Portable NMR Research Articles

Unilateral NMR with a barrel magnet

Unilateral NMR can examine samples without regard to sample size. It is also an easy path to mobile or portable NMR as well as inexpensive NMR. The objective of this work was to develop unilateral NMR with an improved performance in a sample region that was remote from the apparatus. This was accomplished with the creation of a saddle point where all second derivatives of the main component of the field were nulled. A ∼10cm diameter ∼5cm thick magnet combined with a gradiometer coil on the surface detected signals from a sensitive region that extended ∼2cm from the magnet. The relatively homogeneous field of these unilateral NMR devices allows the measurement of rapidly diffusing spins as well as the use of smaller RF amplifiers, which enhances system mobility.

Monitoring of Cellular Changes in the Bone Marrow following PTH(1-34) Treatment of OVX Rats Using a Portable Stray-Field NMR Scanner.

Osteoporosis is characterized by reduction in trabecular bone in conjunction with increased marrow cell adiposity. While these changes occur within weeks, monitoring of treatment efficacy as performed by DEXA is sensitive only to long-term changes. MRI is sensitive to bone marrow changes but is less affordable. In a recent study, we have shown that a stray-field NMR can monitor bone marrow cellular changes that are related to osteoporosis. Objectives. To demonstrate sensitivity of a low-field tabletop NMR scanner to bone marrow dynamics following hormonal treatment in rats. Methods. Two-month-old female rats (n = 36) were ovariectomized (OVX) and dosed for the ensuing 3 or 5 weeks with 20 mg/kg of PTH(1-34). Hind limbs femurs and tibiae were isolated and underwent ex vivo microradiography and histology and NMR relaxometry at 6 weeks (preventive experiment) and 11 weeks (therapeutic treatment experiment) after OVX. Results. OVX rats developed osteoporotic changes including adipogenic marrow compared to Sham and PTH treated rats. T2 and ADC NMR relaxation coefficients were found to correlate with marrow composition. Conclusions. This study suggests that stray-field NMR, an affordable method that is sensitive to the rapid cellular changes in bone marrow, may have a clinical value in monitoring hormonal treatment for osteoporosis.

Optimal Design of a Portable Arc-Shaped NMR Sensor and Its Application in the Aging-Level Detection of Silicone Rubber Insulator

Silicone rubber insulators (SRIs) are widely used in power systems because of their excellent hydrophobicity, high mechanical strength, and light weight; however, detecting SRI degradation remains problematic. Many studies have focused on SRI detection, but reports on rod-sheath detection are limited. We designed a novel nuclear magnetic resonance sensor that could be used to detect the sheath of arc-shaped SRI rods. First, the magnetic structure that generates the main magnetic field (B 0) was designed and optimized, and B 0 was designed purposely for an arc-shaped distribution that can match the sheath of SRI rod well. Second, an arc-shaped spiral radio-frequency coil was designed and optimized. Third, three SRIs serving on a 220-kV power transmission line for different time points were measured using this sensor. The transverse-relaxation decay curves were obtained using the Carr–Purcell–Meiboom–Gill (CPMG) sequence. Inverse Laplace transformation was then used to obtain the T 2 distribution from the CPMG decay curves. T 2 distribution demonstrated that the long component of T 2 decreased with increased serving time. Therefore, the T 2,long mean obtained from the T 2 distribution can be used as an index to reflect the aging level of the sheath of SRI rod.

