High Spinning Frequencies Research Articles

Dipolar Recoupling in Rotating Solids.

Magic angle spinning (MAS) nuclear magnetic resonance (NMR) has evolved significantly over the past three decades and established itself as a vital tool for the structural analysis of biological macromolecules and materials. This review delves into the development and application of dipolar recoupling techniques in MAS NMR, which are crucial for obtaining detailed structural and dynamic information. We discuss a variety of homonuclear and heteronuclear recoupling methods which are essential for measuring spatial restraints and explain in detail the spin dynamics that these sequences generate. We also explore recent developments in high spinning frequency MAS, proton detection, and dynamic nuclear polarization, underscoring their importance in advancing biomolecular NMR. Our aim is to provide a comprehensive account of contemporary dipolar recoupling methods, their principles, and their application to structural biology and materials, highlighting significant contributions to the field and emerging techniques that enhance resolution and sensitivity in MAS NMR spectroscopy.

A novel method for rapidly simulating X-ray pulsar signals at a spacecraft

This paper addresses the challenges posed by the low photon flux and limited atmospheric penetration capabilities of X-ray pulsar signals, which are further exacerbated by technical, economic, and temporal constraints during in-orbit observations. These challenges result in a lack of continuous and high-fidelity data support for ground-based X-ray pulsar navigation (XPNAV) research and validation. To overcome these obstacles, we propose an innovative method for the efficient and rapid simulation of X-ray pulsar signals as received by spacecraft. Building on the physical process that, although the arrival times of the same pulsar signal differ between the spacecraft and the Solar System Barycenter (SSB), these times can be calibrated to the same phase at the SSB using a timing model, we leverage the relationship between the pulsar signal’s arrival rate at the SSB and its arrival phase. Using the Order Statistical Method (OSM), we directly and effectively generate the arrival phase series of pulsar signals received by the spacecraft, which follow a non-homogeneous Poisson process (NHPP). Subsequently, from these phase series, we derive the arrival time series of spacecraft-received pulsar signals, incorporating multiple physical effects based on a relationship model between arrival time series and phases. This method significantly reduces the required simulation time while maintaining high accuracy, thereby greatly enhancing simulation efficiency. Validation against data from the Rossi X-ray Timing Explorer (RXTE) and the Neutron Star Interior Composition Explorer (NICER) shows that the correlation coefficients between the accumulated profiles of simulated and measured data exceed 0.99. Furthermore, our method reduces the simulation time of high-flux pulsar signals by 25.7%, high spin frequency signals by 40.8%, and long observation duration signals by 25.38% compared to the latest fast simulation techniques, highlighting its advantages in accuracy, speed, and versatility for simulating pulsar signals across varying flux rates, spin frequencies, and observation durations. This approach provides continuous and effective data support for XPNAV research, significantly advancing theoretical and practical developments in the field.

Residue-Specific High-Resolution 17O Solid-State Nuclear Magnetic Resonance of Peptides: Multidimensional Indirect 1H Detection and Magic-Angle Spinning.

Oxygen is an integral component of proteins but remains sparsely studied because its only NMR active isotope, 17O, has low sensitivity, low resolution, and large quadrupolar couplings. These issues are addressed here with efficient isotopic labeling, high magnetic fields, fast sample spinning, and 1H detection in conjunction with multidimensional experiments to observe oxygen sites specific to each amino acid residue. Notably, cross-polarization at high sample spinning frequencies provides efficient 13C ↔ 17O polarization transfer. The use of 17O for initial polarization is found to provide better sensitivity per unit time compared to 1H. Sharp isotropic 17O peaks are obtained by using a low-power multiple-quantum sequence, which in turn allows extraction of quadrupolar parameters for each oxygen site. Finally, the potential to determine sequential assignments and long-range distance restraints is demonstrated by using 3D 1H/13C/17O experiments, suggesting that such methods can become an essential tool for biomolecular structure determination.

