Nuclear Magnetic Resonance Probe Research Articles

Comparing the Potential of Helmholtz and Planar NMR Microcoils for Analysis of Intact Biological Samples.

Nuclear magnetic resonance (NMR) spectroscopy has played an integral role in medical and environmental metabolic research. However, smaller biological entities, such as eggs and small tissue samples, are becoming increasingly important to better understand toxicity, biological growth/development, and diseases. Unfortunately, their small sizes make them difficult to study using conventional 5 mm NMR probes due to limited sensitivity. The use of microcoil NMR holds great potential for the analysis of such samples, where the coil can be designed to match the sample size to significantly improve NMR mass sensitivity and the filling factor. Here, we compare the potential of planar and Helmholtz microcoil designs to execute complex experiments for the analysis of intact, mass-limited biological samples. The planar coil offers the advantage of an open access design, potentially allowing flow systems to be incorporated and varying sample sizes to be studied; however, its relatively inhomogeneous B1 field leads to reduced NMR performance. The Helmholtz microcoil overcomes this drawback with its symmetrical design, improving B1 homogeneity across the sample but with the caveat that the size and shape of the sample is limited to the spacing between the two parallel coils. The line shape, sensitivity, and RF performance are compared on both coils using standard samples and biological samples. This study found that the Helmholtz microcoil used here considerably outperforms the planar coil in multipulse experiments and has great potential to study complex biological samples in the 50-200 nL range.

Application of Counter-wound Multi-arm Spirals in HTS Resonator Design.

Significant sensitivity improvements have been achieved by utilizing high temperature superconducting (HTS) resonators in nuclear magnetic resonance (NMR) probes. Many nuclei such as 13C benefit from strong excitation fields which cannot be produced by traditional HTS resonator designs. We investigate the use of double-sided, counter-wound multi-arm spiral HTS resonators with the aim of increasing the excitation field at the required nuclear Larmor frequency for 13C. When compared to double-sided, counter-wound spiral resonators with similar geometry, simulations indicate that the multi-arm spiral version develops a more uniform current distribution. Preliminary tests of a two-arm resonator indicate that it may produce a stronger excitation field.

Effect of Ligands and Transducers on the Neurotensin Receptor 1 Conformational Ensemble.

Using a discrete, intracellular 19F nuclear magnetic resonance (NMR) probe on transmembrane helix 6 of the neurotensin receptor 1 (NTS1), we aim to understand how ligands and transducers modulate the receptor's structural ensemble in a solution. For apo NTS1, 19F NMR spectra reveal an ensemble of at least three conformational substates (one inactive and two active-like) in equilibrium that exchange on the millisecond to second timescale. Dynamic NMR experiments reveal that these substates follow a linear three-site exchange process that is both thermodynamically and kinetically remodeled by orthosteric ligands. As previously observed in other G protein-coupled receptors (GPCRs), the full agonist is insufficient to completely stabilize the active-like state. The inactive substate is abolished upon coupling to β-arrestin-1 (βArr1) or the C-terminal helix of Gαq, which comprises ≳60% of the GPCR/G protein interface surface area. Whereas βArr1 exclusively selects for pre-existing active-like substates, the Gαq peptide induces a new substate. Both transducer molecules promote substantial line broadening of active-like states, suggesting contributions from additional microsecond to millisecond exchange processes. Together, our study suggests that (i) the NTS1 allosteric activation mechanism may be alternatively dominated by induced fit or conformational selection depending on the coupled transducer, and (ii) the available static structures do not represent the entire conformational ensemble observed in a solution.

Evaluation of slim-hole NMR logging for hydrogeologic insights into dolostone and sandstone aquifers

This study assesses the performance and limitations of slim-hole borehole nuclear magnetic resonance (NMR) technology from a hydrogeologic perspective in fractured, porous rock. NMR logging was carried out in dolomitic and sandstone bedrock boreholes at two research test sites in Ontario, Canada, where aquifer and aquitard units provide a range of clay contents as well as a variety of primary and secondary porosity types (e.g. discrete fractures, reefal structures, vugs and karstic conduits). Results were compared to core measurements, geophysical logs, and hydrogeophysical testing. The vertical response curve of the instrument tested was found to produce 60% of the signal from within a 0.2m span surrounding the measuring point. The repeatability of the total porosity measurements in stationary mode is excellent where the porosity is greater than 0.15. Below that threshold, repeatability is scattered at ±0.05 porosity about the mean, with the variability primarily within the clay- and capillary-bound fractions. The NMR porosity estimates agreed with core measurements to within ±0.04 porosity in both the dolostone and sandstone, but the correlation deteriorates in finely bedded lithologies, and where fracturing is present. Much of the discrepancy is attributed to scaling in a finely layered geologic sequence, as the core samples are much smaller than the entire volume measured with NMR probes. Data collection with the probe in motion (continuous logging) added variability to the response when compared to stationary recordings. Although broadscale trends were comparable, the details and depth-specific insights of the bound fluid fractions varied with logging rates. Overall, NMR provides a robust measurement of the bulk matrix porosity and pore size distribution of lithologies intersected, both of which are critically important parameters in understanding hydrogeologic conditions and contaminant distributions in layered sedimentary rock systems.