Advanced NMR methodologies and micro-analytical techniques to investigate the stratigraphy and materials of 14th century Sienese wooden paintings

In this study a multi-analytical approach was used to characterize ancient and modern constitutive materials and the stratigraphy of a Sienese wooden painting consisting of four cusps belonging to a lost Polyptych, by Andrea di Bartolo dated back to the late 14th century, repainted in the 16th century and partially restored and cleaned in the 20th century. In order to distinguish the original layers from the other ones, a comparison with the painting Adorazione dei Magi by Bartolo di Fredi (Andrea's father) dated to the 14th century, was performed. The painting Adorazione dei Magi was found to be in a very good state of conservation and provided a model of the artistic technique used in Sienese painting in the 14th century.In situ measurements by portable NMR were performed to investigate the stratigraphy of the paintings in a non-destructive and non-invasive way. By means of this technique, information about all layers constituting the paintings were obtained and used to plan the successive micro-sampling. High resolution NMR spectroscopy was applied on a few samples to characterize binders and organic substances. Specifically, solid state 13C and 31P CPMAS NMR spectroscopy and 1H NMR spectroscopy in solution were applied to characterize original and non-original materials. Other techniques such as ToF-SIMS, HPLC, IR and Raman spectroscopy were also applied.

Highly uniform single-sided portable NMR sensor and its application in assessing the aging level of silicone rubber insulators

Highly uniform single-sided portable NMR sensor and its application in assessing the aging level of silicone rubber insulators

Miniature mobile NMR sensors for material testing and moisture-monitoring

Miniaturization plays an essential role in modern life of the 21st century. It is encountered, e.g., in communication, personalized and portable computers and in medicine. Miniaturization also affects NMR, one of the most versatile analytical tools, leading to dedicated sensors and portable devices which lead to new applications of NMR in different disciplines. The miniaturization of two portable stray-field NMR sensor types, the NMR-MOUSE® and an inside-out sensor are reported in this work. The sensors are critically evaluated and compared to other standard probes. Applications in material testing and civil engineering are evaluated.

Sensitization of a stray-field NMR to vibrations: A potential for MR elastometry with a portable NMR sensor

An NMR signal from a sample in a constant stray field of a portable NMR sensor is sensitized to vibrations. The CPMG sequence is synchronized to vibrations so that the constant gradient becomes an “effective” square-wave gradient, leading to the vibration-induced phase accumulation. The integrating nature of the spot measurement, combined with the phase distribution due to a non-uniform gradient and/or a wave field, leads to a destructive interference, the drop in the signal intensity and changes in the echo train shape. Vibrations with amplitudes as small as 140nm were reliably detected with the permanent gradient of 12.4T/m. The signal intensity depends on the phase offset between the vibrations and the pulse sequence. This approach opens the way for performing elastometry and micro-rheology measurements with portable NMR devices beyond the walls of a laboratory.Even without synchronization, if a vibration frequency is comparable to 1/2TE of the CPMG sequence, the signal can be severely affected, making it important for potential industrial applications of stray-field NMR.

Unilateral NMR investigation of multifunctional treatments on stones based on colloidal inorganic and organic nanoparticles.

Consolidation and protection are among the most important treatments usually carried out in conservation of stone artifacts and monuments. In this paper, portable unilateral NMR and conventional techniques were used for investigating new multifunctional treatments based on tetraethoxysilane, silica, and polytetrafluoroethylene nanoparticles. The study was carried out on a very complex and heterogeneous porous stone such as tuff. NMR study allowed to obtain detailed information on the penetration depth of treatments, the hydrophobic effect, and changes in the open porosity caused by treatments. Physical and chemical inhomogeneities between the impregnated layers of tuff and the layers underneath were also detected. The average pores radius and pores interconnection obtained from NMR diffusion measurements were used for the first time to compare effects of different consolidating and/or protective treatments on stone. Because unilateral NMR technique is neither destructive nor invasive, investigation of treatments can be also carried out and optimized directly on buildings and monuments of interest for Cultural Heritage.

Scalable NMR spectroscopy with semiconductor chips.

