Zero-field Nuclear Magnetic Resonance Research Articles

Digital quantum simulation of NMR experiments.

Simulations of nuclear magnetic resonance (NMR) experiments can be an important tool for extracting information about molecular structure and optimizing experimental protocols but are often intractable on classical computers for large molecules such as proteins and for protocols such as zero-field NMR. We demonstrate the first quantum simulation of an NMR spectrum, computing the zero-field spectrum of the methyl group of acetonitrile using four qubits of a trapped-ion quantum computer. We reduce the sampling cost of the quantum simulation by an order of magnitude using compressed sensing techniques. We show how the intrinsic decoherence of NMR systems may enable the zero-field simulation of classically hard molecules on relatively near-term quantum hardware and discuss how the experimentally demonstrated quantum algorithm can be used to efficiently simulate scientifically and technologically relevant solid-state NMR experiments on more mature devices. Our work opens a practical application for quantum computation.

Detection of pyridine derivatives by SABRE hyperpolarization at zero field

Nuclear magnetic resonance (NMR) spectroscopy is a powerful analytical tool used in modern science and technology. Its novel incarnation, based on measurements of NMR signals without external magnetic fields, provides direct access to intramolecular interactions based on heteronuclear scalar J-coupling. The uniqueness of these interactions makes each zero-field NMR spectrum distinct and useful in chemical fingerprinting. However, the necessity of heteronuclear coupling often results in weak signals due to the low abundance of certain nuclei (e.g., 15N). Hyperpolarization of such compounds may solve the problem. In this work, we investigate molecules with natural isotopic abundance that are polarized using non-hydrogenative parahydrogen-induced polarization. We demonstrate that spectra of hyperpolarized naturally abundant pyridine derivatives can be observed and uniquely identified whether the same substituent is placed at a different position of the pyridine ring or different constituents are placed at the same position. To do so, we constructed an experimental system using a home-built nitrogen vapor condenser, which allows for consistent long-term measurements, crucial for identifying naturally abundant hyperpolarized molecules at a concentration level of ~1 mM. This opens avenues for future chemical detection of naturally abundant compounds using zero-field NMR.

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.

Site Split of Antiferromagnetic α-Mn Revealed by 55Mn Nuclear Magnetic Resonance

The magnetic structure of antiferromagnetic $\alpha$-Mn has been unclarified for almost 70 years since its magnetism was discovered. We measured the zero-field nuclear magnetic resonance spectra of antiferromagnetic $\alpha$-Mn to obtain further insight into magnetism below $T_{\text{N}} = 95$ K. The site II spectra split into two sites with five subpeaks owing to quadrupole interaction, and this shows that the ordered moments at site II are slightly tilted from the $[001]$ direction. The site III spectra revealed that this site splits into four sites below $T_{\text{N}}$. These findings clearly demonstrate that the antiferromagnetic $\alpha$-Mn symmetry is lower than previously considered.

Emergence of collinear magnetic structure in Tb-doped BiFeO3

The search for ways to realize the multiferroic potential of BiFeO3-based compounds is being relevant for three decades. The major problem is a magnetic spatial spin-modulated structure (SSMS) that nullifies the net magnetic moment over the sample volume. In this paper, we research the effect of bismuth ferrite doping with magnetic Tb3+ ions.With the help of zero-field nuclear magnetic resonance (ZF NMR) spectroscopy, we reveal a change in the type of anisotropy from “easy-axis” to “easy-plane” even at 1.5 % terbium doping. Moreover, at 8.5 % Tb doping, the magnetic structure becomes collinear, SSMS deteriorates, while the crystal structure remains rhombohedral. We also observe an additional high-frequency line, similar to the lines found in the La- and Sr-doped BFO spectra, at a frequency of 75.85 MHz. Such a combination of characteristics gives this composition every chance of being a promising multiferroic compound.

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%).