Highly Efficient Polarizing Agents for MAS‐DNP of Proton‐Dense Molecular Solids

AbstractEfficiently hyperpolarizing proton‐dense molecular solids through dynamic nuclear polarization (DNP) solid‐state NMR is still an unmet challenge. Polarizing agents (PAs) developed so far do not perform well on proton‐rich systems, such as organic microcrystals and biomolecular assemblies. Herein we introduce a new PA, cAsymPol‐POK, and report outstanding hyperpolarization efficiency on 12.76 kDa U‐13C,15N‐labeled LecA protein and pharmaceutical drugs at high magnetic fields (up to 18.8 T) and fast magic angle spinning (MAS) frequencies (up to 40 kHz). The performance of cAsymPol‐POK is rationalized by MAS‐DNP simulations combined with electron paramagnetic resonance (EPR), density functional theory (DFT) and molecular dynamics (MD). This work shows that this new biradical is compatible with challenging biomolecular applications and unlocks the rapid acquisition of 13C–13C and 15N–13C correlations of pharmaceutical drugs at natural isotopic abundance, which are key experiments for structure determination.

Highly Efficient Polarizing Agents for MAS-DNP of Proton-Dense Molecular Solids.

Efficiently hyperpolarizing proton-dense molecular solids through dynamic nuclear polarization (DNP) solid-state NMR is still an unmet challenge. Polarizing agents (PAs) developed so far do not perform well on proton-rich systems, such as organic microcrystals and biomolecular assemblies. Herein we introduce a new PA, cAsymPol-POK, and report outstanding hyperpolarization efficiency on 12.76 kDa U-13 C,15 N-labeled LecA protein and pharmaceutical drugs at high magnetic fields (up to 18.8 T) and fast magic angle spinning (MAS) frequencies (up to 40 kHz). The performance of cAsymPol-POK is rationalized by MAS-DNP simulations combined with electron paramagnetic resonance (EPR), density functional theory (DFT) and molecular dynamics (MD). This work shows that this new biradical is compatible with challenging biomolecular applications and unlocks the rapid acquisition of 13 C-13 C and 15 N-13 C correlations of pharmaceutical drugs at natural isotopic abundance, which are key experiments for structure determination.

Proton-phosphorous connectivities revealed by high-resolution proton-detected solid-state NMR.

Proton-detected solid-state NMR enables atomic-level insight in solid-state reactions, for instance in heterogeneous catalysis, which is fundamental for deciphering chemical reaction mechanisms. We herein introduce a phosphorus-31 radiofrequency channel in proton-detected solid-state NMR at fast magic-angle spinning. We demonstrate our approach using solid-state 1H/31P and 1H/13C correlation experiments at high magnetic fields (850 and 1200 MHz) and high spinning frequencies (100 kHz) to characterize four selected PH-containing compounds from the chemistry of phosphane-borane frustrated Lewis pairs. Frustrated Lewis pairs have gained high interest in the past years, particularly due to their capabilities of activating and binding small molecules, such as di-hydrogen, however, their analytical characterization especially in the solid state is still limited. Our approach reveals proton-phosphorus connectivities providing important information on spatial proximity and chemical bonding within such compounds. We also identify protons that show strongly different chemical-shift values compared to the solution state, which we attribute to intermolecular ring-current effects. The most challenging example presented herein is a cyclotrimeric frustrate Lewis pair-associate comprising three crystallographically distinct phosphonium entities that are unambiguously distinguished by our approach. Such 31P spin-filtered proton-detected NMR can be easily extended to other material classes and can strongly impact the structural characterization of reaction products of hydrogen-activated phosphane/borane FLPs, heterogeneous catalysts and solid-state reactions in general.

Improved NMR transfer of magnetization from protons to half-integer spin quadrupolar nuclei at moderate and high magic-angle spinning frequencies.

