On the effects of quadrupolar relaxation in Earth's field NMR spectra.

There is growing interest in using low-field magnetic resonance experiments for routine chemical characterization. Earth's field NMR is one such technique that can garner structural information and enable sample differentiation with low cost and highly portable designs. The resulting NMR spectra are primarily influenced by J-couplings, resulting in so-called J-coupled spectra (JCS). Many small molecules include atoms with NMR-active nuclei that are quadrupolar either at natural abundance or are often isotopically enriched (e.g.,2H, 6Li, 11B, 14N, 17O, etc.) where the effects of quadrupolar J-couplings and relaxation on JCS of strongly- and weakly-coupled spin systems have not been explored to date. Herein, using a set of seven fluoropyridine samples with unique substitution and J-couplings, we demonstrate that the 14N relaxation rates can induce drastic line-broadening in the JCS. This includes a previously unexplored unique line broadening mechanism enabled by strongly coupled spins at low-field. Numerical simulations are used to model and refine the magnitudes and signs of J-couplings, as well as indirectly determine the 14N relaxation rates in a single 1D experiment that has a higher fidelity than observed in high-field NMR experiments.

Nuclear quadrupole resonance spectroscopy with a femtotesla diamond magnetometer.

Radio frequency (RF) magnetometers based on nitrogen vacancy centers in diamond are predicted to offer femtotesla sensitivity, but previous experiments were limited to the picotesla level. We demonstrate a femtotesla RF magnetometer using a diamond membrane inserted between ferrite flux concentrators. The device provides ~300-fold amplitude enhancement for RF magnetic fields from 70 kHz to 3.6 MHz, and the sensitivity reaches ~70 fT√s at 0.35 MHz. The sensor detected the 3.6-MHz nuclear quadrupole resonance (NQR) of room-temperature sodium nitrite powder. The sensor's recovery time after an RF pulse is ~35 µs, limited by the excitation coil's ring-down time. The sodium-nitrite NQR frequency shifts with temperature as -1.00±0.02 kHz/K, the magnetization dephasing time is T2*=887±51 µs, and multipulse sequences extend the signal lifetime to 332±23 ms, all consistent with coil-based studies. Our results expand the sensitivity frontier of diamond magnetometers to the femtotesla range, with potential applications in security, medical imaging, and materials science.

Quantitation of Nuclear Magnetic Resonance Spectra at Earth's Magnetic Field.

The inherently quantitative nature of nuclear magnetic resonance (NMR) spectroscopy is one of the most attractive aspects of this analytical technique. Quantitative NMR analyses have typically been limited to high-field (>1 T) applications. The aspects for quantitation at low magnetic fields (<1 mT) have not been thoroughly investigated and are shown to be impacted by the complex signatures that arise at these fields from strong heteronuclear J-couplings. This study investigates quantitation at Earth's magnetic field (∼50 µT) for a variety of samples in strongly, weakly, and uncoupled spin systems. To achieve accurate results in this regime, the instrumentation, experimental acquisition, processing, and theoretical aspects must be considered and reconciled. Of particular note is the constant field nuclear receptivity equation, which has been re-derived in this study to account for strong coupling and quality factor effects. The results demonstrate that the quantitation of homonuclear molecular groups, determination of heteronuclear pseudoempirical formulas, and mixture analysis are all feasible at Earth's magnetic field in a greatly simplified experimental system.

The 1H T1 dispersion curve of fentanyl citrate to identify NQR parameters.

We report the 1H T1 dispersion curve between 0 and 5 â€‹MHz for the synthetic opioid fentanyl citrate (C28H36N2O8). The structures in the curve can be used to estimate the 14N nuclear quadrupole resonance (NQR) frequencies of the material. Density functional theory predictions of the NQR parameters of several fentanyl citrate compounds are also reported. The predictions for the aniline nitrogen are consistent with structures in the observed T1 data. To help interpret the fentanyl citrate results the T1 dispersion curve for the explosive ammonium nitrate is also presented.

In vivo Observation of Tree Drought Response with Low-Field NMR and Neutron Imaging.

Using a simple low-field NMR system, we monitored water content in a living tree in a greenhouse over 2 months. By continuously running the system, we observed changes in tree water content on a scale of half an hour. The data showed a diurnal change in water content consistent both with previous NMR and biological observations. Neutron imaging experiments show that our NMR signal is primarily due to water being rapidly transported through the plant, and not to other sources of hydrogen, such as water in cytoplasm, or water in cell walls. After accounting for the role of temperature in the observed NMR signal, we demonstrate a change in the diurnal signal behavior due to simulated drought conditions for the tree. These results illustrate the utility of our system to perform noninvasive measurements of tree water content outside of a temperature controlled environment.

Low-field nuclear magnetic resonance for the in vivo study of water content in trees.

Nuclear magnetic resonance (NMR) and magnetic resonance imaging have long been used to study water content in plants. Approaches have been primarily based on systems using large magnetic fields (~1 T) to obtain NMR signals with good signal-to-noise. This is because the NMR signal scales approximately with the magnetic field strength squared. However, there are also limits to this approach in terms of realistic physiological configuration or those imposed by the size and cost of the magnet. Here we have taken a different approach--keeping the magnetic field low to produce a very light and inexpensive system, suitable for bulk water measurements on trees less than 5 cm in diameter, which could easily be duplicated to measure on many trees or from multiple parts of the same tree. Using this system we have shown sensitivity to water content in trees and their cuttings and observed a diurnal signal variation in tree water content in a greenhouse. We also demonstrate that, with calibration and modeling of the thermal polarization, the system is reliable under significant temperature variation.