Criticality-Enhanced Quantum Sensing via Continuous Measurement

Present protocols of criticality-enhanced sensing with open quantum sensors assume direct measurement of the sensor and omit the radiation quanta emitted to the environment, thereby potentially missing valuable information. Here we propose a protocol for criticality-enhanced sensing via continuous observation of the emitted radiation quanta. Under general assumptions, we establish a scaling theory for the global quantum Fisher information of the joint system and environment state at dissipative critical points. We derive universal scaling laws featuring transient and long-time behavior governed by the underlying critical exponents. Importantly, such scaling laws exceed the standard quantum limit and can in principle saturate the Heisenberg limit. To harness such advantageous scaling, we propose a practical sensing scheme based on continuous detection of the emitted quanta as realized experimentally in various quantum-optical setups. In such a scheme a single interrogation corresponds to a (stochastic) quantum trajectory of the open system evolving under the nonunitary dynamics dependent on the parameter to be sensed and the backaction of the continuous measurement. Remarkably, we demonstrate that the associated precision scaling significantly exceeds that based on direct measurement of the critical steady state, thereby establishing the metrological value of the continuous detection of the emitted quanta at dissipative criticality. We illustrate our protocol via counting the photons emitted by the open Rabi model, a paradigmatic model for the study of dissipative phase transition with finite components. Our protocol is applicable to generic quantum-optical open sensors permitting continuous readout, and may find applications at the frontier of quantum sensing, such as the human-machine interface, magnetic diagnosis of heart disease, and zero-field nuclear magnetic resonance.

Zero-field 57Fe NMR in BiFeO3 based compounds: Problems, solutions and application to Bi1-xSrxFeO3

In this paper, we present a protocol designed to avoid typical problems occurring in the process of the spatial spin modulated structure (SSMS) investigation in BFO-based (BiFeO3) materials by zero-field nuclear magnetic resonance (ZF NMR) spectroscopy on 57Fe nuclei. We have analyzed the significant discrepancies in the parameters of the spectra in the literature and developed the measurement protocol to improve the quality and unify the obtained spectra. The study of the 57Fe spectra of Sr-doped BFO at 4.2 K samples was carried out to illustrate the protocol. The obtained spectra demonstrate suppression of the SSMS by heterovalent substitution. The Sr-concentration dependent evolution of the SSMS anharmonicity parameter was observed as well.

Sudden Suppression of Internal Magnetic Fields under High Pressure in α-Mn

We have clarified that the internal magnetic field in α-Mn is suppressed by pressure and that a first-order phase transition occurs at around 1.4–1.5 GPa by zero-field nuclear magnetic resonance. In the pressure-induced ordered state above about 1.4 GPa, the scenario of the canted-antiferromagnetic order or the ferrimagnetic order seems to be preferable to account for the weak ferromagnetism.

Electron correlations and charge segregation in layered manganese pnictide antiferromagnets showing anomalously large magnetoresistance

A family of layered manganese-pnictide antiferromagnets ${\mathrm{BaMn}}_{2}{Pn}_{2}$ ($\mathit{Pn}$ stands for P, As, Sb, and Bi) has been recently shown to host anomalously large magnetoresistance (MR) with both positive and negative MR components. In search for the microscopic picture of MR in this family, we here report a local-probe $^{55}\mathrm{Mn}$ nuclear magnetic resonance (NMR) study. The zero-field NMR spectra and the temperature dependence of the spin-lattice relaxation rates are fully consistent with the proposed G-type antiferromagnetic order. However, a close inspection of the $^{55}\mathrm{Mn}$ NMR spectra reveals a fine structure, which is due to the weakly localized charge carriers. As these carriers localize and segregate in the presence of electron correlations, they also undergo collective spin fluctuations which freeze-out at low temperatures and thus contribute to the $^{55}\mathrm{Mn}$ spin-lattice relaxation. The characteristic temperatures of the appearance of these additional features in the magnetic response probed by $^{55}\mathrm{Mn}$ NMR correlate well with the anomalies in the resistivity and anomalously large MR, which hints that the two phenomena are connected.

Zero- to Ultralow-Field NMR Spectroscopy of Small Biomolecules.

