C hyperpolarization efficiency of a homebuilt DNP system operating at 6.423T and 1.4K. The DNP hyperpolarizer system was assembled on a wide-bore superconducting magnet, equipped with a standard continuous-flow cryostat, and a 180GHz microwave source with 120mW power output and wide 4GHz frequency tuning range. At 6.423T and 1.4K, solid-state 13 C polarization P levels of 64% and 31% were achieved for 3M [1-13 C] sodium acetate samples in 1:1v/v glycerol:water glassing matrix doped with 15mM trityl OX063 and 40mM 4-oxo-TEMPO, respectively. Upon dissolution, which takes about 15s to complete, liquid-state 13 C NMR signal enhancements as high as 240000-fold (P=21%) were recorded in a nearby high resolution 13 C NMR spectrometer at 1T and 297K. Considering the relatively lower cost of our homebuilt DNP system and the relative simplicity of its design, the dissolution DNP setup reported here could be feasibly adapted for in vitro or in vivo hyperpolarized 13 C NMR or magnetic resonance imaging at least in the pre-clinical setting. Copyright © 2017 John Wiley & Sons, Ltd.

Waveguide transition with vacuum window for multiband dynamic nuclear polarization systems.

A low loss waveguide transition section and oversized microwave vacuum window covering several frequency bands (94 GHz, 140 GHz, 188 GHz) is presented. The transition is compact and was optimized for multiband Dynamic Nuclear Polarization (DNP) systems in a full-wave simulator. The window is more broadband than commercially available windows, which are usually optimized for single band operation. It is demonstrated that high-density polyethylene with urethane adhesive can be used as a low loss microwave vacuum window in multiband DNP systems. The overall assembly performance and dimensions are found using full-wave simulations. The practical aspects of the window implementation in the waveguide are discussed. To verify the design and simulation results, the window is tested experimentally at the three frequencies of interest.

Differentiating inflamed and normal lungs by the apparent reaction rate constants of lactate dehydrogenase probed by hyperpolarized (13)C labeled pyruvate.

Clinically translatable hyperpolarized (HP) (13)C-NMR can probe in vivo enzymatic reactions, e.g., lactate dehydrogenase (LDH)-catalyzed reaction by injecting HP (13)C-pyruvate into the subject, which is converted to (13)C labeled lactate by the enzyme. Parameters such as (13)C-lactate signals and lactate-to-pyruvate signal ratio are commonly used for analyzing the HP (13)C-NMR data. However, the biochemical/biological meaning of these parameters remains either unclear or dependent on experimental settings. It is preferable to quantify the reaction rate constants with a clearer physical meaning. Here we report the extraction of the kinetic parameters of the LDH reaction from HP (13)C-NMR data and investigate if they can be potential predictors of lung inflammation. Male Sprague-Dawley rats (12 controls, 14 treated) were used. One dose of bleomycin (2.5 U/kg) was administered intratracheally to the treatment group. The lungs were removed, perfused, and observed by the HP-NMR technique, where a HyperSense dynamic nuclear polarization system was used to generate the HP (13)C-pyruvate for injecting into the lungs. A 20 mm (1)H/(13)C dual-tuned coil in a 9.4-T Varian vertical bore NMR spectrometer was employed to acquire the (13)C spectral data every 1 s over a time period of 300 s using a non-selective, 15-degree radiofrequency pulse. The apparent rate constants of the LDH reaction and their ratio were quantified by applying ratiometric fitting analysis to the time series data of (13)C labeled pyruvate and lactate. The apparent forward rate constant kp =(3.67±3.31)×10(-4) s(-1), reverse rate constant kl =(4.95±2.90)×10(-2) s(-1), rate constant ratio kp /kl =(7.53±5.75)×10(-3) for the control lungs; kp =(11.71±4.35)×10(-4) s(-1), kl =(9.89±3.89)×10(-2) s(-1), and kp /kl =(12.39±4.18)×10(-3) for the inflamed lungs at the 7(th) day post treatment. Wilcoxon rank-sum test showed that the medians of these kinetic parameters of the 7-day cohort were significantly larger than those of the control cohort (P<0.001, P=0.001, and P=0.019, respectively). The rate constants of individual lungs correlated significantly with the histology scores of neutrophils and organizing pneumonia foci but not macrophages. Both kp and kp /kl positively correlated with lactate labeling signals. No correlation was found between kl and lactate labeling signals. The results indicate bleomycin-induced lung inflammation significantly increased both the forward and reverse reaction rate constants of LDH and their ratio at day-7 after bleomycin treatment.