State-of-the-art NMR spectrometers using superconducting magnets have enabled, with their ultrafine spectral resolution, the determination of the structure of large molecules such as proteins, which is one of the most profound applications of modern NMR spectroscopy. Many chemical and biotechnological applications, however, involve only small-to-medium size molecules, for which the ultrafine resolution of the bulky, expensive, and high-maintenance NMR spectrometers is not required. For these applications, there is a critical need for portable, affordable, and low-maintenance NMR spectrometers to enable in-field, on-demand, or online applications (e.g., quality control, chemical reaction monitoring) and co-use of NMR with other analytical methods (e.g., chromatography, electrophoresis). As a critical step toward NMR spectrometer miniaturization, small permanent magnets with high field homogeneity have been developed. In contrast, NMR spectrometer electronics capable of modern multidimensional spectroscopy have thus far remained bulky. Complementing the magnet miniaturization, here we integrate the NMR spectrometer electronics into 4-mm(2) silicon chips. Furthermore, we perform various multidimensional NMR spectroscopies by operating these spectrometer electronics chips together with a compact permanent magnet. This combination of the spectrometer-electronics-on-a-chip with a permanent magnet represents a useful step toward miniaturization of the overall NMR spectrometer into a portable platform.

Ultra-low-field NMR relaxation and diffusion measurements using an optical magnetometer.

Nuclear magnetic resonance (NMR) relaxometry and diffusometry are important tools for the characterization of heterogeneous materials and porous media, with applications including medical imaging, food characterization and oil-well logging. These methods can be extremely effective in applications where high-resolution NMR is either unnecessary, impractical, or both, as is the case in the emerging field of portable chemical characterization. Here, we present a proof-of-concept experiment demonstrating the use of high-sensitivity optical magnetometers as detectors for ultra-low-field NMR relaxation and diffusion measurements.

Heteronuclear refocusing by nonlinear phase and amplitude modulation on a single transmitter channel

The application of low magnetic fields to heteronuclear NMR has expanded recently alongside the emergence of methods for achieving near unity polarization of spin ensembles, independent of magnetic field strength. The parahydrogen induced hyperpolarization methods in particular, often use a hybrid arrangement where a high field spectrometer is used to detect or image polarized molecules that have been conjured on a separate, dedicated polarizer instrument operating at fields in the mT regime where yields are higher. For controlling polarizer chemistry, spare TTL channels of portable NMR spectrometers can be used to pulse program reaction timings in synchrony with heteronuclear RF transformations. The use of a spectrometer as a portable polarizer control module has the advantage of allowing detection in situ, simplifying the process of optimizing polarization yields prior to in vivo experimental trials. Suitable heteronuclear spectrometers compatible with this application are becoming more common, but are still sparsely available in comparison to a large existing infrastructure of single channel NMR consoles. With the goal of expanding the range of these systems to multinuclear applications, the feasibility of rotating a pair of heteronuclear spins (13C and 1H) at 12mT was investigated in this study. Nonlinear phase and amplitude modulated waveforms designed to simultaneously refocus magnetization at 128kHz (13C) and 510kHz (1H) were generated numerically with optimal control. Although precise quantitative comparisons were not attempted due to limitations of the experimental setup, signals refocused at heteronuclear frequencies with this PANORAMIC approach (Precession And Nutation for Observing Rotation At Multiple Intervals about the Carrier) yielded amplitudes comparable to signals which were refocused using traditional block pulses on heteronuclear channels. Using this PANORAMIC approach to heteronuclear NMR at low field would reduce expense as well as hardware complexity and bulk, weighed against the caveat that elaborate pulses are required. More work will be necessary to test this method on the targeted application of parahydrogen induced hyperpolarization as well as to quantify efficiency, but upon further development we anticipate that this method may offer a viable ‘software’ approach to heteronuclear manipulations of spins at low magnetic fields.

NMR methodologies in the analysis of blueberries

An NMR analytical protocol based on complementary high and low field measurements is proposed for blueberry characterization. Untargeted NMR metabolite profiling of blueberries aqueous and organic extracts as well as targeted NMR analysis focused on anthocyanins and other phenols are reported. Bligh-Dyer and microwave-assisted extractions were carried out and compared showing a better recovery of lipidic fraction in the case of microwave procedure. Water-soluble metabolites belonging to different classes such as sugars, amino acids, organic acids, and phenolic compounds, as well as metabolites soluble in organic solvent such as triglycerides, sterols, and fatty acids, were identified. Five anthocyanins (malvidin-3-glucoside, malvidin-3-galactoside, delphinidin-3-glucoside, delphinidin-3-galactoside, and petunidin-3-glucoside) and 3-O-α-l-rhamnopyranosyl quercetin were identified in solid phase extract. The water status of fresh and withered blueberries was monitored by portable NMR and fast-field cycling NMR. (1) H depth profiles, T2 transverse relaxation times and dispersion profiles were found to be sensitive to the withering.

