SciCombinator

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Journal: Journal of magnetic resonance (San Diego, Calif. : 1997)

28

The goal of this work was to test feasibility of using galvinoxyl (2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy) as a polarizing agent for dissolution dynamic nuclear polarization (DNP) NMR spectroscopy. We have found that galvinoxyl is reasonably soluble in ethyl acetate, chloroform, or acetone and the solutions formed good glasses when mixed together or with other solvents such as dimethyl sulfoxide. W-band electron spin resonance (ESR) measurements revealed that galvinoxyl has an ESR linewidth D intermediate between that of carbon-centered free radical trityl OX063 and the nitroxide-based 4-oxo-TEMPO, thus the DNP with galvinoxyl for nuclei with low gyromagnetic ratio γ such as (13)C and (15)N is expected to proceed predominantly via the thermal mixing process. The optimum radical concentration that would afford the highest (13)C nuclear polarization (approximately 6% for [1-(13)C]ethyl acetate) at 3.35T and 1.4K was found to be around 40mM. After dissolution, large liquid-state NMR enhancements were achieved for a number of (13)C and (15)N compounds with long spin-lattice relaxation time T(1). In addition, the hydrophobic galvinoxyl free radical can be easily filtered out from the dissolution liquid when water is used as the solvent. These results indicate that galvinoxyl can be considered as an easily available free radical polarizing agent for routine dissolution DNP-NMR spectroscopy.

Concepts: Spin, Acetone, Ethanol, Nuclear magnetic resonance, Magnetic moment, Solvent, Electron paramagnetic resonance, Chloroform

4

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated “on-the-fly” re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g.(7)Li and (31)P at 117 and 122MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic (7)Li and (31)P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO4; (2) paramagnetic (17)O VT-NMR of the solid oxide fuel cell cathode material La2NiO4+δ; (3) broadband (93)Nb static NMR of the Li-ion battery material BNb2O5; and (4) broadband static (127)I NMR of a potential Li-air battery product LiIO3. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1-25MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems.

Concepts: Spin, Nuclear magnetic resonance, Magnetic resonance imaging, Solid-state nuclear magnetic resonance, Battery, Capacitor, Magic angle spinning, Magic angle

1

Molecular dynamics (MD) simulations are used to investigate (1)H nuclear magnetic resonance (NMR) relaxation and diffusion of bulk n-C5H12 to n-C17H36 hydrocarbons and bulk water. The MD simulations of the (1)H NMR relaxation times T1,2 in the fast motion regime where T1=T2 agree with measured (de-oxygenated) T2 data at ambient conditions, without any adjustable parameters in the interpretation of the simulation data. Likewise, the translational diffusion DT coefficients calculated using simulation configurations agree with measured diffusion data at ambient conditions. The agreement between the predicted and experimentally measured NMR relaxation times and diffusion coefficient also validate the forcefields used in the simulation. The molecular simulations naturally separate intramolecular from intermolecular dipole-dipole interactions helping bring new insight into the two NMR relaxation mechanisms as a function of molecular chain-length (i.e. carbon number). Comparison of the MD simulation results of the two relaxation mechanisms with traditional hard-sphere models used in interpreting NMR data reveals important limitations in the latter. With increasing chain length, there is substantial deviation in the molecular size inferred on the basis of the radius of gyration from simulation and the fitted hard-sphere radii required to rationalize the relaxation times. This deviation is characteristic of the local nature of the NMR measurement, one that is well-captured by molecular simulations.

Concepts: Molecular dynamics, Molecule, Nuclear magnetic resonance, Magnetic resonance imaging, Computational chemistry, Computer simulation, Relaxation, Relaxometry

1

Pressure-induced changes in the chemical or electronic structure of solids require pressures well into the Giga-Pascal (GPa) range due to the strong bonding. Anvil cell designs can reach such pressures, but their small and mostly inaccessible sample chamber has severely hampered NMR experiments in the past. With a new cell design that has a radio frequency (RF) micro-coil in the high pressure chamber, NMR experiments beyond 20 Giga-Pascal are reported for the first time. (1)H NMR of water shows sensitivity and resolution obtained with the cells, and (63)Cu NMR on a cuprate superconductor (YBa2Cu3O7-δ) demonstrates that single-crystals can be investigated, as well. (115)In NMR of the ternary chalcogenide AgInTe2 discovers an insulator-metal transition with shift and relaxation measurements. The pressure cells can be mounted easily on standard NMR probes that fit commercial wide-bore magnets with regular cryostats for field- and temperature-dependent measurements ready for many applications in physics and chemistry.

Concepts: Chemistry, Pressure, Atmospheric pressure, Atmosphere, Pascal, Superconductivity, Torr, Bar

1

We have successfully developed a 1020MHz (24.0T) NMR magnet, establishing the world’s highest magnetic field in high resolution NMR superconducting magnets. The magnet is a series connection of LTS (low-Tc superconductors NbTi and Nb3Sn) outer coils and an HTS (high-Tc superconductor, Bi-2223) innermost coil, being operated at superfluid liquid helium temperature such as around 1.8K and in a driven-mode by an external DC power supply. The drift of the magnetic field was initially ±0.8ppm/10h without the (2)H lock operation; it was then stabilized to be less than 1ppb/10h by using an NMR internal lock operation. The full-width at half maximum of a (1)H spectrum taken for 1% CHCl3 in acetone-d6 was as low as 0.7Hz (0.7ppb), which was sufficient for solution NMR. On the contrary, the temporal field stability under the external lock operation for solid-state NMR was 170ppb/10h, sufficient for NMR measurements for quadrupolar nuclei such as (17)O; a (17)O NMR measurement for labeled tri-peptide clearly demonstrated the effect of high magnetic field on solid-state NMR spectra.