A multisample dissolution dynamic nuclear polarization system for serial injections in small animals

Several in vivo applications of dissolution dynamic nuclear polarization (DNP) require rapid successive injections of hyperpolarized substrates. Here we present the design and performance of a custom-built multisample dissolution DNP setup for small animal research. The DNP setup consists of a commercial wide-bore magnet charged to 3.35 T, a cryostat, a 94-GHz microwave source, and a custom-built skeleton that accommodates four identical sample sticks. Each sample stick features a dissolver locked into the skeleton port and a lifter, which permits moving the sample cup out of the liquid helium bath for dissolution. The dissolution of the first sample was triggered after 2 hours of polarization buildup during single-shot operation of the cryostat. Thereafter, a time window of 75-90 min was available to dissolve the remaining three polarized samples. The average liquid state polarization over all four sticks was measured as 18.7% ± 2.3% for [1-13C] pyruvate 30 s after dissolution. In vivo applicability of the setup using serial injections of [1-13C] pyruvate to study cardiac metabolism in rats revealed good reproducibility. The proposed four-sample DNP insert provides reproducible liquid state polarization of [1-13C] pyruvate and allows for rapid repeat injections in small animals. Magn Reson Med 77:904-910, 2017. © 2016 International Society for Magnetic Resonance in Medicine.

Abstract B51: Metabolic imaging with hyperpolarized [1-13C]-pyruvate and DCE-MRI

Abstract Purpose: To improve the quality and specificity of metabolic imaging with hyperpolarized pyruvate using prior information from dynamic contrast-enhanced MRI (DCE-MRI). Background: Dynamic nuclear polarization (DNP) and MR spectroscopic imaging of [1-13C]-pyruvate shows tremendous promise for imaging aerobic glycolysis with sensitivity, specificity, and resolution that was previously impossible. Exogeneous, enriched hyperpolarized (HP) pyruvate is injected as a bolus and traverses multiple biological barriers before it is exposed to intracellular enzymes that mediate its fate. Preservation of the spin label through chemical reaction allows visualization of pyruvate and its chemical endpoints (lactate, alanine, and carbon dioxide/bicarbonate). We have previously observed a strong correlation between tumor perfusion and the normalized area under the curve for HP lactate, the chemical endpoint associated with aerobic glycolysis. A pharmacokinetic model of HP substrate evolution that balances physiological accuracy and computational burden includes two physical pools (intravascular/extravascular) and two chemical pools (pyruvate/lactate). In the analytical solution for this model, terms for substrate extravasation and the fractional intravascular volume can be recognized as analogues for KTRANS and Vb that are derived from analysis of DCE-MRI data using the extended Tofts model. Use of these DCE-MRI parameters as prior information could eliminate unknowns in the measurement of HP agents and improve the specificity of quantitative estimates for kPL, the apparent conversion rate for HP pyruvate into lactate. Experimental Procedures: Athymic nude mice bearing orthotopic anaplastic thyroid cancer tumors were anesthetized and scanned using a 7T Biospec small animal MR system (Bruker Biospin Corp.). A dual-tuned 1H/13C volume resonator was used for anatomic imaging and for 13C excitation, and a surface coil was used for 13C detection. HP pyruvate was prepared using a HyperSense DNP system (Oxford Instruments). Dynamic 13C spectroscopic imaging data was acquired using a radial multi-band frequency encoding sequence beginning prior to intravascular administration of HP pyruvate via tail-vein catheter. DCE-MRI data was acquired after HP measurements, using a fast spoiled gradient echo sequence. DCE-MRI data was fit to the extended Tofts model on a pixel-by-pixel basis using software developed in Matlab (The Mathworks). Parametric maps for perfusion and vascular blood volume fraction were resampled to the resolution of HP 13C scans and used as priors in a constrained reconstruction algorithm that enforces consistency between undersampled 13C projection data, the kinetic model, and prior information from 1H MRI. Results: With prior information about extravasation and fractional intravascular blood volume, the constrained reconstruction algorithm needs only solve for a global parameterized vascular input function and values for chemical conversion (kPL) and signal relaxation/loss for each voxel in the imaging volume. Elimination of nuisance parameters with strongly correlated effects reduces the computational burden of constrained reconstruction and clarifies interpretation of changes in biomarkers due to disease progression or response to therapy. Conclusions: The combination of DCE-MRI with constrained reconstruction reduces the number of unknowns in quantitative metabolic imaging using HP pyruvate, eases the computational burden, and decouples correlated effects of perfusion and chemical exchange. Citation Format: James A. Bankson, Christopher M. Walker, Yunyun Chen, Stephen Y. Lai, John D. Hazle. Metabolic imaging with hyperpolarized [1-13C]-pyruvate and DCE-MRI. [abstract]. In: Proceedings of the AACR Special Conference: Metabolism and Cancer; Jun 7-10, 2015; Bellevue, WA. Philadelphia (PA): AACR; Mol Cancer Res 2016;14(1_Suppl):Abstract nr B51.

