Magic Angle Spinning NMR Spectroscopy Research Articles

Trapping of different stages of BaTiO3 reduction with LiH.

We investigated the hydride reduction of tetragonal BaTiO3 using LiH. The reactions employed molar H : BaTiO3 ratios of 1.2, 3, and 10 and variable temperatures up to 700 °C. The air-stable reduced products were characterized by powder X-ray diffraction (PXRD), scanning electron microscopy, thermogravimetric analysis (TGA), X-ray fluorescence (XRF), and 1H magic-angle spinning (MAS) NMR spectroscopy. Effective reduction, as indicated by the formation of dark blue to black colored, cubic-phased, products was observed at temperatures as low as 300 °C. The product obtained at 300 °C corresponded to oxyhydride BaTiO∼2.9H∼0.1, whereas reduction at higher temperatures resulted in simultaneous O defect formation, BaTiO2.9−xH0.1□x, and eventually – at temperatures above 450 °C – to samples void of hydridic H. Concomitantly, the particles of samples reduced at high temperatures (500–600 °C) display substantial surface alteration, which is interpreted as the formation of a TiOx(OH)y shell, and sintering. Diffuse reflectance UV-VIS spectroscopy shows broad absorption in the VIS-NIR region, which is indicative of the presence of n-type free charge carriers. The size of the intrinsic band gap (∼3.2 eV) appears only slightly altered. Mott–Schottky measurements confirm the n-type conductivity and reveal shifts of the conduction band edge in the LiH reduced samples. Thus LiH appears as a versatile reagent to produce various distinct forms of reduced BaTiO3 with tailored electronic properties.

Synthesis of anionic ionic liquids@TpBd-(SO3)2 for the selective adsorption of cationic dyes with superior capacity.

The discharge of industrial printing and dyeing wastewater is one of the main reasons for the increasing water shortage and deterioration. The treatment of dyestuff wastewater is an issue and needs to be urgently solved. In this work, anionic ionic liquid functional covalent organic materials (COMs) were firstly synthesized and used for the selective adsorption of cationic dyes. First, a series of sulfonic acid group (SO3H)-functionalized anionic TpPa-SO3, TpBd-(SO3)2, and TpCR-(SO3)2 were prepared, respectively, and then imidazole was grafted onto TpBd-(SO3)2 to obtain ImI@TpBd-(SO3)2. The full characterization using X-ray diffraction, FT-IR spectroscopy, 13C cross-polarization magic-angle spinning NMR spectroscopy, zeta-potentials, BET surface and pore analysis indicated that these COMs and ImI@TpBd-(SO3)2 exhibited different morphologies, porosities, and potentials. The effects of the type of dye, adsorption time, initial dye concentration, and pH on the adsorption of dyes on ImI@TpBd-(SO3)2 were systematically investigated, respectively. The results revealed that ImI@TpBd-(SO3)2 possessed good adsorption performance for nine different cationic dyes with adsorption capacities in the range from 2865.3 mg g−1 for methylene blue (MB) to 597.9 mg g−1 for basic orange 2 (BO), but little adsorption for anionic and neutral dyes, revealing charge selectivity. The adsorption ratio of ImI@TpBd-(SO3)2 for MB was as high as 74.0% at 10 min by using 1.0 mg material, owing to the post modification of TpBd-(SO3)2 with imidazole. The adsorption of MB on ImI@TpBd-(SO3)2 was pH dependent. The adsorption isotherm and kinetics fitted well with the Freundlich and pseudo second-order kinetic model, respectively. Finally, the very outstanding advantages of superior selective adsorption, desorption, convenient preparation, and low density of ImI@TpBd-(SO3)2 predicted its research and application potential in dye wastewater recovery.

Revealing Intermolecular Hydrogen Bonding Structure and Dynamics in a Deep Eutectic Pharmaceutical by Magic-Angle Spinning NMR Spectroscopy.

Liquid forms of pharmaceuticals (ionic liquids and deep eutectic solvents) offer a number of potential advantages over solid-state drugs; a key question is the role of intermolecular hydrogen bonding interactions in enabling membrane transport. Characterization is challenging since high sample viscosities, typical of liquid pharmaceutical formulations, hamper the use of conventional solution NMR at ambient temperature. Here, we report the application of magic-angle spinning (MAS) NMR spectroscopy to the deep eutectic pharmaceutical, lidocaine ibuprofen. Using variable temperature MAS NMR, the neat system, at a fixed molar ratio, can be studied over a wide range of temperatures, characterized by changing mobility, using a single experimental setup. Specific intermolecular hydrogen bonding interactions are identified by two-dimensional 1H–1H NOESY and ROESY MAS NMR experiments. Hydrogen-bonding dynamics are quantitatively determined by following the chemical exchange process between the labile protons by means of line-width analysis of variable temperature 1H MAS NMR spectra.

Density Functional Theory-Assisted 31P and 23Na Magic-Angle Spinning Nuclear Magnetic Resonance Study of the Na3V2(PO4)2F3–Na3V2(PO4)2FO2 Solid Solution: Unraveling Its Local and Electronic Structures

The local and electronic structures of Na3V2(PO4)2F3–Na3V2(PO4)2FO2 electrode materials have been investigated by a combination of 23Na and 31P magic-angle spinning NMR spectroscopy and density fun...

