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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.

The use of spherical rotors for magic angle spinning offers a number of advantages including improved sample exchange, efficient microwave coupling for dynamic nuclear polarization nuclear magnetic resonance (NMR) experiments and, most significantly, high frequency and stable spinning with minimal risk of rotor crash. Here we demonstrate the sim- ple retrofitting of a commercial NMR probe with MAS spheres for solid-state NMR. We analyze a series of turbine groove geometries to investigate the importance of the rotor surface on spinning performance. Of note, rotors lacking any surface modification spin rapidly and stably even without feedback control. The high stability of a spherical rotor about the magic angle is shown to be dependent on its inertia tensor rather than the presence of turbine grooves.

In this work, Cobalt-Ferrite (CFO) films were grown on silicon substrates with 300 nm amorphous silicon dioxide by Pulsed Laser Deposition (PLD) with different annealing conditions. The results of structural analysis prove that the CFO films have high crystalline quality with (1 1 1) preferred orientation. The Raman spectra and X-ray absorption spectra (XAS) indicate that the Co ions can transfer from tetrahedral sites to octahedral sites with increasing the annealing pressure. The site exchange of Co and Fe ions leads to the change of saturation magnetization in the CFO films. Our experiments provide not only a way to control the magnetism of CFO films, but also a suitable magnetic layer to develop silicon and semiconductor based spintronic devices.

Spherical rotors in magic angle spinning (MAS) experiments have significant advantages over traditional cylindrical rotors including simplified spinning implementation, easy sample exchange, more efficient microwave coupling for dynamic nuclear polarization (DNP), and feasibility of downscaling to access higher spinning frequencies. Here, we implement spherical rotors with 4 mm outside diameter (o.d.) and demonstrate spinning >28 kHz using a single aperture for spinning gas. We show a modified stator geometry to improve fiber optic detection, increase NMR filling factor, and improve alignment for sample exchange and microwave irradiation. Higher NMR Rabi frequencies were obtained using smaller radiofrequency (RF) coils on small-diameter spherical rotors, compared to our previous implementation of MAS spheres with an o.d. of 9.5 mm. We report nutation fields of 110 kHz on 13C with 820 W of input power and 100 kHz on 1H with 800 W of input power. Proton decoupling fields of 78 kHz were applied over 20 ms of signal acquisition without any sign of arcing. Compared to our initial demonstration of a split coil for 9.5 mm spheres, this current implementation of a double-saddle coil inductor for 4 mm spheres not only intensifies the RF fields, but also improves RF homogeneity. We achieve an 810°/90° nutation intensity ratio of 0.84 at 300.197 MHz (1H). We also show electromagnetic simulations predicting a nearly 3-fold improvement in electron Rabi frequency of 0.99 MHz (with 4 mm spheres) compared to 0.38 MHz (with 3.2 mm cylinders), with 5 W of incident microwave power. Further improvements in magnetic resonance spin control are expected as RF inductors and microwave coupling are optimized for spherical rotors and scaled down to the micron scale.

Continuous wave dynamic nuclear polarization (DNP) increases the sensitivity of NMR, yet intense microwave fields are required to transition magic angle spinning (MAS) DNP to the time domain. Here we describe and analyze Teflon lenses for cylindrical and spherical MAS rotors that focus microwave power and increase the electron Rabi frequency, ν1s. Using a commercial simulation package, we solve the Maxwell equations and determine the propagation and focusing of millimeter waves (198 GHz). We then calculate the microwave intensity in a time-independent fashion to compute the ν1s. With a nominal microwave power input of 5 W, the average ν1s is 0.38 MHz within a 22 μL sample volume in a 3.2 mm outer diameter (OD) cylindrical rotor without a Teflon lens. Decreasing the sample volume to 3 μL and focusing the microwave beam with a Teflon lens increases the ν1s to 1.5 MHz. Microwave polarization and intensity perturbations associated with diffraction through the radiofrequency coil, losses from penetration through the rotor wall, and mechanical limitations of the separation between the lens and sample are significant challenges to improving microwave coupling in MAS DNP instrumentation. To overcome these issues, we introduce a novel focusing strategy using dielectric microwave lenses installed within spinning rotors. One such 9.5 mm OD cylindrical rotor assembly implements a Teflon focusing lens to increase the ν1s to 2.7 MHz within a 2 μL sample. Further, to access high spinning frequencies while also increasing ν1s, we analyze microwave coupling into MAS spheres. For 9.5 mm OD spherical rotors, we compute a ν1s of 0.36 MHz within a sample volume of 161 μL, and 2.5 MHz within a 3 μL sample placed at the focal point of a novel double lens insert. We conclude with an analysis and discussion of sub-millimeter diamond spherical rotors for time domain DNP at spinning frequencies >100 kHz. Sub-millimeter spherical rotors better overlap a tightly focused microwave beam, resulting in a ν1s of 2.2 MHz. Lastly, we propose that sub-millimeter dielectric spherical microwave resonators will provide a means to substantially improve electron spin control in the future.