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet.

We sought to build a dynamic nuclear polarization system for operation at 4.6 T (129 GHz) and evaluate its efficiency in terms of (13)C polarization levels using free radicals that span a range of ESR linewidths. A liquid helium cryostat was placed in a 4.6 T superconducting magnet with a 150-mm warm bore diameter. A 129-GHz microwave source was used to irradiate (13)C enriched samples. Temperatures close to 1 K were achieved using a vacuum pump with a 453-m(3)/h roots blower. A hyperpolarized (13)C nuclear magnetic resonance (NMR) signal was detected using a saddle coil and a Varian VNMRS console operating at 49.208 MHz. Samples doped with free radicals BDPA (1,3-bisdiphenylene-2-phenylallyl), trityl OX063 (tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole-4-yl}methyl sodium salt), galvinoxyl ((2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy), 2,2-diphenylpicrylhydrazyl (DPPH) and 4-oxo-TEMPO (4-Oxo-2,2,6,6-tetramethyl-1-piperidinyloxy) were assayed. Microwave dynamic nuclear polarization (DNP) spectra and solid-state (13)C polarization levels for these samples were determined. (13)C polarization levels close to 50 % were achieved for [1-(13)C]pyruvic acid at 1.15 K using the narrow electron spin resonance (ESR) linewidth free radicals trityl OX063 and BDPA, while 10-20 % (13)C polarizations were achieved using galvinoxyl, DPPH and 4-oxo-TEMPO. At this field strength free radicals with smaller ESR linewidths are still superior for DNP of (13)C as opposed to those with linewidths that exceed that of the (1)H Larmor frequency.

THz Gyrotron and BWO Designed for Operation in DNP-NMR Spectrometer Magnet

Dynamic nuclear polarization (DNP) in high-field nuclear magnetic resonance (NMR) spectroscopy requires medium-power terahertz radiation, which nowadays can be provided basically by gyrotrons with superconducting magnets. As the electron cyclotron frequency is very close to the frequency of electron paramagnetic resonance for the same magnetic field, under certain conditions the gyrotron can be installed inside the same solenoid used for NMR spectrometer. This eliminates the need for an additional superconducting magnet, results in a shorter terahertz transmission line, and can make DNP systems practical. In addition to an extremely low-voltage gyrotron (“gyrotrino”), we analyze also advantages of strong magnetic field for a slow-wave electron device as an alternative terahertz source.

Simplified THz Instrumentation for High-Field DNP-NMR Spectroscopy.

We present an alternate simplified concept to irradiate a nuclear magnetic resonance sample with terahertz (THz) radiation for dynamic nuclear polarization (DNP) experiments using the TE(01) circular waveguide mode for transmission of the THz power and the illumination of the DNP sample by either the TE(01) or TE(11) mode. Using finite element method and 3D electromagnetic simulations we demonstrate that the average value of the transverse magnetic field induced by the THz radiation and responsible for the DNP effect using the TE(11) or the TE(01) mode are comparable to that generated by the HE(11) mode and a corrugated waveguide. The choice of the TE(11)/TE(01) mode allows the use of a smooth-walled, oversized waveguide that is easier to fabricate and less expensive than a corrugated waveguide required for transmission of the HE(11) mode. Also, the choice of the TE(01) mode can lead to a simplification of gyrotron oscillators that operate in the TE(0n) mode, by employing an on-axis rippled-wall mode converter to convert the TE(0n) mode into the TE(01) mode either inside or outside of the gyrotron tube. These novel concepts will lead to a significant simplification of the gyrotron, the transmission line and the THz coupler, which are the three main components of a DNP system.