Analysis of NMR Signal for Static Magnetic Field Standard

Abstract This article describes the analysis of the NMR (Nuclear Magnetic Resonance) stabilizer signal. Magnetic field of the standard is created using an electromagnet. Sufficiently high stability of the magnetic field is achieved with the help of a stabilizer with an NMR probe. The NMR phenomenon makes possible very accurate measurements of the static magnetic field, but the resulting stability depends also on supporting electronics. An analysis has been done and tolerances of the measured quantities have been estimated. The calculated tolerances indicate the needed features of the material. First the probe excites the FID (Free Induction Decay) signal in the water sample and acquires the signal answer. It is Fourier transformed and its spectrum is investigated. The actual magnetic field corresponds to the strongest frequency sample. It is utilized for the magnetic field strength correction and stabilization of it. The article brings many equations for such calculation.

Ultra Low Temperature Microturbine for Magic Angle Spinning System

Abstract We investigate the fluid dynamics of a microturbine system that is applied in a device for chemical and biological analysis—a so-called magic angle spinning (MAS) nuclear magnetic resonance (NMR) probe. The present system is utilized in a wide temperature range from 45 K to 293 K. Pressurized air, nitrogen, or helium are used to drive a Pelton type microturbine. This turbine is mounted on a MAS rotor with a diameter between 0.7 mm and 3.2 mm. The rotor system is equipped with a pressurized gas bearing that is operated by the same gas species as the turbine. Computational fluid dynamics (CFD) simulations have been performed and compared with fluid dynamics measurements of the MAS system for different diameters, temperatures, and spinning rates between 23 kHz and 120 kHz. To our knowledge, this work is the first comprehensive CFD and experimental study of such a wide temperature range that has been carried out for microturbines with pressurized gas bearings. The results show good agreement between measurements and CFD simulations with appropriate (real) gas models, i.e., the ideal gas model for air at room temperature, Peng–Robinson model for nitrogen at 105 K, and ideal gas model for helium at 45 K.

Dynamics of Cations around DNA and Protein as Revealed by 23Na Diffusion NMR Spectroscopy

Counterions are vital for the structure and function of biomolecules. However, the behavior of counterions remains elusive due to the difficulty in characterizing mobile ions. Here, we demonstrate that the dynamics of cations around biological macromolecules can be revealed by 23Na diffusion nuclear magnetic resonance (NMR) spectroscopy. NMR probe hardware capable of generating strong magnetic field gradients enables 23Na NMR-based diffusion measurements for Na+ ions in solutions of biological macromolecules and their complexes. The dynamic properties of Na+ ions interacting with the macromolecules can be investigated using apparent 23Na diffusion coefficients measured under various conditions. Our diffusion data clearly show that Na+ ions retain high mobility within the ion atmosphere around DNA. The 23Na diffusion NMR method also permits direct observation of the release of Na+ ions from nucleic acids upon protein–nucleic acid association. The entropy change due to the ion release can be estimated from the diffusion data.