Magic angle spinning (MAS) is commonly used in nuclear magnetic resonance of solids to improve spectral resolution. Rather than using cylindrical rotors for MAS, we demonstrate that spherical rotors can be spun stably at the magic angle. Spherical rotors conserve valuable space in the probe head and simplify sample exchange and microwave coupling for dynamic nuclear polarization. In this current implementation of spherical rotors, a single gas stream provides bearing gas to reduce friction, drive propulsion to generate and maintain angular momentum, and variable temperature control for thermostating. Grooves are machined directly into zirconia spheres, thereby converting the rotor body into a robust turbine with high torque. We demonstrate that 9.5–mm–outside diameter spherical rotors can be spun at frequencies up to 4.6 kHz with N 2 (g) and 10.6 kHz with He(g). Angular stability of the spinning axis is demonstrated by observation of 79 Br rotational echoes out to 10 ms from KBr packed within spherical rotors. Spinning frequency stability of ±1 Hz is achieved with resistive heating feedback control. A sample size of 36 μl can be accommodated in 9.5-mm-diameter spheres with a cylindrical hole machined along the spinning axis. We further show that spheres can be more extensively hollowed out to accommodate 161 μl of the sample, which provides superior signal-to-noise ratio compared to traditional 3.2-mm-diameter cylindrical rotors.

Dynamic nuclear polarization (DNP) with cryogenic magic angle spinning (MAS) provides significant improvements in NMR sensitivity, yet presents unique technical challenges. Here we describe a custom cryostat and suite of NMR probes capable of manipulating nuclear spins with multi-resonant radiofrequency circuits, cryogenic spinning below 6 K, sample exchange, and microwave coupling for DNP. The corrugated waveguide and six transfer lines needed for DNP and cryogenic spinning functionality are coupled to the probe from the top of the magnet. Transfer lines are vacuum-jacketed and provide bearing and drive gas, variable temperature fluid, two exhaust pathways, and a sample ejection port. The cryostat thermally isolates the magnet bore, thereby protecting the magnet and increasing cryogen efficiency. This novel design supports cryogenic MAS-DNP performance over an array of probes without altering DNP functionality. We present three MAS probes (two supporting 3.2 mm rotors and one supporting 9.5 mm rotors) interfacing with the single cryostat. Mechanical details, transmission line radio frequency design, and performance of the cryostat and three probes are described.

This study examines the effects of inspiratory muscle warm-up (IMW) on performance and muscle oxygenation during cycling exercise. In a randomized crossover study of 10 female soccer players, the IMW, placebo (IMWP) and control (CON) trials were conducted before two 6-min submaximal cycling exercises (100 and 150W) followed by intermittent high-intensity sprint (IHIS, 6×10s with 60s recovery). The reduction in tissue saturation index (TSI) in legs in the IMW were significantly less than those in IMWP and CON (P

A significant effort has recently been initiated at ETHZ for the development of high frequency, high power, frequency-agile gyrotrons for DNP-NMR spectroscopy. In this context an in house cavity interaction code is under development. In this paper, some details on the development of the new cavity code and the preliminary results will be presented.