A Super-Wide Bore DNP System for Multiple Sample Polarization: Cryogenic Performance and Polarization at Low Temperature

The volume of polarized sample and the delay required between successive polarizations of samples represent serious constraints for dynamic nuclear polarization (DNP) applications. With these limitations in mind, a DNP polarizer, based on a super-wide bore (150-mm diameter) vertical magnet operating at 3.35 T, was designed. The working diameter for loading/unloading samples is equal to 46 mm and the microwave cavity can accommodate up to three samples. The cryostat can be cooled to 4.2 K in typically 2 h and filled with liquid helium in 1 h. Once filled with liquid helium, the cryostat hold time is on the order of 4 h and a minimum temperature of 1.19 K can be reached. In situ polarization levels at low temperature were measured between 5 and 10 % in single and multiple samples of 13C-labeled urea and glycine.

DNP Methods for Cardiac Metabolic Imaging with Hyperpolarized [1-13C]pyruvate Large Dose Injection in Pigs

In this study we set up and optimized a dynamic nuclear polarization (DNP) procedure for the hyperpolarization of a large dose suitable for cardiac metabolic imaging in vivo in swine models. The dose range proposed in this study allowed chemical shift imaging of cardiac metabolism with hyperpolarized [1-13C]pyruvate in pigs. We investigated the typical pattern of distribution of [1-13C]pyruvate and its downstream metabolites: we analysed the variation of the maximum value of the normalized [1-13C]pyruvate signal and the global pyruvate signal in left ventricle (LV). The study reports data obtained with a large dose increase compared to small animal studies: 20 ml of 230 mM [1-13C]pyruvate with 16 ± 3 % polarization (mean ± SD), using a DNP system operating at ~1.4 K with a magnetic field of 3.35 T. A significant correlation between the maximum value of the normalized [1-13C]pyruvate signal and the global pyruvate signal in the LV was found. The characterization of the dynamic range of the signal and the optimization of the standardized dose could be a starting point for designing pathophysiological studies in experimental large animal models. With this approach the hyperpolarization of metabolic substrates could be applied in biomedical magnetic resonance, which could become one of the most promising models for cardiovascular imaging.

Sci-Fri AM: Imaging - 06: Hyperpolarized 13 C Magnetic Resonance Imaging and Dynamic Spectroscopy for Detection of Radiation-Induced Lung Injury

Carbon-13 (13C) can be hyperpolarized by Dynamic Nuclear Polarization (DNP) to increase the signal by 10,000 times. By hyperpolarizing 13C in the pyruvate molecule, radiation—induced lung injury (RILI) may be studied with Magnetic Resonance Imaging. In-vivo, pyruvate breaks down into lactate, alanine, bicarbonate and other metabolites in a time-dependent manner. The early stages of RILI lead to higher concentration of lactate in tissues. Therefore the ratio of pyruvate to lactate measured in rat lungs, following irradiation may provide an early indication of RILI. In the present study, dynamic MR spectroscopic techniques are developed to ensure proper quantification of these metabolites. [1-13C] labelled pyruvate (CIL, Cambridge, MA) was hyperpolarized by a commercially-available DNP system (Hypersense, Oxford Instruments). The DNP system utilizes low temperature (1.4 °K), high magnetic field strength (3.35 T) and irradiation with a microwave source (94.15 GHz) to polarize the pyruvate. Data were obtained following bolus injection of 3 ml of 0.8 mM [1-13C] pyruvic acid in the tail vein of healthy Sprague Dawley rats (400–450 g) following an animal care protocol approved by the Animal Use Subcommittee of the University Council on Animal Care at the University of Western Ontario. Pyruvate and lactate signals were identified based on their chemical shift from the obtained in-vivo dynamic spectra. The relative signal strength from these metabolites was quantified. This study demonstrated the capability of quantification of hyperpolarized [1-13C] labeled pyruvate and lactate from in-vivo dynamic spectra in rats which represents an important step toward studies of RILI.

A novel variable field system for field-cycled dynamic nuclear polarization spectroscopy

Dynamic nuclear polarization (DNP) is an NMR-based technique which enables detection and spectral characterization of endogenous and exogenous paramagnetic substances measured via transfer of polarization from the saturated unpaired electron spin system to the NMR active nuclei. A variable field system capable of performing DNP spectroscopy with NMR detection at any magnetic field in the range 0–0.38 T is described. The system is built around a clinical open-MRI system. To obtain EPR spectra via DNP, partial cancellation of the detection field B 0 NMR is required to alter the evolution field B 0 EPR at which the EPR excitation is achieved. The addition of resistive actively shielded field cancellation coils in the gap of the primary magnet provides this field offset in the range of 0–100 mT. A description of the primary magnet, cancellation coils, power supplies, interfacing hardware, RF electronics and console are included. Performance of the instrument has been evaluated by acquiring DNP spectra of phantoms with aqueous nitroxide solutions (TEMPOL) at three NMR detection fields of 97 G, 200 G and 587 G corresponding to 413 kHz, 851.6 kHz and 2.5 MHz respectively and fixed EPR evolution field of 100 G corresponding to an irradiation frequency of 282.3 MHz. This variable-field DNP system offers great flexibility for the performance of DNP spectroscopy with independent optimum choice of EPR excitation and NMR detection fields.

