Ultra-low Field Nuclear Magnetic Resonance Research Articles

Zero-field J-spectroscopy of quadrupolar nuclei

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) allows molecular structure elucidation via measurement of electron-mediated spin-spin J-couplings. This study examines zero-field J-spectra from molecules with quadrupolar nuclei, exemplified by solutions of various isotopologues of ammonium cations. The spectra reveal differences between various isotopologues upon extracting precise J-coupling values from pulse-acquire measurements. A primary isotope effect, △J=γ14N/γ15NJ15NH−J14NH≈−58\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\ riangle J=\\left({\\gamma }_{{}^{14}{{{{{\\rm{N}}}}}}}/{\\gamma }_{{}^{15}{{{{{\\rm{N}}}}}}}\\right){J}_{{}^{15}{{{{{\\rm{N}}}}}}{{{{{\\rm{H}}}}}}}-{J}_{{}^{14}{{{{{\\rm{N}}}}}}{{{{{\\rm{H}}}}}}}\\approx -58$$\\end{document} mHz, is deduced by analysis of the proton-nitrogen J-coupling ratios. This study points toward further experiments with symmetric cations containing quadrupolar nuclei, promising applications in biomedicine, energy storage, and benchmarking quantum chemistry calculations.

Possible Applications of Dissolution Dynamic Nuclear Polarization in Conjunction with Zero- to Ultralow-Field Nuclear Magnetic Resonance

Possible Applications of Dissolution Dynamic Nuclear Polarization in Conjunction with Zero- to Ultralow-Field Nuclear Magnetic Resonance

Background-Free Detection of Spin-Exchange Dynamics at Ultra-Low Magnetic Field.

Ultra-low field nuclear magnetic resonance spectroscopy (NMR) and imaging (MRI) inherently suffer from a low signal-to-noise ratio due to the small thermal polarization of nuclear spins. Transfer of polarization from a pre-polarized spin system to a thermally polarized spin system via the Spin Polarization Induced Nuclear Overhauser Effect (SPINOE) could potentially be used to overcome this limitation. SPINOE is particularly advantageous at ultra-low magnetic field, where the transferred polarization can be several orders of magnitude higher than thermal polarization. Here we demonstrate direct detection of polarization transfer from highly polarized 129 Xe gas spins to 1 H spins in solution via SPINOE. At ultra-low field, where thermal nuclear spin polarization is close to background noise levels and where different nuclei can be simultaneously detected in a single spectrum, the dynamics of the polarization transfer can be observed in real time. We show that by simply bubbling hyperpolarized 129 Xe into solution, we can enhance 1 H polarization levels by a factor of up to 151-fold. While our protocol leads to lower enhancements than those previously reported under extreme Xe gas pressures, the methodology is easily repeatable and allows for on-demand enhanced spectroscopy. SPINOE at ultra-low magnetic field could also be employed to study 129 Xe interactions in solutions.

Zero- to Ultralow-Field Nuclear Magnetic Resonance Enhanced with Dissolution Dynamic Nuclear Polarization.

Zero- to ultralow-field nuclear magnetic resonance is a modality of magnetic resonance experiment which does not require strong superconducting magnets. Contrary to conventional high-field nuclear magnetic resonance, it has the advantage of allowing high-resolution detection of nuclear magnetism through metal as well as within heterogeneous media. To achieve high sensitivity, it is common to couple zero-field nuclear magnetic resonance with hyperpolarization techniques. To date, the most common technique is parahydrogen-induced polarization, which is only compatible with a small number of compounds. In this article, we establish dissolution dynamic nuclear polarization as a versatile method to enhance signals in zero-field nuclear magnetic resonance experiments on sample mixtures of [13C]sodium formate, [1-13C]glycine, and [2-13C]sodium acetate, and our technique is immediately extendable to a broad range of molecules with >1 s relaxation times. We find signal enhancements of up to 11,000 compared with thermal prepolarization in a 2 T permanent magnet. To increase the signal in future experiments, we investigate the relaxation effects of the TEMPOL radicals used for the hyperpolarization process at zero- and ultralow-fields.

Visualization of dynamics in coupled multi-spin systems.

