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The design and development for a compact 1 GHz (23.5 T)-class NMR magnet are presented. The magnet uses inner coils wound with Ni alloy-reinforced Bi-2223 conductors in combination with LTS outer coils. The series-connected coils are operated in a power supply-driven mode. The total magnet size is very compact, and is comparable to that of a currently commercialized 600-MHz (14.1 T) NMR magnet. This owes to a high current density operation of the Bi-2223 inner coils, which contribute as much as 53% of the total magnetic field. This paper investigated the following properties of the Bi-2223 inner coils: First, joint resistance under external magnetic fields; second, tensile stress tolerances of the Bi-2223 conductor under bending condition; third, high compressive stress on Bi-2223 coils; fourth, the effect of screening current-induced magnetic field on the field homogeneity and stability; and fifth, the maximum permissible Joule heating to avoid a thermal runaway. Two Bi-2223 inner coils for the magnet were built and tested in liquid nitrogen, which provided important knowledge for the magnet excitation.

An important method to improve the sensitivity of a nuclear magnetic resonance (NMR) system is to increase the quality factor ( Q ) of the pickup coils. In this paper, we focus on the following three items: 1) effect of the surface resistance ( R s) of the YBa2Cu3O7-δ (YBCO) films on the Q of the NMR pickup coil; 2) relationship between coil line width and current flowing through coil; and 3) effect of Si-ion irradiation to YBCO films on the Q of the NMR pickup coils. In the study of 1), we examined the Q of the NMR pickup coils made by YBCO films with different R s and found that reduction of R s is useful in increasing the Q of the NMR pickup coils. In the study of 2), we simulated the current flowing in the NMR coils by an electromagnetic simulator, and found that wider microstrip lines of the NMR pickup coil increase the current. In the study of 3), we examined Si-ion irradiation effect to reduce R s of YBCO films, and found low irradiation energy and low irradiation density of Si-ion is useful to decrease R s and useful to obtain the high Q NMR pickup coils.

NMR spectroscopy permits real-time monitoring of reactions that involve changes in the spectra of reactants. MICCS (MIcro Channelled Cell for Synthesis monitoring) is a microfluidic chip for such purposes, which is used to rapidly activate reactions by mixing the reactant solutions in the chip inserted into the typical NMR tube. Although it allows monitoring of chemical reactions of small compounds, its simple mixing system dependent on diffusion in the microchannel was not suitable for macromolecules such as proteins with low diffusion rates. Here, we developed a new microfluidic chip based on MICCS by incorporating a mixer of split-and-recombination type within the microchannel. We applied it to monitoring of the protein-folding reaction in a stopped-flow mode. A solution of denaturant-unfolded RNase A was injected from a syringe pump into the microchip set inside the NMR magnet and mixed with a buffer for dilution to reach the folding condition. Immediately after dilution, the reaction was initiated and detected by a series of NMR measurements that were synchronized with activation and inactivation of the pump. The process was repeated for accumulation of the data. By analysing the change of the spectra by factor analysis, a kinetic constant of 0.57 min−1 was obtained.

The low sensitivity of NMR spectroscopy is of historical concern in the field, and various approaches have been developed to mitigate this limitation. On the shoulder of giants, today one can routinely implement, for example, the pulse/Fourier transform NMR with the cross polarization together with the ultra-low temperature MAS DNP under high-field conditions. We show in this work this current opportunity should further be augmented by combining them with the cryogenic signal amplification. Our presented MAS DNP probe operates with the closed-cycle helium MAS system, and cools the internal preamplifier-duplexer module with the "return" helium gas on its way back to the compressor in the loop. The signal-to-noise (S/N) gain relative to the room-temperature measurements of a factor of 4.6 and 2.4 was found for the measurement using the cold- and room-temperature preamplifier, respectively, at the sample temperature of T = 20 K at B

Solid-state NMR observations of low-gamma half-integer quadrupolar nuclei, 35Cl and 37Cl, were demonstrated using a 24 T hybrid magnet (1H resonance frequency of 1.02 GHz) comprised of the high-temperature (HTS) and low-temperature (LTS) superconductors, and compared with results using a 14.1 T standard NMR magnet. While at 24 T the linewidth is 1.7 times narrower than that at 14.1 T, the gain in the sensitivity is 7.0 times because of enhanced polarization, reduced linewidth, and the use of larger rotor. A simple theoretical model was used to rationalize the sensitivity enhancements. The ratio of 35Cl and 37Cl quadrupolar couplings agrees well with the ratio of quadrupolar moments, and no isotope-dependent chemical shift has been observed. In addition, the 3QMAS spectrum of 35Cl is shown to demonstrate the high sensitivity rendered by the 24 T spectrometer.