The CMS Magnetic Field Measuring and Monitoring Systems

This review article describes the performance of the magnetic field measuring and monitoring systems for the Compact Muon Solenoid (CMS) detector. To cross-check the magnetic flux distribution obtained with the CMS magnet model, four systems for measuring the magnetic flux density in the detector volume were used. The magnetic induction inside the 6 m diameter superconducting solenoid was measured and is currently monitored by four nuclear magnetic resonance (NMR) probes installed using special tubes at a radius of 2.9148 m outside the barrel hadron calorimeter at ±0.006 m from the coil median XY-plane. Two more NRM probes were installed at the faces of the tracking system at Z-coordinates of −2.835 and +2.831 m and a radius of 0.651 m from the solenoid axis. The field inside the superconducting solenoid was precisely measured in 2006 in a cylindrical volume of 3.448 m in diameter and 7 m in length using ten three-dimensional (3D) B-sensors based on the Hall effect (Hall probes). These B-sensors were installed on each of the two propeller arms of an automated field-mapping machine. In addition to these measurement systems, a system for monitoring the magnetic field during the CMS detector operation has been developed. Inside the solenoid in the horizontal plane, four 3D B-sensors were installed at the faces of the tracking detector at distances X = ±0.959 m and Z-coordinates of −2.899 and +2.895 m. Twelve 3D B-sensors were installed on the surfaces of the flux-return yoke nose disks. Seventy 3D B-sensors were installed in the air gaps of the CMS magnet yoke in 11 XY-planes of the azimuthal sector at 270°. A specially developed flux loop technique was used for the most complex measurements of the magnetic flux density inside the steel blocks of the CMS magnet yoke. The flux loops are installed in 22 sections of the flux-return yoke blocks in grooves of 30 mm wide and 12–13 mm deep and consist of 7–10 turns of 45 wire flat ribbon cable. The areas enclosed by these coils varied from 0.3 to 1.59 m2 in the blocks of the barrel wheels and from 0.5 to 1.12 m2 in the blocks of the yoke endcap disks. The development of these systems and the results of the magnetic flux density measurements across the CMS magnet are presented and discussed in this review article.

High-precision nuclear magnetic resonance probe suitable for in situ studies of high-temperature metallic melts

High-temperature nuclear magnetic resonance (NMR) has proven to be very useful for detecting the temperature-induced structural evolution and dynamics in melts. However, the sensitivity and precision of high-temperature NMR probes are limited. Here we report a sensitive and stable high-temperature NMR probe based on laser-heating, suitable for in situ studies of metallic melts, which can work stably at the temperature of up to 2000 K. In our design, a well-designed optical path and the use of a water-cooled copper radio-frequency (RF) coil significantly optimize the signal-to-noise ratio (S/NR) at high temperatures. Additionally, a precise temperature controlling system with an error of less than ± 1 K has been designed. After temperature calibration, the temperature measurement error is controlled within ± 2 K. As a performance testing, 27Al NMR spectra are measured in Zr-based metallic glass-forming liquid in situ. Results show that the S/NR reaches 45 within 90 s even when the sample’s temperature is up to 1500 K and that the isothermal signal drift is better than 0.001 ppm per hour. This high-temperature NMR probe can be used to clarify some highly debated issues about metallic liquids, such as glass transition and liquid–liquid transition.

Site-Specific Incorporation of 7-Fluoro-L-tryptophan into Proteins by Genetic Encoding to Monitor Ligand Binding by 19F NMR Spectroscopy.

A mutant aminoacyl-tRNA synthetase identified by a library selection system affords site-specific incorporation of 7-fluoro-L-tryptophan in response to an amber stop codon. The enzyme allows the production of proteins with a single hydrogen atom replaced by a fluorine atom as a sensitive nuclear magnetic resonance (NMR) probe. The substitution of a single hydrogen atom by another element that is as closely similar in size and hydrophobicity as possible minimizes possible perturbations in the structure, stability, and solubility of the protein. The fluorine atom enables site-selective monitoring of the protein response to ligand binding by 19F NMR spectroscopy, as demonstrated with the Zika virus NS2B-NS3 protease.

Spinnoise gradient echoes.

Nuclear spinnoise spectroscopy in the absence of radio frequency pulses was studied under the influence of pulsed field gradients (PFGs) on pure and mixed liquids. Under conditions where the radiation-damping-induced line broadening is smaller than the gradient-dependent inhomogeneous broadening, echo responses can be observed in difference spectra between experiments employing pulsed field gradient pairs of the same and opposite signs. These observed spinnoise gradient echoes (SNGEs) were analyzed through a simple model to describe the effects of transient phenomena. Experiments performed on high-resolution nuclear magnetic resonance (NMR) probes demonstrate how refocused spin noise behaves and how it can be exploited to determine sample properties. In bulk liquids and their mixtures, transverse relaxation times and translational diffusion constants can be determined from SNGE spectra recorded following tailored sequences of magnetic field gradient pulses.

On the use of residual dipolar couplings in multi-state structure calculation of two-domain proteins

Residual dipolar couplings (RDCs) are powerful nuclear magnetic resonance (NMR) probes for the structure calculation of biomacromolecules. Typically, an alignment tensor that defines the orientation of the entire molecule relative to the magnetic field is determined either before refinement of individual bond vectors or simultaneously with this refinement. For single-domain proteins this approach works well since all bond vectors can be described within the same coordinate frame, which is given by the alignment tensor. However, novel approaches are sought after for systems where no universal alignment tensor can be used. Here, we present an approach that can be applied to two-domain proteins that enables the calculation of multiple states within each domain as well as with respect to the relative positions of the two domains.