Half-integer spin quadrupolar nuclei are the only magnetic isotopes for the majority of the chemical elements. Therefore, the transfer of polarization from protons to these isotopes under magic-angle spinning (MAS) can provide precious insights into the interatomic proximities in hydrogen-containing solids, including organic, hybrid, nanostructured and biological solids. This transfer has recently been combined with dynamic nuclear polarization (DNP) in order to enhance the NMR signal of half-integer quadrupolar isotopes. However, the cross-polarization transfer lacks robustness in the case of quadrupolar nuclei, and we have recently introduced as an alternative technique a -RINEPT (through-space refocused insensitive nuclei enhancement by polarization transfer) scheme combining a heteronuclear dipolar recoupling built from adiabatic pulses and a continuous-wave decoupling. This technique has been demonstrated at 9.4 T with moderate MAS frequencies, -15 kHz, in order to transfer the DNP-enhanced H polarization to quadrupolar nuclei. Nevertheless, polarization transfers from protons to quadrupolar nuclei are also required at higher MAS frequencies in order to improve the H resolution. We investigate here how this transfer can be achieved at and 60 kHz. We demonstrate that the -RINEPT sequence using adiabatic pulses still produces efficient and robust transfers but requires large radio-frequency (rf) fields, which may not be compatible with the specifications of most MAS probes. As an alternative, we introduce robust and efficient variants of the -RINEPT and PRESTO (phase-shifted recoupling effects a smooth transfer of order) sequences using symmetry-based recoupling schemes built from single and composite pulses. Their performances are compared using the average Hamiltonian theory and experiments at T on -alumina and isopropylamine-templated microporous aluminophosphate (AlPO-14), featuring low and significant H-H dipolar interactions, respectively. These experiments demonstrate that the H magnetization can be efficiently transferred to Al nuclei using -RINEPT with (27090) recoupling and using PRESTO with (180) or (27090) schemes at or 62.5 kHz, respectively. The -RINEPT and PRESTO recoupling schemes complement each other since the latter is affected by dipolar truncation, whereas the former is not. We also analyze the losses during these recoupling schemes, and we show how these magnetization transfers can be used at kHz to acquire in 72 min 2D HETCOR (heteronuclear correlation) spectra between H and quadrupolar nuclei, with a non-uniform sampling (NUS).

High frequency dynamic nuclear polarization: New directions for the 21st century.

• We review the current state and future of high frequency dynamic nuclear polarization. • Polarizing agents tailored for experiments at high spinning frequencies are essential. • Microwave sources on the horizon are diodes, klystrons, tunable gyrotrons and amplifiers. • Helium recirculation will enable higher spinning frequencies and lower temperature operation. • High frequency gyroamplifiers will enable pulsed DNP experiments.

Perspectives on microwave coupling into cylindrical and spherical rotors with dielectric lenses for magic angle spinning dynamic nuclear polarization.

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.

PSR J1618−3921: a recycled pulsar in an eccentric orbit

Context.The 11.99 ms pulsar PSR J1618−3921 orbits a He white dwarf companion of probably low mass with a period of 22.7 d. The pulsar was discovered in a survey of the intermediate Galactic latitudes at 1400 MHz that was conducted with the Parkes radio telescope in the late 1990s. Although PSR J1618−3921 was discovered more than 15 years ago, only limited information has been published about this pulsar, which has a surprisingly high orbital eccentricity (e≃ 0.027) considering its high spin frequency and the likely low mass of the companion.Aims.The focus of this work is a precise measurement of the spin and the astrometric and orbital characteristics of PSR J1618−3921. This was done with timing observations made at the Nançay Radio Telescope from 2009 to 2017.Methods.We analyzed the timing data recorded at the Nançay Radio Telescope over several years to characterize the properties of PSR J1618−3921. A rotation ephemeris for this pulsar was obtained by analyzing the arrival times of the radio pulses at the telescope.Results.We confirm the unusual eccentricity of PSR J1618−3921 and discuss several hypotheses regarding its formation in the context of other discoveries of recycled pulsars in eccentric orbits.

Kinematic effects on high order spin frequency derivatives

AbstractThe radial velocity of a pulsar induces the Doppler effect on its intrinsic spin properties. In particular, it can generate a contribution to the frequency second derivative. We estimated this effect for each of the International Pulsar Timing Array pulsars. We also assessed the possibility of measuring the frequency second derivative in the observational data.

Methylammonium lead chloride: A sensitive sample for an accurate NMR thermometer

A new solid-state nuclear magnetic resonance (NMR) thermometry sample is proposed. The 207Pb NMR chemical shift of a lead halide perovskite, methylammonium lead chloride (MAPbCl3) is very sensitive to temperature, 0.905±0.010ppmK−1. The response to temperature is linear over a wide temperature range, from its tetragonal to cubic phase transition at 178K to >410K, making it an ideal standard for temperature calibrations in this range. Because the 207Pb NMR lineshape for MAPbCl3 appears symmetric, the sample is ideal for calibration of variable temperature NMR data acquired for spinning or non-spinning samples. A frequency-ratio method is proposed for referencing 207Pb chemical shifts, based on the 1H and 13C frequencies of the methylammonium cation, which are used asan internal standard. Finally, this new NMR thermometer has been used to measure the degree of frictional heating asa function of spinning frequency for a series of MAS rotors ranging in outer diameter from 1.3 to 7.0mm. As expected, the largest diameter rotors are more susceptible to frictional heating, but lower diameter rotors are subjected to higher frictional heating temperatures as they are typically spun at much higher spinning frequencies.