This paper presents the results of a high field generation test for layer-wound HTS coils in a background magnetic field. The test revealed new types of degradation for a REBCO coil caused by an electromagnetic force. A series-connected REBCO coil and a Bi-2223 coil were charged at 4.2 K in a background magnetic field of 17.2 T to generate a central magnetic field of 28.2 T (nuclear-magnetic-resonace frequency of 1.2 GHz). However, a premature normal voltage appeared on the REBCO coil, and the charging was stopped at 25 T. Unwinding the REBCO coil after the experiment found: 1) delamination, due to a cleavage and peeling, of the conductor in a soldered joint inside the winding; and 2) axial movement and edgewise bend deformation of the REBCO conductor at the outermost layer. The keyword of the present degradation is stress concentration, which is also the origin of the more widely known thermal stress-induced degradation.

Using a Bi-2223 innermost coil, the world's first NMR magnet with a frequency beyond 1 GHz has been developed and operated at the National Institute for Materials Science during 2014-2015. The existing 920 MHz (21.6 T) NMR magnet was successfully upgraded to a 1030 MHz (24.2 T) magnet by replacing the Nb3Sn innermost coil with a Bi-2223 coil. After charging the magnet to 1020 MHz (24.0 T), a shimming operation was started to obtain the homogeneous magnetic field required for NMR measurements. However, a large magnetic field inhomogeneity appeared, which could not be compensated using conventional shimming methods, i.e., superconducting and room temperature shim coils. Therefore, a new ferromagnetic shimming technology was applied, which achieved powerful and fast-acting field compensation and performed comparably to active shimming. This enabled effective compensation of the magnetic field inhomogeneity, leading to a subsequently excellent NMR resolution test result of 0.7 ppb. This NMR resolution enables NMR measurements for a membrane protein sample.

This study reports a first successful demonstration of a single channel proton 3D and 2D high-throughput ultrafast magic angle spinning (MAS) solid-state NMR techniques in an ultra-high magnetic field (1020 MHz) NMR spectrometer comprised of HTS/LTS magnet. High spectral resolution is well demonstrated.

Magic-angle spinning (MAS) NMR is a powerful tool for studying molecular structure and dynamics, but suffers from its low sensitivity. Here, we developed a novel helium-cooling MAS NMR probe system adopting a closed-loop gas recirculation mechanism. In addition to the sensitivity gain due to low temperature, the present system has enabled highly stable MAS (vR=4–12kHz) at cryogenic temperatures (T=35–120K) for over a week without consuming helium at a cost for electricity of 16kW/h. High-resolution 1D and 2D data were recorded for a crystalline tri-peptide sample at T=40K and B0=16.4T, where an order of magnitude of sensitivity gain was demonstrated versus room temperature measurement. The low-cost and long-term stable MAS strongly promotes broader application of the brute-force sensitivity-enhanced multi-dimensional MAS NMR, as well as dynamic nuclear polarization (DNP)-enhanced NMR in a temperature range lower than 100K.

High-temperature superconductors (HTS) are the key technology to achieve super-high magnetic field nuclear magnetic resonance (NMR) spectrometers with an operating frequency far beyond 1 GHz (23.5 T). (RE)Ba 2 Cu 3 O 7− x (REBCO, RE: rare earth) conductors have an advantage over Bi 2 Sr 2 Ca 2 Cu 3 O 10− x (Bi-2223) and Bi 2 Sr 2 CaCu 2 O 8− x (Bi-2212) conductors in that they have very high tensile strengths and tolerate strong electromagnetic hoop stress, thereby having the potential to act as an ultra-compact super-high field NMR magnet. As a first step, we developed the world’s first NMR magnet comprising an inner REBCO coil and outer low-temperature superconducting (LTS) coils. The magnet was successfully charged without degradation and mainly operated at 400 MHz (9.39 T). Technical problems for the NMR magnet due to screening current in the REBCO coil were clarified and solved as follows: (i) A remarkable temporal drift of the central magnetic field was suppressed by a current sweep reversal method utilizing ∼10% of the peak current. (ii) A Z2 field error harmonic of the main coil cannot be compensated by an outer correction coil and therefore an additional ferromagnetic shim was used. (iii) Large tesseral harmonics emerged that could not be corrected by cryoshim coils. Due to those harmonics, the resolution and sensitivity of NMR spectra are ten-fold lower than those for a conventional LTS NMR magnet. As a result, a HSQC spectrum could be achieved for a protein sample, while a NOESY spectrum could not be obtained. An ultra-compact 1.2 GHz NMR magnet could be realized if we effectively take advantage of REBCO conductors, although this will require further research to suppress the effect of the screening current.