Nuclear Magnetic Resonance Relaxometry and Thermoelectrodynamic Spectroscopy Study of Heat Accumulating/Emitting Salt CaCl<sub>2</sub>•6H<sub>2</sub>O

Using nuclear magnetic resonance relaxometry and thermoelectric dynamical methods studied phase transitions and electric power generation properties of hydrate salt CaCl2•6H2O . It can be used as a phase-changing materials (PCM) for heat accumulating/emitting thermal electric energy storage. For studies of phase transitions temperature and time dependences on protons was used Portable Relaxometer NMR NP-2 on resonance frequency nо = 14,5МГц. Was received data on structure-dynamical NMR-parameters, determining phase transition properties of salt.

High-resolution heteronuclear multi-dimensional NMR spectroscopy in magnetic fields with unknown spatial variations

Heteronuclear NMR spectroscopy is an extremely powerful tool for determining the structures of organic molecules and is of particular significance in the structural analysis of proteins. In order to leverage the method’s potential for structural investigations, obtaining high-resolution NMR spectra is essential and this is generally accomplished by using very homogeneous magnetic fields. However, there are several situations where magnetic field distortions and thus line broadening is unavoidable, for example, the samples under investigation may be inherently heterogeneous, and the magnet’s homogeneity may be poor. This line broadening can hinder resonance assignment or even render it impossible. We put forth a new class of pulse sequences for obtaining high-resolution heteronuclear spectra in magnetic fields with unknown spatial variations based on distant dipolar field modulations. This strategy’s capabilities are demonstrated with the acquisition of high-resolution 2D gHSQC and gHMBC spectra. These sequences’ performances are evaluated on the basis of their sensitivities and acquisition efficiencies. Moreover, we show that by encoding and decoding NMR observables spatially, as is done in ultrafast NMR, an extra dimension containing J-coupling information can be obtained without increasing the time necessary to acquire a heteronuclear correlation spectrum. Since the new sequences relax magnetic field homogeneity constraints imposed upon high-resolution NMR, they may be applied in portable NMR sensors and studies of heterogeneous chemical and biological materials.

Design and Construction of Light Weight Portable Nmr Halbach Magnet

Abstract A light weight, simple design NMR apparatus consists of 24 identical magnets arranged in Halbach array was designed and built. The homogeneity of the magnetic field B0 can be improved by dividing a long magnets into several rings. The size of the useful volume depends on both the gap between each ring and some others shim magnets. Our aim is to enhance the sensitive volume and to maintain the highest magnetic static field (B0). This apparatus generates a B0 field strength of about 0.1 T. This work focuses on the magneto-static simulation of NdFeB magnets arrangement and on the comparison with the measurement of the magnetic field strength and homogeneity in three dimensions (3D). The homogeneity of the magnetic field B0 is optimized with the help of CAD and mathematical software. Our results were also validated with a Finite Element Method (FEM). The simulation results of the strength and of the homogeneity of B0 field were compared to those obtained with a digital gaussmeter. The homogeneity in the magnet longitudinal axis and the field B0 strength are similar. However, the homogeneity in transverse plane differs from simulation and measurement because of the quality of the magnets. In order to improve the homogeneity, we propose a new shim method.