71Ga-77Se connectivities and proximities in gallium selenide crystal and glass probed by solid-state NMR

We introduce two-dimensional (2D) 71Ga-77Se through-bond and through-space correlation experiments. Such correlations are achieved using (i) the J-mediated Refocused Insensitive Nuclei Enhanced by Polarization Transfer (J-RINEPT) method with 71Ga excitation and 77Se Carr-Purcell-Meiboon-Gill (CPMG) detection, as well as (ii) the J- or dipolar-mediated Hetero-nuclear Multiple-Quantum Correlation (J- or D-HMQC) schemes with 71Ga excitation and quadrupolar CPMG (QCPMG) detection. These methods are applied to the crystalline β-Ga2Se3 and the 0.2Ga2Se3-0.8GeSe2 glass. Such glass leads to a homogeneous and reproducible glass–ceramic, which is a good alternative to single-crystalline Ge and polycrystalline ZnSe materials for making lenses transparent in the IR range for thermal imaging applications. We show that 2D 71Ga-77Se correlation experiments allow resolving the 77Se signals of molecular units, which are not resolved in the 1D 77Se CPMG spectrum. Additionally, the build-up curves of the J-RINEPT and the J-HMQC experiments allow the estimate of the 71Ga-77Se J-couplings via one and three-bonds in the three-dimensional network of β-Ga2Se3. Furthermore, these build-up curves show that the one-bond 1J71Ga-77Se couplings in the 0.2Ga2Se3-0.8GeSe2 glass are similar to those measured for β-Ga2Se3. We also report 2D 71Ga Satellite Transition Magic-Angle Spinning (STMAS) spectrum of β-Ga2Se3 using QCPMG detection at high magnetic field and high Magic-Angle Spinning frequency using large radio frequency field. Such spectrum allows separating the signal of β-Ga2Se3 and that of an impurity.

Dynamic stabilization of Janus sphere trans-dimers.

We experimentally investigated the self-assembly of chemically active colloidal Janus spheres into dimers. The trans-dimer conformation, in which the two active sites are oriented roughly in opposite directions and the particles are osculated at their equators, becomes dominant as the hydrogen peroxide fuel concentration increases. Our observations suggest high spinning frequency combined with little translational motion is at least partially responsible for the stabilization of the trans-dimer as activity increases.

Proton-detected solid-state NMR spectroscopy of fully protonated proteins at slow to moderate magic-angle spinning frequencies

1H-detection offers a substitute to the sensitivity-starved experiments often used to characterize biomolecular samples using magic-angle spinning solid-state NMR spectroscopy (MAS-ssNMR). To mitigate the effects of the strong 1H–1H dipolar coupled network that would otherwise severely broaden resonances, high MAS frequencies (>40kHz) are often employed. Here, we have explored the alternative of stroboscopic 1H-detection at moderate MAS frequencies of 5–30kHz using windowed version of supercycled-phase-modulated Lee-Goldburg homonuclear decoupling. We show that improved resolution in the 1H dimension, comparable to that obtainable at high spinning frequencies of 40–60kHz without homonuclear decoupling, can be obtained in these experiments for fully protonated proteins. Along with detailed analysis of the performance of the method on the standard tri-peptide f-MLF, experiments on micro-crystalline GB1 and amyloid-β aggregates are used to demonstrate the applicability of these pulse-sequences to challenging biomolecular systems. With only two parameters to optimize, broadbanded performance of the homonuclear decoupling sequence, linear dependence of the chemical-shift scaling factor on resonance offset and a straightforward implementation under experimental conditions currently used for many biomolecular studies (viz. spinning frequencies and radio-frequency amplitudes), we expect these experiments to complement the current 13C-detection based methods in assignments and characterization through chemical-shift mapping.