The use of REBCO coils is a promising approach to achieve super-high field NMR magnets. As the first step in this direction, we have started to develop an LTS/REBCO NMR magnet operated at 400-600 MHz (9.4-14.1 T). In this paper, based on numerical simulations, we describe a study of the thermal runaway of the REBCO innermost coil, which is one of the major problems of this type of magnet. Based on the simulation results, if an LTS coils quench occurs, the current in the REBCO coil continues to increase due to the electromagnetic induction and leads to a natural thermal runaway with a very high current density. The thermal runaway is limited to only the top and bottom ends of the REBCO coil, as the radial magnetic field is highest there and the quench propagation velocity is quite low. The current density for this type of thermal runaway is much higher than that of the operating current, resulting in the catastrophic overheating of the coil. This is the worst case scenario which must be prevented for the LTS/REBCO NMR magnet. An optimal size dump resistor for the REBCO coil can prevent the natural thermal runaway by suppressing the current increase due to electromagnetic induction.

Solid-state NMR observations of low-gamma half-integer quadrupolar nuclei

Conventional low-temperature superconducting (LTS) NMR magnets cannot exceed 23.5 T, as the critical current density decreases steeply beyond 23 T. The high-temperature superconducting (HTS) magnet provides a high current density even at the field above 23 T, enabling 1H NMR at a frequency above 1 GHz. Thus, super-high-field NMR magnets are possible if we employ LTS outer coils and HTS inner coils; that is, an LTS/HTS NMR magnet. We firstly conducted basic experiments and made a precise comparison between two 500 MHz-class LTS/HTS NMR spectrometers operated in driven mode; one with a Bi-2223 innermost coil and another with an REBCO innermost coil. We then evaluated the effect of screening current induced in the HTS coil, the NMR sensitivity and NMR signal resolution, and the quality of protein NMR spectra. Based on these results, we constructed the world's first beyond 1 GHz LTS/Bi-2223 NMR spectrometer; the magnet was successfully charged to 1.02 GHz (24.0 T). It was demonstrated that the quality of the 2-D solid-state NMR spectrum of a membrane protein was considerably better than that obtained by a conventional 700 MHz NMR magnet. Finally, a perspective on the super-high-field NMR spectrometers (1H at 1.2 GHz), is discussed. Keywords: super high field NMR magnet; high temperature superconductor (HTS); driven mode operation; internal/external lock; screening current induced magnetic field; temporal magnetic field drift; magnetic shielding due to screening current; NMR magnet operated beyond 1 GHz; membrane protein; quadrupolar nuclei

The development of an NMR interface microchip and its applications to the real-time monitoring of chemical reactions are described. The microchip device was named "MICCS" (MIcro Channeled Cell for Synthesis monitoring), and the method using it was named "MICCS-NMR". MICCS was inserted into a 5 mm Phi NMR sample tube. Thus standard solution NMR probes without any modifications can be used in MICCS-NMR measurements. A gap between MICCS and the sample tube was filled with a deuterated solvent for an NMR lock. The reaction temperature and reaction time in MICCS can be easily changed by adjusting the temperature of the NMR probe and changing the flow rates, respectively. The effectiveness of the MICCS-NMR was verified in the real-time monitoring of the Wittig reaction. Preliminary data on the direct detection of intermediates of the Grignard reaction is also reported. Besides real-time monitoring of chemical reactions, MICCS-NMR would be useful as a qualitative detection method for microchip-based synthesis.