Since the dawn of quantum mechanics, ways to visualize spins and their interactions have attracted the attention of researchers and philosophers of science. In this work we present a generalized measurement-based 3D-visualization approach for describing dynamics in strongly coupled spin ensembles. The approach brings together angular momentum probability surfaces (AMPS), Husimi functions, and DROPS (discrete representations of operators for spin systems) and finds particular utility when the total angular momentum basis is used for describing Hamiltonians. We show that, depending on the choice of a generalized measurement operator, the plotted surfaces either represent probabilities of finding the maximal projection of an angular momentum along any direction in space or represent measurable coherences between the states with different total angular momenta. Such effects are difficult to grasp by looking at (time-dependent) numerical values of density-matrix elements. The approach is complete in a sense that there is one-to-one correspondence between the plotted surfaces and the density matrix. Three examples of nuclear spin dynamics in two-spin systems are visualized: (i)a zero- to ultralow-field (ZULF) nuclear magnetic resonance (NMR) experiment in the presence of a magnetic field applied perpendicularly to the sensitive axis of the detector, (ii)interplay between chemical exchange and spin dynamics during high-field signal amplification by reversible exchange (SABRE), and (iii)a high-field spin-lock-induced crossing (SLIC) sequence, with the initial state being the singlet state between two spins. The presented visualization technique facilitates intuitive understanding of spin dynamics during complex experiments as exemplified here by the considered cases. Temporal sequences ("the movies") of such surfaces show phenomena like interconversion of spin order between the coupled spins and are particularly relevant in ZULF NMR.

Relayed hyperpolarization for zero-field nuclear magnetic resonance.

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) is a rapidly developing form of spectroscopy that provides rich spectroscopic information in the absence of large magnetic fields. However, signal acquisition still requires a mechanism for generating a bulk magnetic moment for detection, and the currently used methods only apply to a limited pool of chemicals or come at prohibitively high cost. We demonstrate that the parahydrogen-based SABRE (signal amplification by reversible exchange)–Relay method can be used as a more general means of generating hyperpolarized analytes for ZULF NMR by observing zero-field J-spectra of [13C]-methanol, [1-13C]-ethanol, and [2-13C]-ethanol in both 13C-isotopically enriched and natural abundance samples. We explore the magnetic field dependence of the SABRE-Relay efficiency and show the existence of a second maximum at 19.0 ± 0.3 mT. Despite presence of water, SABRE-Relay is used to hyperpolarize ethanol extracted from a store-bought sample of vodka (%PH ~ 0.1%).

In SituCompensation of Triaxial Magnetic Field Gradient for Atomic Magnetometers

Magnetic field gradients affect numerous modern sensitive measurements and physics studies using atomic ensemble, resulting in the loss of coherence. In some cases, the presence of small gradients can reduce the performance significantly. In this study, we propose an effective <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">in situ</i> method to compensate the triaxial magnetic field gradient for atomic magnetometers, based on multichannel atomic signals in one vapor cell. We design two novel gradient coils by solving closed-form equations to improve the accuracy and efficiency of compensation. We demonstrate the performance of the compensation method in a spin-exchange relaxation-free atomic magnetometer, which reduces the magnetic linewidth by 4.2%–7.6% under the same conditions at a compensation resolution of 50 pT/cm. The proposed coils generate gradients only along two axes and achieve triaxial decoupling, which compensates for the gradient completely without iteration. Our results may aid in suppressing atomic spin relaxations due to magnetic field gradients in several modern measurements and improve their performance, such as the detection of electric dipole moments, ultralow-field nuclear magnetic resonance, and biomagnetism.

Magnetic sensing at zero field with a single nitrogen-vacancy center

Single nitrogen-vacancy (NV) centers are widely used as nanoscale sensors for magnetic and electric fields, strain and temperature. Nanoscale magnetometry using NV centers allows for example to quantitatively measure local magnetic fields produced by vortices in superconductors, topological spin textures such as skyrmions, as well as to detect nuclear magnetic resonance signals. However, one drawback when used as magnetic field sensor has been that an external bias field is required to perform magnetometry with NV centers. In this work we demonstrate a technique which allows access to a regime where no external bias field is needed. This enables new applications in which this bias field might disturb the system under investigation. Furthermore, we show that our technique is sensitive enough to detect spins outside of the diamond which enables nanoscale zero-to ultralow-field nuclear magnetic resonance.

Correlation of high-field and zero- to ultralow-field NMR properties using 2D spectroscopy.

