H DNP at 1.4 T of Water Doped with a Triarylmethyl-Based Radical

Recently a triarylmethyl-based (TAM) radical has been developed for research in biological and other aqueous systems, and in low magnetic fields, 10 mT or less, large ¹H dynamic nuclear polarization (DNP) enhancements have been reported. In this paper the DNP properties of this radical have been investigated in a considerably larger field of 1.4 T, corresponding to proton and electron Larmor frequencies of 60 MHz and 40 GHz, respectively. To avoid excessive microwave heating of the sample, an existing DNP NMR probe was modified with a screening coil, wound around the sample capillary and with its axis perpendicular to the electric component of the microwave field. It was found that with this probe the temperature increase in the sample after 4 s of microwave irradiation with an incident power of 10 W was only 16°C. For the investigations, 10 mM of the TAM radical was dissolved in deionized, but not degassed, water and put into a 1-mm i.d. and 6-mm long capillary tube. At 26°C the following results were obtained: (I) The relaxivity of the radical is 0.07 (mMs)⁻¹, in accordance with the value extrapolated from low-field results; (II) The leakage factor is 0.63, the saturation factor at maximum power is 0.85, and the coupling factor is −0.0187. It is shown that these results agree very well with an analysis where the electron–dipolar interactions are the dominant DNP mechanism, and where the relaxation transitions resulting from these interactions are governed by translational diffusion of the water molecules. Finally, the possibilities of combining DNP with magnetic resonance microscopy (MRM) are discussed. It is shown that at 26°C the overall DNP-enhanced proton polarization should become maximal in an external field of 0.3 T and become comparable to the thermal equilibrium polarization in a field of 30 T, considerably larger than the largest high-resolution magnet available to date. It is concluded that DNP MRM in this field, which corresponds to a standard microwave frequency of 9 GHz, has the potential to significantly increase the sensitivity in NMR and MRI experiments of small aqueous samples doped with the TAM radical.     

1H dynamic nuclear polarization in supercritical ethylene at 1.4 T

(1)H dynamic nuclear polarization (DNP) has been measured in supercritical ethylene in the pressure range 60-300 bar in an external field of 1.4 T. A single-cell sapphire tube was used as a high-pressure cell, and powdered 1,3-bisdiphenylene-2-phenyl allyl (BDPA) free radicals were added and distributed at the wall of the cell. At all pressures the dominant DNP mechanism was a positive Overhauser enhancement, caused by proton-electron contact interactions at the fluid/solid radical interface. The observed enhancements varied from 12 at 60 bar to 17 at 300 bar. Besides the Overhauser enhancement, small solid state and thermal mixing enhancements also were observed, indicating that part of the ethylene was adsorbed at the radical surface for a prolonged time. The impacts of the experimental conditions on the Overhauser enhancement factors are discussed, and enhancements of at least 40-60 are estimated when the EPR saturation factor and the leakage factor become maximal. These data indicate that DNP-enhanced NMR has the potential of extending the impact of NMR in research areas involving supercritical fluids.     

Dissolution DNP NMR with solvent mixtures: substrate concentration and radical extraction

Dynamic nuclear polarization (DNP) followed by sudden sample dissolution, is a topic of active investigation owing to the method's unique prospects for the delivery of NMR spectra and images with unprecedented sensitivity. This experiment achieves hyperpolarization by the combined effects of electron-nuclear irradiation and cryogenic operation; the exploitation of these states occurs following a sudden melting and flushing of the resulting pellet from its original environment into a conventional, liquid-state setting. This melting and flushing usually demands using the equivalent of a few milliliters of hot solvent, a procedure which although well suited for in vivo studies leads to an excessive sample volume when considering typical analytical settings. The present study explores a way of reducing the ensuing dilution of the hyperpolarized analytes, by employing a combination of immiscible liquids for performing the melting and flushing. It is shown that suitable combinations of immiscible solvents - both in terms of their heat capacities and densities - allow one to melt the targeted cryogenic pellet and dissolve the hyperpolarized analytes in a fraction of the solvent hitherto required. By tailoring the resulting volume to the needs of a conventional 5mm NMR probe, a substantial sensitivity enhancement can be added to the hyperpolarization process. An extra benefit may arise from using radicals that preferentially dissolve in the immiscible organic phase, by way of a lengthening of the relaxation time of the investigated analytes. Examples of these principles are given, and further potential extensions of this approach are discussed.     