Nuclear magnetic resonance (NMR) spectroscopy is a well-established analytical technique used to study chemicals and their transformations. However, high-field NMR spectroscopy necessitates advanced infrastructure, and even cryogen-free benchtop NMR spectrometers cannot be readily assembled from commercially available components. We demonstrate construction of a portable zero-field NMR spectrometer employing a commercially available magnetometer and investigate its applications in analytical chemistry. In particular, J-spectra of small representative biomolecules [13C]-formic acid, [1-13C]-glycine, [2,3-13C]-fumarate, and [1-13C]-d-glucose were acquired, and an approach relying on the presence of a transverse magnetic field during the detection was investigated for relaxometry purposes. We found that the water relaxation time strongly depends on the concentration of dissolved d-glucose in the range of 1-10 mM suggesting opportunities for indirect assessment of glucose concentration in aqueous solutions. Extending analytical capabilities of zero-field NMR to aqueous solutions of simple biomolecules (amino acids, sugars, and metabolites) and relaxation studies of aqueous solutions of glucose highlights the analytical potential of noninvasive and portable ZULF NMR sensors for applications outside of research laboratories.

Zero-Field NMR J-Spectroscopy of Organophosphorus Compounds.

Organophosphorus compounds are a wide and diverse class of chemicals playing a crucial role in living organisms. This aspect has been often investigated using nuclear magnetic resonance (NMR), which provides information about molecular structure and function. In this paper, we report the results of theoretical and experimental studies on basic organophosphorus compounds using zero-field NMR, where spin dynamics are investigated in the absence of a magnetic field with the dominant heteronuclear J-coupling. We demonstrate that the zero-field NMR enables distinguishing the chemicals owing to their unique electronic environment even though their spin systems have the same alphabetic designation. Such information can be obtained just in a single measurement, while amplitudes and widths of observed low-field NMR resonances enable the study of processes affecting spin dynamics. An excellent agreement between simulations and measurements of the spectra, particularly in the largest frequency J-couplings range ever reported in zero-field NMR, is demonstrated.

Microscopic evidence for Mn-induced long range magnetic ordering in MAX phase compounds

Zero and low field nuclear magnetic resonance measurements have been performed on MAX phase samples (Cr1−x Mn x )2AC with A = Ge and Ga in order to obtain local microscopic information on the nature of magnetism in this system. Our results unambiguously provide evidence for the existence of long-range magnetic order in (Cr0.96Mn0.04)2GeC and for (Cr0.93Mn0.07)2GaC, but not for (Cr0.97Mn0.03)2GaC. We point to a possible dependence of long range magnetic order in these MAX phase compounds on the A atom.

Chemical Reaction Monitoring using Zero-Field Nuclear Magnetic Resonance Enables Study of Heterogeneous Samples in Metal Containers.

We demonstrate that heterogeneous/biphasic chemical reactions can be monitored with high spectroscopic resolution using zero‐field nuclear magnetic resonance spectroscopy. This is possible because magnetic susceptibility broadening is negligible at ultralow magnetic fields. We show the two‐step hydrogenation of dimethyl acetylenedicarboxylate with para‐enriched hydrogen gas in conventional glass NMR tubes, as well as in a titanium tube. The low frequency zero‐field NMR signals ensure that there is no significant signal attenuation arising from shielding by the electrically conductive sample container. This method paves the way for in situ monitoring of reactions in complex heterogeneous multiphase systems and in reactors made of conductive materials while maintaining resolution and chemical specificity.

Two-dimensional single- and multiple-quantum correlation spectroscopy in zero-field nuclear magnetic resonance

We present single- and multiple-quantum correlation J-spectroscopy detected in zero (<1μG) magnetic field using a 87Rb vapor-cell magnetometer. At zero field the spectrum of ethanol appears as a mixture of 13C isotopomers, and correlation spectroscopy is useful in separating the two composite spectra. We also identify and observe the zero-field equivalent of a double-quantum transition in 13C2-acetic acid, and show that such transitions are of use in spectral assignment. Two-dimensional spectroscopy further improves the high resolution attained in zero-field NMR since selection rules on the coherence-transfer pathways allow for the separation of otherwise overlapping resonances into distinct cross-peaks.

Molecular parity nonconservation in nuclear spin couplings

The weak interaction does not conserve parity, which is apparent in many nuclear and atomic phenomena. However, thus far, parity nonconservation has not been observed in molecules. Here we consider nuclear-spin-dependent parity nonconserving contributions to the molecular Hamiltonian. These contributions give rise to a parity nonconserving indirect nuclear spin-spin coupling which can be distinguished from parity conserving interactions in molecules of appropriate symmetry, including diatomic molecules. We estimate the magnitude of the coupling, taking into account relativistic corrections. Finally, we propose and simulate an experiment to detect the parity nonconserving coupling using liquid- or gas-state zero-field nuclear magnetic resonance of electrically oriented molecules and show that $^{1}$H$^{19}$F should give signals within the detection limits of current atomic vapor-cell magnetometers.