The field of zero- to ultralow-field (ZULF) nuclear magnetic resonance (NMR) is currently experiencing rapid growth, owing to progress in optical magnetometry and attractive features of ZULF-NMR such as low hardware cost and excellent spectral resolution achieved under ZULF conditions. In this work, an approach is proposed and demonstrated for simultaneous acquisition of ZULF-NMR spectra of individual 13C-containing isotopomers of chemical compounds in a complex mixture. The method makes use of fast field cycling such that the spin evolution takes place under ZULF conditions, whereas signal detection is performed in a high-field NMR spectrometer. This method has excellent sensitivity, also allowing easy assignment of ZULF-NMR spectra to specific analytes in the mixture. We demonstrate that the spectral information is the same as that given by ZULF-NMR, which makes the method suitable for creating a library of ZULF-NMR spectra of various compounds and their isotopomers. The results of the field-cycling experiments can be presented in a convenient way as 2D-NMR spectra with the direct dimension giving the high-field 13C-NMR spectrum (carrying the chemical-shift information) and the indirect dimension giving the ZULF-NMR spectrum (containing information about proton-carbon J-couplings). Hence, the method can be seen as a variant of heteronuclear J-resolved spectroscopy, one of the first 2D-NMR techniques.

Magnetic graphene quantum dots facilitate closed-tube one-step detection of SARS-CoV-2 with ultra-low field NMR relaxometry.

The rapid and sensitive diagnosis of the highly contagious severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is one of the crucial issues at the outbreak of the ongoing global pandemic that has no valid cure. Here, we propose a SARS-CoV-2 antibody conjugated magnetic graphene quantum dots (GQDs)-based magnetic relaxation switch (MRSw) that specifically recognizes the SARS-CoV-2. The probe of MRSw can be directly mixed with the test sample in a fully sealed vial without sample pretreatment, which largely reduces the testers' risk of infection during the operation. The closed-tube one-step strategy to detect SARS-CoV-2 is developed with home-made ultra-low field nuclear magnetic resonance (ULF NMR) relaxometry working at 118 μT. The magnetic GQDs-based probe shows ultra-high sensitivity in the detection of SARS-CoV-2 due to its high magnetic relaxivity, and the limit of detection is optimized to 248 Particles mL‒1. Meanwhile, the detection time in ULF NMR system is only 2 min, which can significantly improve the efficiency of detection. In short, the magnetic GQDs-based MRSw coupled with ULF NMR can realize a rapid, safe, and sensitive detection of SARS-CoV-2.

A built-in coil system attached to the inside walls of a magnetically shielded room for generating an ultra-high magnetic field homogeneity.

The homogeneity of the magnetic field generated by a coil inside a magnetic shield is essential for many applications, such as ultra-low field nuclear magnetic resonance or spin precession experiments. In the course of upgrading the Berlin Magnetically Shielded Room (BMSR-2) with a new inserted Permalloy layer of side length 2.87m, we designed a built-in coil consisting of four identical square windings attached to its inside walls. The spacings of the four windings were optimized using a recently developed semi-analytic model and finite element analysis. The result reveals a strong dependence of the field homogeneity on the asymmetric placement of the inner two windings and on the chosen material permeability value μs. However, our model calculations also show that these experimental variations can be counterbalanced by an adjustment of the inner winding positions in the millimeter range. Superconducting quantum interference device-based measurements yield for our implementation after fine adjustments of a single winding position a maximum field change of less than 10 pT for a total field of B0 = 2.3 µT within a 10cm region along the coil axis, which is already better than the residual field of the upgraded BMSR-2.1 after degaussing. Measurements of free spin precession decay signals of polarized Xe129 nuclei show that the transverse relaxation time for the used cell is not limited by the inhomogeneity of the new built-in coil system.

Lower than low: Perspectives on zero- to ultralow-field nuclear magnetic resonance

The less-traveled low road in nuclear magnetic resonance is discussed, honoring the contributions of Prof. Bernhard Blümich, aspiring towards reaching ‘a new low.’ A history of the subject and its current status are briefly reviewed, followed by an effort to prophesy possible directions for future developments.