Stable magic angle spinning with Low-Cost 3D-Printed parts

A 3D-printed double-bearing magic angle spinning (MAS) system was developed with a home-built 4.0 mm MAS nuclear magnetic resonance (NMR) probe at 7 T. Various fused deposition modelling 3D printers were used to produce spinning modules of ignorable materials costs for rotors with a diameter of 7.0, 4.0, and 3.5 mm. High-performance MAS experiments on the 4.0 mm-diameter model using a pencil-type ceramic rotor and 3D-printed drive cap resulted in a high-resolution 1H NMR signal of silicone grease. The 3.5 mm-diameter MAS system reached a spinning frequency of 23 kHz. Furthermore, 3D-printed inserts were designed for various rotor sizes which can isolate the sample from humidity for a duration of more than a week. Single crystal inserts for MAS rotors of commercial probes can readily be printed using two-color printers. Those developments enable customized low-cost MAS NMR for both adapting existing and manufacturing new probes, respectively.

Paramagnetic spin labeling of a bacterial DnaB helicase for solid-state NMR

Labeling of biomolecules with a paramagnetic probe for nuclear magnetic resonance (NMR) spectroscopy enables determining long-range distance restraints, which are otherwise not accessible by classically used dipolar coupling-based NMR approaches. Distance restraints derived from paramagnetic relaxation enhancements (PREs) can facilitate the structure determination of large proteins and protein complexes. We herein present the site-directed labeling of the large oligomeric bacterial DnaB helicase from Helicobacter pylori with cysteine-reactive maleimide tags carrying either a nitroxide radical or a lanthanide ion. The success of the labeling reaction was followed by quantitative continuous-wave electron paramagnetic resonance (EPR) experiments performed on the nitroxide-labeled protein. PREs were extracted site-specifically from 2D and 3D solid-state NMR spectra. A good agreement with predicted PRE values, derived by computational modeling of nitroxide and Gd3+ tags in the low-resolution DnaB crystal structure, was found. Comparison of experimental PREs and model-predicted spin label-nucleus distances indicated that the size of the “blind sphere” around the paramagnetic center, in which NMR resonances are not detected, is slightly larger for Gd3+ (∼14 Å) than for nitroxide (∼11 Å) in 13C-detected 2D spectra of DnaB. We also present Gd3+-Gd3+ dipolar electron–electron resonance EPR experiments on DnaB supporting the conclusion that DnaB was present as a hexameric assembly.

Progress Towards a Higher Sensitivity 13C-Optimized 1.5 mm HTS NMR Probe.

Nuclear magnetic resonance (NMR) probes using thin-film high temperature superconducting (HTS) resonators offer high sensitivity and are particularly suitable for small-sample applications. We are developing an improved 1.5 mm HTS NMR probe designed for operation at 14.1 T and optimized for 13C detection. The total sample volume is about 35 μL and the active sample volume is 20 μL. The probe employs HTS resonators for 13C and 1H transmission and detection and the 2H lock. We examine the interactions of multiple superconducting resonators and normal metal tuning loops on coil resonance frequency and probe sensitivity. We test a recently introduced 13C resonator design, engineered to significantly increase 13C detection sensitivity over previous all-HTS probes. At zero field, we observe a 13C quality factor of 6000 which is several times higher than previous resonators. In this work the coil design considerations and probe build-out procedure are discussed.

Two millimeter diameter spherical rotors spinning at 68 kHz for MAS NMR

Spherical rotors are a new paradigm in magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR). The simple geometry makes smaller diameter spheres and their utilization within narrow-bore NMR probes feasible. Here we report a 68 kHz spinning frequency of 2 mm diameter spheres using helium spinning gas outside the magnet and demonstrate the use of KMnO4 to adjust the magic angle at a spinning frequency of 59.3 kHz for MAS NMR. We observe third-order spinning sidebands in the 55Mn spectrum clearly showing the MAS frequency of 59.3 kHz, with KBr showing nearly no first-order spinning sidebands at a similar frequency. The spinning stability was ±0.5% during data acquisition without spinning regulation. To address concerns about the low NMR filling factor of MAS spheres, we employ a modified stator and a smaller coil and achieve three times higher NMR sensitivity then our previous coil geometries for MAS spheres. Advanced coil and rotor fabrication technologies are expected to further increase the spinning frequency and NMR sensitivity of MAS spheres.