Faster imaging with a portable unilateral NMR device

Unilateral NMR devices are important tools in various applications such as non-destructive testing and well logging, but are not applied routinely for imaging, primarily because B0 inhomogeneity in these scanners leads to a relatively low signal and requires use of the slow single point imaging scan scheme. Enabling high quality, fast imaging could make this affordable and portable technology practical for various imaging applications as well as for new applications that are not yet feasible with MRI technology.The goal of this work was to improve imaging times in a portable unilateral NMR scanner. Both Compressed Sensing and Fast Spin Echo were modified and applied to fit the unique characteristics of a unilateral device. Two printed phantoms, allowing high resolution images, were scanned with both methods and compared to a standard scan and to a low pass scan to evaluate performance. Both methods were found to be feasible with a unilateral device, proving ways to accelerate single point imaging in such scanners. This outcome encourages us to explore how to further accelerate imaging times in unilateral NMR devices so that this technology might become clinically applicable in the future.

Unilateral NMR: a Noninvasive Tool for Monitoring In Situ the Effectiveness of Intervention to Reduce the Capillary Raise of Water in an Ancient Deteriorated Wall Painting

Portable unilateral NMR was used to quantitatively map in a fully noninvasive way the moisture distribution in an ancient deteriorated wall painting before and after an intervention to reduce the capillary raise of water through the wall. Maps obtained at a depth of 0.5 cm clearly showed the path of the capillary raise and indicated that, after the intervention, the moisture level was reduced. Maps obtained by measuring the first layers of the wall painting were affected by the critical environmental conditions of the second hypogeous level of St. Clement Basilica, Rome, and by the presence of salts efflorescence and encrustations on the surface of the wall painting. The morphology and the elemental composition of salts investigated by SEM-EDS indicated that efflorescences and encrustations were mostly constituted of gypsum and calcite. The presence of these salts is explained with the presence of high concentration of carbon dioxide and sulphur-rich particles due to pollution which, along with the high-moisture level and the extremely feeble air circulation, cause recarbonation and sulphation processes on the plaster surface.

Ancient Roman wall paintings mapped nondestructively by portable NMR

The stratigraphies of decorated walls in ancient Herculaneum, Italy, were analyzed by single-sided (1)H NMR. A large version of the NMR-MOUSE® with a maximum penetration depth of 25 mm was used to map proton density profiles at different positions of the Mosaic of Neptune and Amphitrite showing considerable differences between different tesserae and the mortar bed at different times of the year. In the House of the Black Room, different mortar layers were observed on painted walls as well as different proton content in different areas due to different moisture levels and different conservation treatments. The proton density profiles of the differently treated areas indicated that one method leads to higher moisture content than the other. Untreated wall paintings from different times were profiled in a recently excavated room at the Villa of the Papyri showing two different types of mortar layer structures which identify two different techniques of preparing the walls for painting. Reflectance Fourier mid-infrared spectroscopy and in situ X-ray fluorescence measurements complemented the NMR measurements and provided additional insight into the identification of organic coatings as well as the nature of the pigments used, respectively. The information acquired nondestructively by NMR is valued for elaborating conservation strategies and for identifying different schools of craftsmen who prepared the mortar supports of the wall paintings.

Assessment of the weathering effects on cellulose based materials through a multianalytical approach

Paper and papyrus endurance depends on their intrinsic properties that are related to the manufacture processes and to the environmental conditions (temperature, humidity, presence of micro-organisms, etc.). During the time, paper and papyrus undergo unavoidable ageing processes causing mainly the degradation of the cellulose. In the framework of the European Project “PAPERTECH” a multi-analytical approach was selected to carefully study the behaviour, properties, and the quality of different samples of paper with different provenience, before and after artificial ageing. This work was focused to understand and explain the degradation processes occurring in paper during the time. Portable EDXRF, NMR, Raman, FTIR, ATR, mechanical properties, colour measurement and XRD analyses were performed before and after the accelerated weathering. The light and the chemical oxidation were found to cause the most aggressive ageing processes.

Aspiring cancer diagnostic

Massachusetts researchers have developed a portable NMR technology and used it to diagnose cancer more quickly and accurately than is possible with conventional biopsies. But the technology does not involve visual confirmation of a cancer's presence and thus is most likely to complement histological analysis as the diagnostic standard.