A Squid-Detected NMR Relaxation Study of Banana Fruit Ripening

HighlightsMeasurements of relaxation times in intact banana at micro-Tesla field was achieved.Bulk spin-spin relaxation time highly correlated with best descriptors of banana ripening.A basis for quasi-continuous distribution of spin-spin relaxation in banana was given.Abstract. Achieving fast, low-cost, and non-destructive internal quality testing techniques in the horticultural industry is a challenge. Developing techniques such as ultra-low field nuclear magnetic resonance (NMR) is a promising solution. Banana is a fast ripening fruit, which undergoes many changes in quality characteristics during ripening, and was chosen as a fit choice for extensive fruit quality study by NMR. A commercial NMR system using a superconducting quantum interference device (SQUID) as a sensor and operating at 100µT was used to measure changes that occurred in banana fruit during ripening. The longitudinal and transverse relaxation times (T1 and T2, respectively), were measured on fruit samples progressively drawn from a larger batch under storage. Physico-chemical attributes such as total soluble solids (TSS), titratable acidity (TA), pH, and color parameters were measured and used as reference measurements. Statistical analysis using cross-correlation, linear regression, analysis of variance (ANOVA), and principal components analysis (PCA) were performed to probe the relationships between various quality attributes. T1 showed high correlations with total soluble solids (R = 0.84), sugar:acid ratio (R = 0.84) and color parameters (R from 0.49 to 0.88). T2, on the other hand, was most highly correlated to pH (R = 0.76) but also had a statistically significant but negative correlation with Ri (-0.58 at p &amp;lt;0.05). PCA results separated the first day from the remaining days of the ripening process and the overall variation was mostly explained by color attributes (a* and h), T1, TSS, and TSS/TA. During seven days of ripening in storage, the trend of change in the peel color of banana was best described by L*, a*, h and total color difference (TCD). The index of ripening, Ri, defined based on the apparent change in peel color was highly correlated to TSS, TSS/TA, L*, a*, h, TCD, and T1. The strong similarity between the evolution of T1 and the most commonly approved characteristics of banana ripening suggest that T1 has great potential for characterizing the ripening process of banana. However, an investigation of the full metabolic profile of banana during ripening would provide an understanding of the link between NMR relaxation and ripening characteristics. A distribution of T1 relaxation time of intact banana fruit at the micro-Tesla field was successfully generated using Laplace inversion. A suitable framework of T1-domain based studies on banana ripening also applicable to other fruit was discussed; it would provide a comprehensive understanding of structural changes and water mobility that occur in ripening banana. The SQUID-detected ultra-low field NMR used here shows promise as a tool for probing the quality of intact banana fruit. Keywords: Banana quality, Laplace inversion, Relaxometry, SQUID-NMR.

Detection of ultra-low field NMR signal with a commercial QuSpin single-beam atomic magnetometer

We experimentally demonstrate the nuclear magnetic resonance (NMR) detection at 1.9 kHz using a detection system comprised of a high-sensitivity single-beam atomic magnetometer and a flux transformer. The single-beam atomic magnetometer has been commercialized by QuSpin for typical operation at low frequencies below 200 Hz with a bandwidth of 135 Hz [1]. However, this magnetometer operation can be extended to much higher frequencies about 2 kHz by applying optimal-bias magnetic fields. The sensitivity of the detection system with a demonstrated signal-to-noise ratio of about 50 for a 20 ml water sample, even without magnetic field shimming, is quite competitive with that in other ultra-low field NMR detection systems, such as the Magritek Terranova system or the system based on our home-built atomic magnetometer installed inside a magnetically shielded room [2]. This ultra-low field NMR approach can be applied to Earth-field NMR detection and imaging. We estimate that the detection system with a modified flux transformer can be sensitive to underground-water detection at depth of 1 meter and deeper, and to field mapping applications.

Effective Suppression of Residual Magnetic Interference in a Conductive Shielded Room for Ultra-Low Field Nuclear Magnetic Resonance

Residual magnetic interference induced by applied magnetic field pulses inside a conductive shielded room (SR) has been a common issue in ultra-low-field (ULF) nuclear magnetic resonance (NMR). The rapid cutoff of the applied pre-polarizing field (Bp) induces eddy currents in the walls of the SR, which produces a decaying residual magnetic interference that may cause severe image distortions and signal loss. In this study, a pair of cancellation coils (CC) and control electronics were designed for the suppression of the residual magnetic interference in a SR. Simulations show that this method was effective in suppressing the residual magnetic field (Br) after removal of the pre-polarizing magnetic field. Then, a small-scale SR was designed and the effectiveness of this cancellation scheme was experimentally verified. The test results showed a good agreement with the simulation, which indicated that the cancellation scheme was capable of reducing Br field to a much lower level. The scheme proposed in this study provides a solution for suppressing the residual magnetic field in the ULF NMR system. After decoupling the eddy–current field, the effect of the suppression may be further improved by optimization of the cancellation coil in further work.

Design and implementation of a J-coupled spectrometer for multidimensional structure and relaxation detection at low magnetic fields.

