In order to better understand the structure and dynamics of methylammonium lead halide perovskites, we performed NMR, NQR, and DFT studies of CHNHPbI in the tetragonal and cubic phase. Our results indicate that the space group of the tetragonal phase is the nonpolar I4/mcm. The highly dynamic methylammonium moiety shows no indication of the occurrence of additional orientations of the C-N bond close to the c-axis at temperatures approaching the cubic phase. Crystal quality effects are shown to influence the N NMR andI NQR spectra, and the effects of high-temperature annealing on defects can be observed. A strong increase in T relaxation time of the Pb NMR signal on cooling is found, and is an indication of slow motions in the PbI octahedra at room temperature. These results aid in the understanding of the structure of methylammonium lead halides and enable further studies of defects in these materials.
Nuclear magnetic resonance (NMR) techniques play an essential role in natural science and medicine. In spite of the tremendous utility associated with the small energies detected, the most severe limitation is the low signal‐to‐noise ratio. Dynamic nuclear polarization (DNP), a technique based on transfer of polarization from electron to nuclear spins, has emerged as a tool to enhance sensitivity of NMR. However, the approach in liquids still faces several challenges. Herein we report the observation of room‐temperature, liquid DNP 13C signal enhancements in organic small molecules as high as 600 at 9.4 Tesla and 800 at 1.2 Tesla. A mechanistic investigation of the 13C‐DNP field dependence shows that DNP efficiency is raised by proper choice of the polarizing agent (paramagnetic center) and by halogen atoms as mediators of scalar hyperfine interaction. Observation of sizable DNP of 13CH2 and 13CH3 groups in organic molecules at 9.4 T opens perspective for a broader application of this method.
We demonstrate that solid-state NMR spectra of challenging nuclei with a low gyromagnetic ratio such as yttrium-89 can be acquired quickly with indirect dynamic nuclear polarization (DNP) methods. Proton to 89Y cross polarization (CP) magic angle spinning (MAS) spectra of Y3+ in a frozen aqueous solution were acquired in minutes using the AMUPol biradical as a polarizing agent. Subsequently, the detection of the 89Y and 1H NMR signals from technologically important hydrated yttrium-doped zirconate ceramics, in combination with DFT calculations, allows the local yttrium and proton environments present in these protonic conductors to be detected and assigned to different hydrogen-bonded environments.
Recent advances in the structural biology of disease-relevant α-synuclein fibrils have revealed a variety of structures, yet little is known about the process of fibril aggregate formation. Characterization of intermediate species that form during aggregation is crucial; however, this has proven very challenging because of their transient nature, heterogeneity, and low population. Here, we investigate the aggregation of α-synuclein bound to negatively charged phospholipid small unilamellar vesicles. Through a combination of kinetic and structural studies, we identify key time points in the aggregation process that enable targeted isolation of prefibrillar and early fibrillar intermediates. By using solid-state nuclear magnetic resonance, we show the gradual buildup of structural features in an α-synuclein fibril filament, revealing a segmental folding process. We identify distinct membrane-binding domains in α-synuclein aggregates, and the combined data are used to present a comprehensive mechanism of the folding of α-synuclein on lipid membranes.