Use of high-temperature superconducting (HTS) inner coils in combination with conventional low-temperature superconducting (LTS) outer coils for an NMR magnet, i.e. a LTS/HTS NMR magnet, is a suitable option to realize a high-resolution NMR spectrometer with operating frequency >1GHz. From the standpoint of creating a compact magnet, (RE: Rare earth) Ba2Cu3O7-x (REBCO) HTS inner coils which can tolerate a strong hoop stress caused by a Lorentz force are preferred. However, in our previous work on a first-generation 400MHz LTS/REBCO NMR magnet, the NMR resolution and sensitivity were about ten times worse than that of a conventional LTS NMR magnet. The result was caused by a large field inhomogeneity in the REBCO coil itself and the shielding effect of a screening current induced in that coil. In the present paper, we describe the operation of a modified 400MHz LTS/REBCO NMR magnet with an advanced field compensation technology using a combination of novel ferromagnetic shimming and an appropriate procedure for NMR spectrum line shape optimization. We succeeded in obtaining a good NMR line shape and 2D NOESY spectrum for a lysozyme aqueous sample. We believe that this technology is indispensable for the realization of a compact super-high-field high-resolution NMR.

We have successfully developed a 1020MHz (24.0T) NMR magnet, establishing the world's highest magnetic field in high resolution NMR superconducting magnets. The magnet is a series connection of LTS (low-Tc superconductors NbTi and Nb3Sn) outer coils and an HTS (high-Tc superconductor, Bi-2223) innermost coil, being operated at superfluid liquid helium temperature such as around 1.8K and in a driven-mode by an external DC power supply. The drift of the magnetic field was initially ±0.8ppm/10h without the (2)H lock operation; it was then stabilized to be less than 1ppb/10h by using an NMR internal lock operation. The full-width at half maximum of a (1)H spectrum taken for 1% CHCl3 in acetone-d6 was as low as 0.7Hz (0.7ppb), which was sufficient for solution NMR. On the contrary, the temporal field stability under the external lock operation for solid-state NMR was 170ppb/10h, sufficient for NMR measurements for quadrupolar nuclei such as (17)O; a (17)O NMR measurement for labeled tri-peptide clearly demonstrated the effect of high magnetic field on solid-state NMR spectra.

The first 920 MHz high-resolution NMR (nuclear magnetic resonance) magnet was successfully installed at the Tsukuba Magnet Laboratory of the National Institute for Materials Science. A persistent operation at 21.6 T has continued since April 2002 without any problems. Excellent field stability of 0.31 Hz/h was observed from December 2002 to January 2003. Since July 2002, the magnet was used as an essential part of the only 920 MHz high-resolution NMR spectrometer in the world. The signal-to-noise ratio of 0.1% ethylbenzene using a proton-selective probe was as high as 2981. An HCN triple-resonance probe is now attached to the spectrometer to contribute to the National Project on Protein Structural and Functional Analysis in Japan. The completion of the second 920 MHz-class NMR spectrometer is scheduled for spring 2004.

Recently, we have successfully developed a 1020-MHz (24.0 T) NMR system. The NMR magnet consists of superconducting coils having low critical temperature and high critical temperature. It was confi...

We have developed a 920 MHz NMR system and performed the proton NMR measurement of ethylbenzene and water using the superconducting magnet operating at 21.6 T ( 920 MHz for proton), which is the highest field produced by a superconducting NMR magnet in the persistent mode. From the NMR measurements, it is verified that both homogeneity and stability of the magnet have a specification sufficient for a high-resolution NMR. The sensitivity has been examined by 1 H NMR of 0.1% ethylbenzene in Wilmad 555 tube and obtained the signal-to-noise ratio as S/N=2981, which is the highest record, to our knowledge, among the room temperature measurements.

This paper describes a field shimming technology to obtain a spatially homogeneous magnetic field required for a high-resolution nuclear magnetic resonance (NMR) magnet under the influence of a screening current in a (RE)Ba2Cu3O7–x (REBCO) coil. Use of REBCO inner coils is one solution to realize a super-high field (>23.5 T, 1 GHz) NMR magnet. However, a REBCO coil generates a large amount of field error harmonics due to the inhomogeneous coil winding introduced by a thin tape conductor. In addition, the performance of a field correction coil and outer superconducting (SC) shim coils are significantly reduced due to the shielding effect of the screening current in the REBCO coil. Therefore, conventional shimming technology using SC shim coils and room temperature shim coils cannot adequately compensate those field error harmonics and high-resolution NMR measurements are not possible. In the present paper, an advanced field shimming technology including an inner SC shim coil and a novel type of ferromagnetic shim were installed in a 400 MHz low-temperature SC/REBCO NMR magnet. The inner SC shim coil and the ferromagnetic shim compensated for the reduction in the performances of the field correction coil and the SC shim coils, respectively. The field error harmonics were greatly compensated with the technology and a high NMR resolution