In recent years, it has been realized that low and ultra-low field (mT-nT magnetic field range) nuclear magnetic resonance spectroscopy can be used for molecular structural analysis. However, spectra are often hindered by lengthy acquisition times or require large sample volumes and high concentrations. Here, we report a low field (50 μT) instrument that employs a linear actuator to shuttle samples between a 1 T prepolarization field and a solenoid detector in a laboratory setting. The current experimental setup is benchmarked using water and 13C-methanol with a single scan detection limit of 2 × 1020 spins (3 µl, 55M H2O) and detection limit of 2.9 × 1019 (200 µl, 617 mM 13C-methanol) spins with signal averaging. The system has a dynamic range of >3 orders of magnitude. Investigations of room-temperature relaxation dynamics of 13C-methanol show that sample dilution can be used in lieu of sample heating to acquire spectra with linewidths comparable to high-temperature spectra. These results indicate that the T1 and T2 mechanisms are governed by both the proton exchange rate and the dissolved oxygen in the sample. Finally, a 2D correlation spectroscopy experiment is reported, performed in the strong coupling regime that resolves the multiple resonances associated with the heteronuclear J-coupling. The spectrum was collected using 10 times less sample and in less than half the time from previous reports in the strong coupling limit.

Zero- to ultralow-field nuclear magnetic resonance J-spectroscopy with commercial atomic magnetometers

Zero- to ultralow-field nuclear magnetic resonance (ZULF NMR) is an alternative spectroscopic method to high-field NMR, in which samples are studied in the absence of a large magnetic field. Unfortunately, there is a large barrier to entry for many groups, because operating the optical magnetometers needed for signal detection requires some expertise in atomic physics and optics. Commercially available magnetometers offer a solution to this problem. Here we describe a simple ZULF NMR configuration employing commercial magnetometers, and demonstrate sufficient functionality to measure samples with nuclear spins prepolarized in a permanent magnet or initialized using parahydrogen. This opens the possibility for other groups to use ZULF NMR, which provides a means to study complex materials without magnetic susceptibility-induced line broadening, and to observe samples through conductive materials.

Constraints on bosonic dark matter from ultralow-field nuclear magnetic resonance.

The nature of dark matter, the invisible substance making up over 80% of the matter in the universe, is one of the most fundamental mysteries of modern physics. Ultralight bosons such as axions, axion-like particles, or dark photons could make up most of the dark matter. Couplings between such bosons and nuclear spins may enable their direct detection via nuclear magnetic resonance (NMR) spectroscopy: As nuclear spins move through the galactic dark-matter halo, they couple to dark matter and behave as if they were in an oscillating magnetic field, generating a dark-matter-driven NMR signal. As part of the cosmic axion spin precession experiment (CASPEr), an NMR-based dark-matter search, we use ultralow-field NMR to probe the axion-fermion "wind" coupling and dark-photon couplings to nuclear spins. No dark matter signal was detected above background, establishing new experimental bounds for dark matter bosons with masses ranging from 1.8 × 10-16 to 7.8 × 10-14 eV.

Ultralow-field nuclear magnetic resonance of liquids confined in ferromagnetic and paramagnetic materials

A nuclear magnetic resonance (NMR) procedure is used to measure weak magnetic fields in the vicinity of dilute ferromagnetic and/or paramagnetic materials. By detecting 1H Larmor precession in common solvents at extremely low frequencies (&amp;lt;50 Hz), the magnetic field produced by remanent magnetization of the material is measured by NMR to a precision of &amp;lt;1 nT. In one example, the technique is used to quantify the magnitude and direction of remanent magnetization in a common aluminum alloy. In another example, a 1H NMR linewidth &amp;lt;1 Hz is demonstrated for liquid decane (n-C10H22) embedded inside a mesoporous silica matrix, despite the high concentration of paramagnetic cobalt sites that produce magnetic susceptibility gradients in the system. Application to systems of industrial relevance is discussed.

Zero-field nuclear magnetic resonance of chemically exchanging systems

Zero- to ultralow-field (ZULF) nuclear magnetic resonance (NMR) is an emerging tool for precision chemical analysis. In this work, we study dynamic processes and investigate the influence of chemical exchange on ZULF NMR J-spectra. We develop a computational approach that allows quantitative calculation of J-spectra in the presence of chemical exchange and apply it to study aqueous solutions of [15N]ammonium (15N{mathrm{H}}_4^ +) as a model system. We show that pH-dependent chemical exchange substantially affects the J-spectra and, in some cases, can lead to degradation and complete disappearance of the spectral features. To demonstrate potential applications of ZULF NMR for chemistry and biomedicine, we show a ZULF NMR spectrum of [2-13C]pyruvic acid hyperpolarized via dissolution dynamic nuclear polarization (dDNP). We foresee applications of affordable and scalable ZULF NMR coupled with hyperpolarization to study chemical exchange phenomena in vivo and in situations where high-field NMR detection is not possible to implement.