Cryogenic-compatible spherical rotors and stators for magic angle spinning dynamic nuclear polarization

Cryogenic magic angle spinning (MAS) is a standard technique utilized for dynamic nuclear polarization (DNP) in solid-state nuclear magnetic resonance (NMR). Here we describe the optimization and implementation of a stator for cryogenic MAS with 9.5gmm diameter spherical rotors, allowing for DNP experiments on large sample volumes. Designs of the stator and rotor for cryogenic MAS build on recent advancements of MAS spheres and take a step further to incorporate sample insert and eject and a temperature-independent spinning stability of ±1gHz. At a field of 7gT and spinning at 2.0gkHz with a sample temperature of 105-107gK, DNP enhancements of 256 and 200 were observed for 124 and 223gμL sample volumes, respectively, each consisting of 4gM 13C, 15N-labeled urea and 20gmM AMUPol in a glycerol-water glassy matrix.ISSN:2699-001

Improving the sensitivity of MAS spheres using a 9.5 mm spherical shell with 219 μL sample volume spinning in a spherical solenoid coil

Spherical rotors in magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments have potential advantages relative to cylindrical rotors in terms of ease of fabrication, low risk of rotor crash, easy sample exchange, and better microwave access. However, one major disadvantage so far of spherical rotors is poor NMR filling factor due to the small sample volume and large cylindrical radiofrequency (RF) coil. Here we present a novel NMR coil geometry in the form of a spherical coil. The spherical coil best fits the spherical sample to maximize sensitivity, while also providing excellent RF homogeneity. We further improve NMR sensitivity by employing a spherical shell as the rotor, thereby maximizing sample volume (219 μL in this case of 9.5 mm outer diameter spheres). The spinning gas is supplied by a 3D-printed ring stator external to the coil, thereby introducing a simplified form of MAS stators. In this apparatus, the RF field generated along the coil axis is perpendicular to the external magnetic field, regardless of rotor orientation. We observe a linear increase in sensitivity with increasing sample volume. We also simulate the RF performance of spherical and cylindrical solenoid coils with constant or variable pitch for spherical and cylindrical rotors, respectively. The simulation results show that spherical solenoid coils generate comparable B1 field intensities but have better homogeneity than cylindrical solenoid coils do.ISSN:1090-780

Nucleotide Binding Modes in a Motor Protein Revealed by 31 P‐ and 1 H‐Detected MAS Solid‐State NMR Spectroscopy

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Cross-polarization for dissolution dynamic nuclear polarization

Dynamic nuclear polarization (DNP) in combination with subsequent dissolution of the sample allows the detection of low-γ nuclei in the solution state with a signal gain of up to tens of thousand times compared to experiments starting from Boltzmann conditions. The long polarization build-up times of typically more than one hour are a drawback of this technique. The combination of dissolution DNP with cross-polarization (CP) in the solid state was shown to have the potential to overcome this disadvantage. In this article we discuss the cross-polarization step under dissolution DNP conditions in more detail. We show that adiabatic half-passage pulses allow us to enhance the CP efficiency in power-limited DNP probes. As a low-power alternative to Hartmann–Hahn CP we also demonstrate the applicability of frequency-swept de- and re-magnetization pulses for polarization transfer via dipolar order. We investigate the implications and restrictions of the common solid-state DNP mechanisms to the DNP–CP technique and apply a spin-thermodynamic model based on the thermal-mixing mechanism. The model allows us to investigate the dynamics of the polarization levels in a system with two nuclear Zeeman reservoirs and explains the enhanced DNP efficiency upon solvent deuteration within a spin-thermodynamic picture

A spin-thermodynamic approach to characterize spin dynamics in TEMPO-based samples for dissolution DNP at 7 T field

The spin dynamics of dissolution DNP samples consisting of 4.5 M [13C]urea in a mixture of (1/1)Vol glycerol/water using 4-Oxo-TEMPO as a radical was investigated. We analyzed the DNP dynamics as function of radical concentration at 7 T and 3.4 T static magnetic field as well as function of deuteration of the solvent matrix at the high field. The spin dynamics could be reproduced in all cases, at least qualitatively, by a thermodynamic model based on spin temperatures of the nuclear Zeeman baths and an electron non-Zeeman (dipolar) bath. We find, however, that at high field (7 T) and low radical concentrations (25 mM) the nuclear spins do not reach the same spin temperature indicating a weak coupling of the two baths. At higher radical concentrations, as well as for all radical concentrations at low field (3.4 T), the two nuclear Zeeman baths reach the same spin temperature within experimental errors. Additionally, the spin system was prepared with different initial conditions. For these cases, the thermodynamic model was able to predict the time evolution of the system well. While the DNP profiles do not give clear indications to a specific polarization transfer mechanism, at high field (7 T) increased coupling is seen. The EPR line shapes cannot clarify this in absence of ELDOR type experiments, nevertheless DNP profiles and dynamics under frequency-modulated microwave irradiation illustrate the expected increase in coupling between electrons with increasing radical concentration

Dissolution dynamic nuclear polarization efficiency enhanced by Hartmann–Hahn cross polarization

Dynamic nuclear polarization (DNP) can be used to increase the polarization of nuclei by utilizing the higher electron polarization. Typically, in dissolution DNP heteronuclei are directly polarized due to their longer relaxation times. We present the combination of DNP to protons with subsequent cross polarization to 13C followed by dissolution to solution state. The experiment was implemented using a modified dissolution DNP probe. For a [13C]urea sample doped with TEMPO the carbon polarization and its build-up rate could be increased by a factor of two using CP. With small losses, this gain could be transferred to the solution by dissolution

Dissolution DNP using trityl radicals at 7 T field

Characterization of direct 13C DNP at 1.4 K and 7 T field using trityl radicals