A structural characterization of the hydrated form of the brownmillerite-type phase Ba2In2O5, Ba2In2O4(OH)2, is reported using experimental multinuclear NMR spectroscopy and density functional theory (DFT) energy and GIPAW NMR calculations. When the oxygen ions from H2O fill the inherent O vacancies of the brownmillerite structure, one of the water protons remains in the same layer (O3) while the second proton is located in the neighboring layer (O2) in sites with partial occupancies, as previously demonstrated by Jayaraman et al. (Solid State Ionics20041702532) using X-ray and neutron studies. Calculations of possible proton arrangements within the partially occupied layer of Ba2In2O4(OH)2 yield a set of low energy structures; GIPAW NMR calculations on these configurations yield 1H and 17O chemical shifts and peak intensity ratios, which are then used to help assign the experimental MAS NMR spectra. Three distinct 1H resonances in a 2:1:1 ratio are obtained experimentally, the most intense resonance being assigned to the proton in the O3 layer. The two weaker signals are due to O2 layer protons, one set hydrogen bonding to the O3 layer and the other hydrogen bonding alternately toward the O3 and O1 layers. 1H magnetization exchange experiments reveal that all three resonances originate from protons in the same crystallographic phase, the protons exchanging with each other above approximately 150 °C. Three distinct types of oxygen atoms are evident from the DFT GIPAW calculations bare oxygens (O), oxygens directly bonded to a proton (H-donor O), and oxygen ions that are hydrogen bonded to a proton (H-acceptor O). The 17O calculated shifts and quadrupolar parameters are used to assign the experimental spectra, the assignments being confirmed by 1H–17O double resonance experiments.
While solid-state NMR spectroscopic techniques have helped clarify the local structure and dynamics of ionic conductors, similar studies of mixed ionic–electronic conductors (MIECs) have been hampered by the paramagnetic behavior of these systems. Here we report high-resolution 17O (I = 5/2) solid-state NMR spectra of the mixed-conducting solid oxide fuel cell (SOFC) cathode material La2NiO4+δ, a paramagnetic transition-metal oxide. Three distinct oxygen environments (equatorial, axial, and interstitial) can be assigned on the basis of hyperfine (Fermi contact) shifts and quadrupolar nutation behavior, aided by results from periodic DFT calculations. Distinct structural distortions among the axial sites, arising from the nonstoichiometric incorporation of interstitial oxygen, can be resolved by advanced magic angle turning and phase-adjusted sideband separation (MATPASS) NMR experiments. Finally, variable-temperature spectra reveal the onset of rapid interstitial oxide motion and exchange with axial sites at ∼130 °C, associated with the reported orthorhombic-to-tetragonal phase transition of La2NiO4+δ. From the variable-temperature spectra, we develop a model of oxide-ion dynamics on the spectral time scale that accounts for motional differences of all distinct oxygen sites. Though we treat La2NiO4+δ as a model system for a combined paramagnetic 17O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides.
Pathological aggregation of the protein tau into insoluble aggregates is a hallmark of neurodegenerative diseases. The emergence of disease-specific tau aggregate structures termed tau strains, however, remains elusive. Here we show that full-length tau protein can be aggregated in the absence of co-factors into seeding-competent amyloid fibrils that sequester RNA. Using a combination of solid-state NMR spectroscopy and biochemical experiments we demonstrate that the co-factor-free amyloid fibrils of tau have a rigid core that is similar in size and location to the rigid core of tau fibrils purified from the brain of patients with corticobasal degeneration. In addition, we demonstrate that the N-terminal 30 residues of tau are immobilized during fibril formation, in agreement with the presence of an N-terminal epitope that is specifically detected by antibodies in pathological tau. Experiments in vitro and in biosensor cells further established that co-factor-free tau fibrils efficiently seed tau aggregation, while binding studies with different RNAs show that the co-factor-free tau fibrils strongly sequester RNA. Taken together the study provides a critical advance to reveal the molecular factors that guide aggregation towards disease-specific tau strains.
The available magnetic field strength for high resolution NMR in persistent superconducting magnets has recently improved from 23.5 to 28 Tesla, increasing the proton resonance frequency from 1 to 1.2 GHz. For magic-angle spinning (MAS) NMR, this is expected to improve resolution, provided the sample preparation results in homogeneous broadening. We compare two-dimensional (2D) proton detected MAS NMR spectra of four membrane proteins at 950 and 1200 MHz. We find a consistent improvement in resolution that scales superlinearly with the increase in magnetic field for three of the four examples. In 3D and 4D spectra, which are now routinely acquired, this improvement indicates the ability to resolve at least 2 and 2.5 times as many signals, respectively.
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