Comparison of Overhauser DNP at 0.34 and 3.4?T with Frémy’s Salt

Dynamic nuclear polarization (DNP) is investigated in the liquid state using a model system of Frémy's salt dissolved in water. Nuclear magnetic resonance signal enhancements at 0.34 and 3.4?T of the bulk water protons are recorded as a function of the irradiation time and the polarizer concentration. The build-up rates are consistent with the T(1n) of the observed water protons at room temperature (for 9?GHz/0.34?T) and for about 50?±?10?°C at 94?GHz/3.4?T. At 94?GHz/3.4?T, we observe in our setup a maximal enhancement of -50 at 25?mM polarizer concentration. The use of Frémy's salt allows the determination of the saturation factors at 94?GHz by pulsed ELDOR experiments. The results are well consistent with the Overhauser DNP mechanism and indicate that higher enhancements at this intermediate frequency require higher sample temperatures.     

Auger spectroscopy of the fracture surface of 1X18H10T stainless steel doped with helium and hydrogen

Variation of the element composition of the fracture surface of 1X18H10T steel specimens in unirradiated and helium and hydrogen doped states during strain at 300, 600, and 800°C in the chamber of the special Auger-spectrometer has been investigated. It has been shown that in helium and hydrogen doped steel versus unirradiated state the fracture surface is enriched with phosphorus and nickel and impoverished with sulphur more intensively.     

1H NMR Detection of superparamagnetic nanoparticles at 1T using a microcoil and novel tuning circuit

Magnetic beads containing superparamagnetic iron oxide nanoparticles (SPIONs) have been shown to measurably change the nuclear magnetic resonance (NMR) relaxation properties of nearby protons in aqueous solution at distances up to approximately 50 microm. Therefore, the NMR sensitivity for the in vitro detection of single cells or biomolecules labeled with magnetic beads will be maximized with microcoils of this dimension. We have constructed a prototype 550 microm diameter solenoidal microcoil using focused gallium ion milling of a gold/chromium layer. The NMR coil was brought to resonance by means of a novel auxiliary tuning circuit, and used to detect water with a spectral resolution of 2.5 Hz in a 1.04 T (44.2MHz) permanent magnet. The single-scan SNR for water was 137, for a 200 micros pi/2 pulse produced with an RF power of 0.25 mW. The nutation performance of the microcoil was sufficiently good so that the effects of magnetic beads on the relaxation characteristics of the surrounding water could be accurately measured. A solution of magnetic beads (Dynabeads MyOne Streptavidin) in deionized water at a concentration of 1000 beads per nL lowered the T(1) from 1.0 to 0.64 s and the T2 * from 110 to 0.91 ms. Lower concentrations (100 and 10 beads/nL) also resulted in measurable reductions in T2 *, suggesting that low-field, microcoil NMR detection using permanent magnets can serve as a high-sensitivity, miniaturizable detection mechanism for very low concentrations of magnetic beads in biological fluids.     

In vivo 1H spectroscopic studies of human gastrocnemius muscle at 1.5 T

In vivo high resolution 1H magnetic resonance spectra are observed from the gastrocnemius muscle in 12 normal volunteers. The gross spectral features do not appear to significantly change from individual to individual. However, the number and the relative amplitudes of the resonances from the fatty acid chains are found to exhibit significant variation from normal to normal. The spectra observed on different occasions in the same individual exhibit very little variation. Our studies indicate that it is preferable to use the spin echo sequence with a long echo time to observe water-suppressed proton spectra from the muscle tissue.     

First2H NMR at 58 T

The first nuclear magnetic resonance (NMR) experiments in pulsed field magnets at fields up to 58 T are reported. The basic features of the pulsed field source and the strategy to observe the first spectra are described. A²H NMR spectrum at 58 T is shown and the first results are discussed.     

EPR and 1H and 13C dynamic nuclear polarization studies of a molecularly doped polymer: bisphenol A polycarbonate doped with trianisylamine and trianisylaminium perchlorate.

We have investigated the EPR and DNP behavior of a molecularly doped polymer modeling those used to transport electronic charge in electrophotography. The EPR spectra show no evidence of the superexchange reported for a closely related system based on tri-p-tolylamine. The difference may be due to larger charge-transfer matrix elements in the latter system. An unambiguous interpretation of the observed 1H DNP was rendered difficult by the unanticipated asymmetry of the EPR spectra. We report extensive data on the "three-spin" effect evident in the DNP-enhanced 13C NMR spectra, and comment on its potential for characterizing polymer interfaces.     