An advanced Bi-2223 conductor with Ni–Cr reinforcement is a likely candidate to achieve a compact super-high field nuclear magnetic resonance (NMR) magnet capable of operation beyond 1 GHz (23.5 T). However, the conductors must show both high hoop stress tolerance, typically >300 MPa, and a small screening current-induced magnetic field, both of which are essential for a compact magnet generating a highly accurate field. These two conditions have not yet been demonstrated in a working coil. This is the first paper to systematically investigate both characteristics for a layer-wound coil made with the advanced Bi-2223 conductor operated mainly at 4.2 K in an external field of ≤17 T. The coil tolerated a hoop stress of 370 MPa, even though the conductor had a bending strain corresponding to a diameter of 120 mm. On the other hand, the coil showed a notable screening current-induced field in a low external field, which may be explained by weak-link and direct contacts between highly packed Bi-2223 filaments in the silver matrix. The field sharply decreased with increasing external field between 0–1 T. Thus, the conductor should be useful for inner coils in compact super-high field NMR magnets.

RE-Ba-Cu-O (REBCO) layer-wound coils were operated to investigate their properties under electromagnetic forces in an external magnetic field of up to 17.2 T. While REBCO coils were successfully operated under electromagnetic forces over 200 MPa, some showed degradation after quenching. To develop high-temperature superconducting (HTS) magnets, the reasons for the degradation of REBCO coils should be investigated. In this study, the degraded REBCO coils were carefully rewound. The critical current (Ic) of the rewound REBCO conductor was measured to check the damaged parts in the degraded REBCO coils, and the possible causes for the degradation were discussed.

RE-Ba-Cu-O (REBCO) high-temperature superconducting conductors have the advantage of high critical current density in a magnetic field above 10 T as well as tolerance to high tensile stress. REBCO high-temperature superconducting coils are expected to be applied to superconducting magnets using cryocoolers. While epoxy-resin-impregnated superconducting coils are considered to be appropriate for superconducting magnets using cryocoolers because the impregnation provides sufficient thermal conductivity, the degradation of epoxy-resin-impregnated REBCO coils due to extremely low nominal cleavage strength is a serious problem. This problem is negligible for wax (paraffin)-impregnated REBCO coils. A wax-impregnated GdBCO layer-wound coil using cryocoolers was successfully operated at a current between $-$ 300 and 300 A.

A nuclear magnetic resonance (NMR) system using a high-temperature superconducting (HTS) magnet and a probe with an HTS radio frequency coil is currently under development. The HTS NMR magnet is expected to reduce the volume occupied by the magnet and to encourage users to install higher field NMR systems. RE-Ba-Cu-O-coated (REBCO-coated) conductors offer the advantages of a higher critical current density than low-temperature superconductors in magnetic fields above 10 T as well as tolerance to high tensile stress. Both of these factors are expected to lead to a reduction in the volume of the magnet. Four REBCO layer-wound test coils were fabricated in order to investigate their properties under electromagnetic forces in an external magnetic field of up to 17. 2 T. The REBCO coils with a practical inner diameter were successfully operated under electromagnetic forces of over 200 MPa in high magnetic fields.

High-temperature superconducting (HTS) magnets are believed to be a practical option in the development of high field nuclear magnetic resonance (NMR) systems. The development of a 600 MHz NMR system that uses an HTS magnet and a probe with an HTS radio frequency coil is underway. The HTS NMR magnet is expected to reduce the volume occupied by the magnet and to encourage users to install higher field NMR systems. The tolerance to high tensile stress is expected for HTS conductors in order to reduce the magnet in volume. A layer-wound Gd–Ba–Cu–O (GdBCO) insert coil was fabricated in order to investigate its properties under a high electromagnetic force in a high magnetic field. The GdBCO insert coil was successfully operated at a current of up to 321 A and an electromagnetic force BJR of 408 MPa in an external magnetic field generated by Nb3Sn and Nb–Ti low-temperature superconducting coils. The GdBCO insert coil also managed to generate a magnetic field of 6.8 T at the center of the coil in an external magnetic field of 17.2 T. The superconducting magnet consisting of GdBCO, Nb3Sn and Nb–Ti coils successfully generated a magnetic field of 24.0 T at 4.2 K, which represents a new record for a superconducting magnet.