Magnetic properties of biofunctionalized iron oxide nanoparticles as magnetic resonance imaging contrast agents.

Background: One of the future applications of magnetic nanoparticles is the development of new iron-oxide-based magnetic resonance imaging (MRI) negative contrast agents, which are intended to improve the results of diagnostics and complement existing Gd-based contrast media.Results: Iron oxide nanoparticles designed for use as MRI contrast media are precisely examined by a variety of methods: powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, Mössbauer spectroscopy and zero-field nuclear magnetic resonance (ZF-NMR) spectroscopy. TEM and XRD measurements reveal a spherical shape of the nanoparticles with an average diameter of 5–8 nm and a cubic spinel-type crystal structure of space group Fd−3m. Raman, Mössbauer and NMR spectroscopy clearly indicate the presence of the maghemite γ-Fe2O3 phase. Moreover, a difference in the magnetic behavior of uncoated and human serum albumin coated iron oxide nanoparticles was observed by Mössbauer spectroscopy.Conclusion: This difference in magnetic behavior is explained by the influence of biofunctionalization on the magnetic and electronic properties of the iron oxide nanoparticles. The ZF-NMR spectra analysis allowed us to determine the relative amount of iron located in the core and the surface layer of the nanoparticles. The obtained results are important for understanding the structural and magnetic properties of iron oxide nanoparticles used as T2 contrast agents for MRI.

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.

Zero-Field Magnetometry Based on Nitrogen-Vacancy Ensembles in Diamond

Ensembles of nitrogen-vacancy (NV) centers in diamonds are widely utilized for magnetometry, magnetic-field imaging and magnetic-resonance detection. They have not been used for magnetometry at zero ambient field because Zeeman sublevels lose first-order sensitivity to magnetic fields as they are mixed due to crystal strain or electric fields. In this work, we realize a zero-field (ZF) magnetometer using polarization-selective microwave excitation in a 12C-enriched HPHT crystal sample. We employ circularly polarized microwaves to address specific transitions in the optically detected magnetic resonance and perform magnetometry with a noise floor of 250 pT/Hz^(1/2). This technique opens the door to practical applications of NV sensors for ZF magnetic sensing, such as ZF nuclear magnetic resonance, and investigation of magnetic fields in biological systems.

Estimation of structural composition of the inverse spinel ferrites using 57Fe-Zero Field Nuclear Magnetic Resonance

We have demonstrated 57Fe Zero Field Nuclear Magnetic Resonance (ZFNMR) as a powerful tool in determining the structural composition of nickel-cadmium spinel ferrites of various compositions of Ni1-x Cdx Fe2O4 from x = 0 to1, which are synthesized via one-step auto combustion technique. The XRD measurements confirm the phase purity of all the samples. Vibrating Sample Magnetometry (VSM) measurements show that saturation magnetization (MS) increases initially (up to x = 0.3) and then decreases for higher concentrations of cadmium. The Fe3+ ions in the inverted spinel ferrite distribute equally among two possible sites (tetrahedral A and octahedral B) with different hyperfine fields. Therefore for x = 0 under the assumption that Ni enters B sites, 57Fe NMR of Fe3+ ions yield two signals of equal integral intensities in spectral lines corresponding to these sites. Thus, for the sample series Ni1-x Cdx Fe2O4, the contribution of Fe3+ nuclei varies for A and B sub-spectra with the substitution of a non-magnetic Cd2+ ion. By measuring the Fe3+ distribution on A and B sites which is determined from relative spectral areas of A and B NMR sub-spectra the cation distribution is estimated and has been verified by the binomial distribution. Further, XRD Rietveld refinement results are also in good agreement with the composition estimated by NMR technique and the ideal composition. We have demonstrated the usefulness of NMR technique to quantify the accurate composition of the mixed spinel ferrite systems using Ni-Cd ferrite as a test case. Further, the estimated inversion parameter (at around x = 0.4), for the studied system, obtained from ZFNMR, XRD, and VSM techniques are in excellent agreement with each other.