(Invited) Magnetism and Electrochemistry of Fullerene-Based Composites

Endohedral metallofullerenes (EMFs), a negatively sp 2-hybridized spherical carbon surface containing alternating hexagons and pentagons doped with metal ion(s) or cluster inside, have attracted more and more interests owing to their unique nesting structures and alluring chemical/physical properties. Herein, we will discuss several typical spin-active endohedral metallofullerenes. To steer the electron spin of paramagnetic fullerene molecules, a solid-state spin system was constructed via encapsulating paramagnetic fullerenes into the pores of metal-organic frameworks (MOFs) forming a EMF/MOF compostie, and an axisymmetric paramagnetic property was found. This kind of solid spin system can be used as a probe for nanoscale nuclear magnetic resonance or for motion imaging of a single biomolecule.Besides, as a representative allotrope of carbon, fullerene-based composite also exhibit fascinating electrochemistry, e.g., serving as electrocatalyst. In this work, a novel hybrid electrocatalyst comprising fullerene carbon dot (FQD)-decorated cobalt nickel layered double hydroxide (CoNi-LDH) nanosheets anchored on porous nickel foam (NF) is elaborately fabricated. The obtained FQD/CoNi-LDH/NF exhibits superior electrocatalytic activity for hydrogen and oxygen evolution as well as urea oxidation under ambient atmosphere. Both experiment and density functional theory (DFT) calculations demonstrate that the charge transfer from FQD to CoNi-LDH could account for the excellent catalytic performance of the newly-synthesized catalyst, and the decorated FQD finely modulates the electronic structure of CoNi-LDH, favoring the adsorption of active hydrogen atom, and thus promote the catalytic process. The present work would provide useful guidance for designing and developing fullerene-based electrocatalysts for hydrogen production.

Measurement of the Positive Muon Anomalous Magnetic Moment to 0.46ppm.

We present the first results of the Fermilab National Accelerator Laboratory (FNAL) Muon g-2 Experiment for the positive muon magnetic anomaly a_{μ}≡(g_{μ}-2)/2. The anomaly is determined from the precision measurements of two angular frequencies. Intensity variation of high-energy positrons from muon decays directly encodes the difference frequency ω_{a} between the spin-precession and cyclotron frequencies for polarized muons in a magnetic storage ring. The storage ring magnetic field is measured using nuclear magnetic resonance probes calibrated in terms of the equivalent proton spin precession frequency ω[over ˜]_{p}^{'} in a spherical water sample at 34.7 °C. The ratio ω_{a}/ω[over ˜]_{p}^{'}, together with known fundamental constants, determines a_{μ}(FNAL)=116 592 040(54)×10^{-11} (0.46ppm). The result is 3.3 standard deviations greater than the standard model prediction and is in excellent agreement with the previous Brookhaven National Laboratory (BNL) E821 measurement. After combination with previous measurements of both μ^{+} and μ^{-}, the new experimental average of a_{μ}(Exp)=116 592 061(41)×10^{-11} (0.35ppm) increases the tension between experiment and theory to 4.2 standard deviations.

13C-Optimized HTS NMR RF Coil Design at 21.1 T.

We present the design of a novel high-temperature superconductor double-sided racetrack resonator for a 13C optimized nuclear magnetic resonance (NMR) transmitter/receiver coil. The coils operate in a 21.1 T magnet and accommodate a 3 mm × 6.2 mm cross-section rectangular sample tube. The design includes the incorporation of revised finger lengths to improve the homogeneity of current density across the fingers, a new laser trimming approach for adjusting the resonance frequency, and improved ability to shift higher-order modes for suitability in 1H/13C NMR probes. Resonator design methodology, simulations and experimental results are presented.

High-Temperature Pulsed-Field-Gradient 7Li-NMR Measurements of Li2CO3 over 700 K.

Understanding the transport property of Li ions is crucial for improving the performance of Li-ion batteries. To investigate the ion diffusion at high temperatures, we constructed a high-temperature pulsed-field-gradient (PFG) nuclear magnetic resonance (NMR) probe capable of measurements at temperatures >700 K. The accuracy of the sample temperature was confirmed via 79Br NMR measurements of KBr. 7Li PFG-NMR measurements of Li2CO3 were performed at temperatures up to 724 K using the probe. The apparent diffusion coefficient of Li ions in Li2CO3 was obtained experimentally.