Calculation of EELS at a doped semiconductor surface

We calculate electron energy loss spectra (EELS) within a simple model of a doped semiconductor surface. The model is designed to mimic an n-type GaAs surface for which experimental results exist. Coupling is only allowed via the dipole mechanism and the external electron is presumed to follow a specular trajectory. Using a cumulant expansion, we can treat multiple losses and gains as well as Debye-Waller factors. The basic theoretical quantity is an effective surface dielectric function that depends on frequency and wavevector parallel to the surface. Its calculation requires in general the specification of an additional boundary condition (ABC) in order to match fields at the surface. We explore the consequences of two possible ABC choices. At early stages of these calculations there are large differences between results from different ABC's; but by the time all the broadening (e.g. due to Ohmic damping, to multiple losses, and to finite spatial and energy resolution) has been included in order to compare with experiment, there survives much less dependence on ABC. We conclude that it is difficult to probe fine theoretical details, such as the influence of spatial dispersion, with EELS in such systems.     

Metallization degree of hydrogen at a pressure of 1.4 Mbar and a temperature a 3000 K

The electrical resistivity of liquid metallic hydrogen at a temperature of 3000 K and a density of 0.35 mol/cm³ is calculated. Hydrogen is considered as a three-component system consisting of electrons, protons, and neutral hydrogen atoms. The second order of perturbation theory in electron-proton and electron-atom interactions is used to determine the inverse relaxation time for electric conductivity. The Coulomb electron-electron interaction is taken into account in the random phase approximation and the exchange interaction and correlation of conductivity electrons are included in the local-field approximation. The model of hard spheres is used for the proton and atomic subsystems. The concentration of the electrically neutral atomic component proved to be significantly lower than the value assumed by the discoverers of metallic hydrogen.     

Osmotic and aging effects in caviar oocytes throughout water and lipid changes assessed by 1H NMR T1 and T2 relaxation and MRI

By combining NMR relaxation spectroscopy and magnetic resonance imaging techniques, unsalted (us) and salted (s) caviar (Acipenser transmontanus) oocytes were characterized over a storage period of up to 90 days. The aging and the salting effects on the two major cell constituents, water and lipids, were separately assessed. T1 and T2 decays were interpreted by assuming a two-site exchange model. At Day 0, two water compartments that were not in fast exchange were identified by the T1 relaxation measurements on the us oocytes. In the s samples, T1 decay was monoexponential. During the time of storage, an increment of the free water amount was found for the us oocytes, ascribed to an increased metabolism. T1 and T2 of the s oocytes shortened as a consequence of the osmotic stress produced by salting. Selective images showed the presence of water endowed with different regional mobility that severely changed during the storage. Lipid T1 relaxation decays collected on us and s samples were found to be biexponential, and the T1 values lengthened during storage. In us and s oocytes, the increased lipid mobility with the storage was ascribed to lipolysis. Selective images of us samples showed lipids that were confined to the cytoplasm for up to 60 days of storage.     

A comparative study of myo-inositol quantification using LCmodel at 1.5 T and 3.0 T with 3 D 1H proton spectroscopic imaging of the human brain

Myo-inositol is a strongly coupled system and resonates at four chemical shift positions. At 1.5 T, only the singlet component at 3.57 ppm is detected. However, at 3 T this resonance is resolved into its components at 3.55 ppm and 3.61 ppm. Due to the increased spectral resolution and signal-to-noise ratio, it is anticipated that the quantification of myo-inositol should improve at 3 T. Using data from normal controls and the LCmodel quantification procedure, we found that the quantification precision, reproducibility and detection sensitivity of myo-inositol is significantly better at 3 T relative to 1.5 T.     

Rapid temperature tuning of a 1.4-mum diode laser with application to high-pressure H(2)O absorption spectroscopy

Enhanced wavelength tuning of a distributed-feedback InGaAsP diode laser is demonstrated by use of rapid temperature cycling. The laser-active region is cycled from -10 to +50 degrees C (scanning the output from 1399 to 1403 nm) at kilohertz rates by pulsed heating with an auxiliary 532-nm laser. Such 4-nm scans represent a ten-fold increase in the wavelength-scanning range offered by standard current-tuning techniques and thus extend the capabilities of scan-wavelength sensors and systems. As an example application, we demonstrate absorption spectroscopy of H(2)O vapor at a pressure of 10 atm.