We review experimental techniques in our laboratory for nuclear magnetic resonance (NMR) in zero and ultralow magnetic field (below 0.1 μT) where detection is based on a low-cost, non-cryogenic, spin-exchange relaxation free 87Rb atomic magnetometer. The typical sensitivity is 20-30 fT/Hz1/2 for signal frequencies below 1 kHz and NMR linewidths range from Hz all the way down to tens of mHz. These features enable precision measurements of chemically informative nuclear spin-spin couplings as well as nuclear spin precession in ultralow magnetic fields.

We present a Cs atomic magnetometer with a sensitivity of 150fT/Hz(1/2) operating near room temperature. The nuclear magnetic resonance (NMR) signal of 125μL tap water was detected at an ultralow magnetic field down to 47nT, with the signal-to-noise ratio (SNR) of the NMR signal approaching 50 after eight averages. Relaxivity experiments with a Gd(DTPA) contrast agent in zero field were performed, in order to show the magnetometer's ability to measure spin-lattice relaxation time with high accuracy. This demonstrates the feasibility of an ultralow field NMR spectrometer based on a Cs atomic magnetometer, which has a low working temperature, short data acquisition time and high sensitivity. This kind of NMR spectrometer has great potential in applications such as chemical analysis and magnetic relaxometry detection in ultralow or zero fields. Copyright © 2013 Elsevier Inc. All rights reserved.

Demonstration of coherent control and characterization of the control fidelity is important for the development of quantum architectures such as nuclear magnetic resonance (NMR). We introduce an experimental approach to realize universal quantum control, and benchmarking thereof, in zero-field NMR, an analog of conventional high-field NMR that features less-constrained spin dynamics. We design a composite pulse technique for both arbitrary one-spin rotations and a two-spin controlled-not (CNOT) gate in a heteronuclear two-spin system at zero field, which experimentally demonstrates universal quantum control in such a system. Moreover, using quantum information-inspired randomized benchmarking and partial quantum process tomography, we evaluate the quality of the control, achieving single-spin control for C-13 with an average fidelity of 0.9960(2) and two-spin control via a CNOT gate with a fidelity of 0.9877(2). Our method can also be extended to more general multispin heteronuclear systems at zero field. The realization of universal quantum control in zero-field NMR is important for quantum state/coherence preparation, pulse sequence design, and is an essential step toward applications to materials science, chemical analysis, and fundamental physics.

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 [N]ammonium (N[Formula: see text]) 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-C]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.

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, -spectra of small representative biomolecules [C]-formic acid, [1-C]-glycine, [2,3-C]-fumarate, and [1-C]-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.

Conventionally implemented MRI is performed in a strong magnetic field, typically >1T. The high fields, however, can lead to many limitations. To overcome these limitations, ultra-low field (ULF) [or microtesla] MRI systems have been proposed and implemented. To-date such systems rely on low-Tc Superconducting Quantum Interference Devices (SQUIDs) leading to the requirement of cryogens. In this letter, we report ULF-MRI obtained with a non-cryogenic atomic magnetometer. This demonstration creates opportunities for developing inexpensive and widely applicable MRI scanners.

We report on the development of a microfabricated atomic magnetic gradiometer based on optical spectroscopy of alkali atoms in the vapor phase. The gradiometer, which operates in the spin-exchange relaxation free regime, has a length of 60 mm and cross sectional diameter of 12 mm, and consists of two chip-scale atomic magnetometers which are interrogated by a common laser light. The sensor can measure differences in magnetic fields, over a 20 mm baseline, of 10 fT/Hz1/2 at frequencies above 20 Hz. The maximum rejection of magnetic field noise is 1000 at 10 Hz. By use of a set of compensation coils wrapped around the sensor, we also measure the sensor sensitivity at several external bias field strengths up to 150 mG. This device is useful for applications that require both sensitive gradient field information and high common-mode noise cancellation.

In recent years, substantial progress has been made in developing a new generation of magnetoencephalography (MEG) with a spin-exchange relaxation free (SERF)-based atomic magnetometer (AM). An AM employs alkali atoms to detect weak magnetic fields. A compact AM array with high sensitivity is crucial to the design; however, most proposed compact AMs are potassium (K)- or rubidium (Rb)-based with single beam configurations. In the present study, a pump-probe two beam configuration with a Cesium (Cs)-based AM (Cs-AM) is introduced to detect human neuronal magnetic fields. The length of the vapor cell is 4 mm, which can fully satisfy the need of designing a compact sensor array. Compared with state-of-the-art compact AMs, our new Cs-AM has two advantages. First, it can be operated in a SERF regime, requiring much lower heating temperature, which benefits the sensor with a closer distance to scalp due to ease of thermal insulation and less electric heating noise interference. Second, the two-beam configuration in the design can achieve higher sensitivity. It is free of magnetic modulation, which is necessary in one-beam AMs; however, such modulation may cause other interference in multi-channel circumstances. In the frequency band between 10 Hz and 30 Hz, the noise level of the proposed Cs-AM is approximately 10 f T/Hz1/2, which is comparable with state-of-the-art K- or Rb-based compact AMs. The performance of the Cs-AM was verified by measuring human auditory evoked fields (AEFs) in reference to commercial superconducting quantum interference device (SQUID) channels. By using a Cs-AM, we observed a clear peak in AEFs around 100 ms (M100) with a much larger amplitude compared with that of a SQUID, and the temporal profiles of the two devices were in good agreement. The results indicate the possibility of using the compact Cs-AM for MEG recordings, and the current Cs-AM has the potential to be designed for multi-sensor arrays and gradiometers for future neuroscience studies.

We have recently demonstrated that sensitive and chemically specific NMR spectra can be recorded in the absence of a magnetic field using hydrogenative parahydrogen induced polarization (PHIP) (1-3) and detection with an optical atomic magnetometer. Here, we show that non-hydrogenative parahydrogen-induced polarization (4-6) (NH-PHIP) can also dramatically enhance the sensitivity of zero-field NMR. We demonstrate the detection of pyridine, at concentrations as low as 6 mM in a sample volume of 250 μL, with sufficient sensitivity to resolve all identifying spectral features, as supported by numerical simulations. Because the NH-PHIP mechanism is nonreactive, operates in situ, and eliminates the need for a prepolarizing magnet, its combination with optical atomic magnetometry will greatly broaden the analytical capabilities of zero-field and low-field NMR.© 2012 American Chemical Society

Optically pumped magnetometers (OPMs) based on alkali-atom vapors are ultra-sensitive devices for dc and low-frequency ac magnetic measurements. Here, in combination with fast-field-cycling hardware and high-resolution spectroscopic detection, we demonstrate applicability of OPMs in quantifying nuclear magnetic relaxation phenomena. Relaxation rate dispersion across the nT to mT field range enables quantitative investigation of extremely slow molecular motion correlations in the liquid state, with time constants > 1 ms, and insight into the corresponding relaxation mechanisms. The 10-20 fT/[Formula: see text] sensitivity of an OPM between 10 Hz and 5.5 kHz H Larmor frequency suffices to detect magnetic resonance signals from ~ 0.1 mL liquid volumes imbibed in simple mesoporous materials, or inside metal tubing, following nuclear spin prepolarization adjacent to the OPM. High-resolution spectroscopic detection can resolve inter-nucleus spin-spin couplings, further widening the scope of application to chemical systems. Expected limits of the technique regarding measurement of relaxation rates above 100 s are discussed.