Concepts: Electron, Magnetic field, Fundamental physics concepts, Magnet, Solid-state nuclear magnetic resonance, Superconductivity, Superconducting magnet, Electromagnet

0

The latest developments in the field of long-lived spin states are merged with pulsed-field gradient techniques to extend the diffusion time beyond what is currently achievable in standard q-space diffusive-diffraction studies. The method uses nearly-equivalent spin-½ pairs that let diffusion times of the order of many minutes to be measured allowing access to the long-time limit in cavities of macroscopic size (millimeters). A pulse sequence suitable to exploit this regime has been developed and validated with the use of numerical simulations and experiments.

0

Dynamic Nuclear Polarization (DNP) has proven itself most powerful for the orientation of nuclear spins in polarized targets and for hyperpolarization in magnetic resonance imaging (MRI). Unfortunately, the theoretical description of some of the processes involved in DNP invokes the high temperature approximation, in which Boltzmann factors are expanded up to first order, while the high electron and nuclear spin polarization required for many applications do not justify such an approximation. A previous article extended the description of one of the mechanisms of DNP-thermal mixing-beyond the high temperature approximation (Wenckebach, 2017). But that extension is still limited: it assumes that fast spectral diffusion creates a local equilibrium in the electron spin system. Provotorov’s theory of cross-relaxation enables a consistent further extension to slower spectral diffusion, but also invokes the high temperature approximation. The present article extends the theory of cross-relaxation to low temperature and applies it to spectral diffusion in glasses doped with paramagnetic centres with anisotropic g-tensors. The formalism is used to describe DNP via the mechanism of the cross effect. In the limit of fast spectral diffusion the results converge to those obtained in Wenckebach (2017) for thermal mixing. In the limit of slow spectral diffusion a hole is burnt in the electron spin resonance (ESR) signal, just as predicted by more simple models. The theory is applied to DNP of proton and (13)C spins in samples doped with the radical TEMPO.

Concepts: Electron, Magnetic field, Fundamental physics concepts, Spin, Nuclear magnetic resonance, Magnetic resonance imaging, Magnetism, Magnetic moment

0

Adiabatic half and full passages are invaluable for achieving uniform, B1-insensitive excitation or inversion of macroscopic magnetization across a well-defined range of NMR frequencies. To accomplish narrow frequency ranges with adiabatic pulses (<100Hz), long pulse durations at low RF power levels are necessary, and relaxation during these pulses may no longer be negligible. A numerical, discrete recursive combination of the Bloch equations for longitudinal and transverse relaxation with the optimized equation for adiabatic angular motion of magnetization is used to calculate the trajectory of magnetization including its relaxation during adiabatic hyperbolic secant pulses. The agreement of computer-calculated data with experimental results demonstrates that, in non-viscous, small-molecule fluids, it is possible to model magnetization and relaxation by considering standard T1 and T2 relaxation in the traditional rotating frame. The proposed model is aimed at performance optimizations of applications in which these pulses are employed. It differs from previous reports which focused on short high-power adiabatic pulses and relaxation that is governed by dipole-dipole interactions, cross polarization, or chemical exchange.

Concepts: Fundamental physics concepts, Maxwell's equations, Nuclear magnetic resonance, Magnetic resonance imaging, Frequency, Rotation, Range of a projectile, Relaxometry

0

Ceramic-based dielectric resonators can be used for high frequency magnetic resonance imaging and microscopy. When used as elements in a transmit array, the intrinsically low inter-element coupling allows flexibility in designing different geometric arrangements for different regions-of-interest. However, without being able to detune such resonators, they cannot be used as elements in a receive-only array. Here, we propose and implement a method, based on mode-disruption, for detuning ceramic-based dielectric resonators to enable them to be used as receive-only elements.

Concepts: Resonator, Nuclear magnetic resonance, Magnetic resonance imaging, Design, Resonance, Acoustic resonance, Mechanical resonance, Tesla coil

0

A new solid-state nuclear magnetic resonance (NMR) thermometry sample is proposed. The (207)Pb NMR chemical shift of a lead halide perovskite, methylammonium lead chloride (MAPbCl3) is very sensitive to temperature, 0.905±0.010ppmK(-1). The response to temperature is linear over a wide temperature range, from its tetragonal to cubic phase transition at 178K to >410K, making it an ideal standard for temperature calibrations in this range. Because the (207)Pb NMR lineshape for MAPbCl3 appears symmetric, the sample is ideal for calibration of variable temperature NMR data acquired for spinning or non-spinning samples. A frequency-ratio method is proposed for referencing (207)Pb chemical shifts, based on the (1)H and (13)C frequencies of the methylammonium cation, which are used asan internal standard. Finally, this new NMR thermometer has been used to measure the degree of frictional heating asa function of spinning frequency for a series of MAS rotors ranging in outer diameter from 1.3 to 7.0mm. As expected, the largest diameter rotors are more susceptible to frictional heating, but lower diameter rotors are subjected to higher frictional heating temperatures as they are typically spun at much higher spinning frequencies.

Concepts: Fundamental physics concepts, Nuclear magnetic resonance, Chemical shift, Temperature, Thermodynamics, Resonance, Thermometer, Fahrenheit