Sensitivity improvement during heteronuclear spin decoupling in solid-state nuclear magnetic resonance experiments at high spinning frequencies and moderate radio-frequency amplitudes

Searching for optimal conditions during one- and multi-dimensional solid-state NMR experiments in high static fields may require spinning the sample at frequencies above 40kHz. This implies challenging requirements for heteronuclear spin decoupling. We have compared the performance of the latest heteronuclear decoupling schemes at high magic-angle spinning frequencies. The results demonstrate that at commonly used rf amplitudes between 80 and 120kHz, PISSARRO decoupling provides substantial sensitivity improvement. The performance of low-amplitude decoupling at different spinning speeds is also compared and its dependence on the inherent inhomogeneity of the rf field is probed by numerical simulations.

Rapid Proton-Detected NMR Assignment for Proteins with Fast Magic Angle Spinning

Using a set of six 1H-detected triple-resonance NMR experiments, we establish a method for sequence-specific backbone resonance assignment of magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of 5–30 kDa proteins. The approach relies on perdeuteration, amide 2H/1H exchange, high magnetic fields, and high-spinning frequencies (ωr/2π ≥ 60 kHz) and yields high-quality NMR data, enabling the use of automated analysis. The method is validated with five examples of proteins in different condensed states, including two microcrystalline proteins, a sedimented virus capsid, and two membrane-embedded systems. In comparison to contemporary 13C/15N-based methods, this approach facilitates and accelerates the MAS NMR assignment process, shortening the spectral acquisition times and enabling the use of unsupervised state-of-the-art computational data analysis protocols originally developed for solution NMR.

Instability windows and evolution of rapidly rotating neutron stars.

We consider an instability of rapidly rotating neutron stars in low-mass x-ray binaries (LMXBs) with respect to excitation of r modes (which are analogous to Earth's Rossby waves controlled by the Coriolis force). We argue that finite temperature effects in the superfluid core of a neutron star lead to a resonance coupling and enhanced damping (and hence stability) of oscillation modes at certain stellar temperatures. Using a simple phenomenological model we demonstrate that neutron stars with high spin frequency may spend a substantial amount of time at these "resonance" temperatures. This finding allows us to explain puzzling observations of hot rapidly rotating neutron stars in LMXBs and to predict a new class of hot, nonaccreting, rapidly rotating neutron stars, some of which may have already been observed and tentatively identified as quiescent LMXB candidates. We also impose a new theoretical limit on the neutron star spin frequency, which can explain the cutoff spin frequency ∼730 Hz, following from the statistical analysis of accreting millisecond x-ray pulsars. In addition to explaining the observations, our model provides a new tool to constrain superdense matter properties by comparing measured and theoretically predicted resonance temperatures.

Efficiency at high spinning frequencies of heteronuclear decoupling methods designed to quench rotary resonance

The performance of two recently developed heteronuclear decoupling schemes designed to quench rotary resonance, phase-inverted supercycled sequence for attenuation of rotary resonance (PISSARRO) and high-phase two-pulse phase modulation (high-phase TPPM), are probed at high spinning frequencies. High-phase TPPM may be useful at the n=1 rotary resonance condition while PISSARRO permits efficient decoupling over a broad commonly used range of rf amplitudes, even at very high spinning frequencies. New insights into the response of spin systems to both decoupling schemes have been gained. High-phase TPPM is sensitive to the offsets of remote protons, their chemical shift anisotropies, and the relative orientations of the heteronuclear dipolar and proton chemical shift tensors. Since PISSARRO is virtually immune against such effects, the method is especially suited for very high magnetic fields.

Sensitive 13C–13C correlation spectra of amyloid fibrils at very high spinning frequencies and magnetic fields

Sensitive 2D solid-state (13)C-(13)C correlation spectra of amyloid β fibrils have been recorded at very fast spinning frequencies and very high magnetic fields. It is demonstrated that PARIS-xy recoupling using moderate rf amplitudes can provide structural information by promoting efficient magnetization transfer even under such challenging experimental conditions. Furthermore, it has been shown both experimentally and by numerical simulations that the method is not very sensitive to dipolar truncation effects and can reveal direct transfer across distances of about 3.5-4 Å.