L-band Overhauser dynamic nuclear polarization

We present the development of an Overhauser dynamic nuclear polarization (DNP) instrument at 0.04 T using 1.1 GHz (L-band) electron spin resonance frequencies (ESR) and 1.7 MHz 1H nuclear magnetic resonance frequencies. Using this home-built DNP system, the electron–nucleus coupling factor of 4-oxo-TEMPO dissolved in water was determined as 0.39 ± 0.06 at 0.04 T. The higher coupling factor obtained at this field compared to higher magnetic fields, such as 0.35 T, directly translates to higher enhancement of the NMR signal and opens up a wider time scale window for observing water dynamics interacting with macromolecular systems, including proteins, polymers or lipid vesicles. The higher enhancements obtained will facilitate the observation of water dynamics at correlation times up to 10 ns, that corresponds to more than one order of magnitude slower dynamics than accessible at 0.35 T using X-band ESR frequencies.

Dynamic nuclear polarization system for the SANS-J-II spectrometer at JAEA

We have developed a dynamic nuclear polarization (DNP) system for the SANS-J-II spectrometer at the JRR-3 atomic research reactor of Japan Atomic Energy Agency (JAEA). The DNP system is composed of a split-type horizontal superconducting magnet (3.3 T), a Gunn oscillator as a microwave source (94 GHz), and a cryostat (1.2 K). In particular, a sample cell with ∅40 in inner diameter and the magnet with a field homogeneity of 5×10−5 in a volume of ∅25 mm×8 mm were employed to polarize samples with a diameter of ∅20 mm for the ultra small-angle scattering experiment using the magnetic lens installed at the SANS-J-II spectrometer [S. Koizumi, H. Iwase, J. Suzuki, T. Oku, R. Motokawa, H. Sasao, H. Tanaka, D. Yamaguchi, H.M. Shimizu, T. Hashimoto, J. Appl. Crystallogr. 40 (2007) s474]. We obtained the proton polarization |P|=32% in the polyethylene doped with 2,2,6,6-tetra-methyl-piperidine-1-oxyl (TEMPO).

Magnetic-field cycling instrumentation for dynamic nuclear polarization-nuclear magnetic resonance using photoexcited triplets

To advance static solid-state NMR with hyperpolarized nuclear spins, a system has been developed enabling dynamic nuclear polarization (DNP) using electron spins in the photoexcited triplet state with X-band microwave apparatus, followed by static solid-state nuclear magnetic resonance (NMR) experiments using the polarized nuclear-spin system with a goniometer. In order to perform the DNP and NMR procedures in different magnetic fields, the DNP system and the NMR system are spatially separated, between which the sample can be shuttled while its orientation is controlled in a reproducible fashion. We demonstrate that the system developed in this work is operational for solid-state NMR with hyperpolarized nuclear-spin systems in static organic materials, and also discuss the application of our system.

Portable X-band system for solution state dynamic nuclear polarization

This paper concerns instrumental approaches to obtain large dynamic nuclear polarization (DNP) enhancements in a completely portable system. We show that at fields of 0.35T under ambient conditions and at X-band frequencies, 1H enhancements of >100-fold can be achieved using nitroxide radical systems, which is near the theoretical maximum for 1H polarization using the Overhauser effect at this field. These large enhancements were obtained using a custom built microwave transmitter and a commercial TE102 X-band resonant cavity. The custom built microwave transmitter is compact, so when combined with a permanent magnet it is readily transportable. Our commercial X-band resonator was modified to be tunable over a range of ∼9.5–10GHz, giving added versatility to our fixed field portable DNP system. In addition, a field adjustable Halbach permanent magnet has also been employed as another means for matching the electron spin resonance condition. Both portable setups provide large signal enhancements and with improvements in design and engineering, greater than 100-fold 1H enhancements are feasible.