Physicochemical and Catalytic Properties of Ni,H/ZSM-5 and Ni,H/ZSM-5–Binder Catalysts Prepared in the Absence and in the Presence of Binder

Physicochemical and catalytic properties of H/ZSM-5 and Ni,H/ZSM-5 along with Ni,H/ZSM-5–Al2O3 (1 : 1) systems were examined. The systems with a binder were prepared by two different methods of mixing zeolite with aluminum hydroxide. The samples were characterized by N2 sorption (at 77 K), X-ray diffraction, 27Al magic-angle spinning (MAS) NMR spectroscopy, temperature-programmed desorption of ammonia and adsorption of pyridine. Preparation of the zeolite catalyst with aluminium hydroxide was made by two methods: (1) mixing of powders and (2) combining appropriate pastes. Regardless of the method used for mixing there was no blocking of zeolite channels by aluminum oxide. The method of mixing zeolite with aluminium hydroxide powders promotes migration of aluminum from aluminum hydroxide/oxide to the zeolite framework. The results of n-hexane conversion showed that with Ni,H/ZSM-5 a slightly lower conversion than with H/ZSM-5 catalyst was observed that can be explained by a reduced yield of cracking products. Ni,H/ZSM-5–Al2O3 (1 : 1) catalytic systems were insignificantly less efficient in n-hexane transformation than alumina free samples but at the same time they were less selective towards hydrocarbons with boiling temperatures higher than this of n-hexane, precursors of carbonaceous deposits.

Unraveling the Dynamic Network in the Reactions of an Alkyl Aryl Ether Catalyzed by Ni/γ-Al2O3 in 2-Propanol.

The reductive cleavage of aryl ether linkages is a key step in the disassembly of lignin to its monolignol components, where selectivity is determined by the kinetics of multiple parallel and consecutive liquid-phase reactions. Triphasic hydrogenolysis of 13C-labeled benzyl phenyl ether (BPE, a model compound for the major β-O-4 linkage in lignin), catalyzed by Ni/γ-Al2O3, was observed directly at elevated temperatures (150-175 °C) and pressures (79-89 bar) using operando magic-angle spinning NMR spectroscopy. Liquid-vapor partitioning in the NMR rotor was quantified using the 13C NMR resonances for the 2-propanol solvent, whose chemical shifts report on the internal reactor temperature. At 170 °C, BPE is converted to toluene and phenol with k1 = 0.17 s-1 gcat-1 and an apparent activation barrier of (80 ± 8) kJ mol-1. Subsequent phenol hydrogenation occurs much more slowly (k2 = 0.0052 s-1 gcat-1 at 170-175 °C), such that cyclohexanol formation is significant only at higher temperatures. Toluene is stable under these reaction conditions, but its methyl group undergoes facile H/D exchange (k3 = 0.046 s-1 gcat-1 at 175 °C). While the source of the reducing equivalents for both hydrogenolysis and hydrogenation is exclusively H2/D2(g) rather than the alcohol solvent at these temperatures, the initial isotopic composition of adsorbed H/D on the catalyst surface is principally determined by the solvent isotopic composition (2-PrOH/D). All reactions are preceded by a pronounced induction period associated with catalyst activation. In air, Ni nanoparticles are passivated by a surface oxide monolayer, whose removal under H2 proceeds with an apparent activation barrier of (72 ± 13) kJ mol-1. The operando NMR spectra provide molecularly specific, time-resolved information about the multiple simultaneous and sequential processes as they occur at the solid-liquid interface.

Investigating the Dynamic Behavior of Zinc Oxide Discharge Product in Rechargeable Zinc Electrodes

Rechargeable zinc-alkaline batteries are attractive alternatives to established battery technologies such as lithium-ion and lead-acid in certain applications because of their inherent low cost, safety, and environmental friendliness. Commercialization of zinc-alkaline batteries has been largely unsuccessful because of the limited cycle life of zinc electrodes at high depth of discharge. At high depths of discharge, dissolved zinc precipitates from the electrolyte as solid zinc oxide. Zinc oxide buildup causes passivation of zinc metal particles, which increases resistance within the battery and results in eventual cell death. It can also electrically isolate metal particles from the current collector, resulting in loss of active zinc mass. Zinc oxide in alkaline batteries has been studied for decades, but an understanding of the properties of the material and effects on battery performance is still not complete. A complete understanding of the discharge products of zinc electrodes is a necessary step toward wide-spread commercialization of zinc metal electrodes. We demonstrate in this work that zinc oxide produced during discharge undergoes chemical changes as a function of electrode potential. In operando optical microscopy shows that the oxide reversibly changes color from blue at more negative zinc electrode potentials to white at more positive zinc electrode potentials. In operando Raman spectroscopy shows differences in Raman scattering between the blue and the white oxide species, indicating that additional bonds are present in the blue material, which are not observed in the white material. Solid-state 1H magic angle spinning NMR spectroscopy on extracted oxide material suggests that changes to electrode potential result in simultaneous insertion or disinsertion of protons and electrons into the oxide material. More immobile species are present in the blue material compared to the white, indicating inserted protons may be more abundant in the blue oxide. Additionally, two-dimensional 1H-1H exchange spectroscopy shows more chemical exchange between sites in the white material compared to the blue, indicating protons may be more strongly bound in the blue oxide. The behavior observed in these studies is similar to that observed for electrochromic materials. In electrochromic materials, inserted electrons can increase the electrical conductivity of the oxide by orders of magnitude. At more positive zinc potentials, an increase in the electrical resistance of the oxide may result in conductivity losses between zinc metal particles. Additionally, when protons are disinserted from the oxide, they result in a local pH decrease in the electrolyte surrounding the oxide, which affects the ionic conductivity of the electrolyte. The work outlined in this study demonstrates the effects of this behavior on electrode performance and explores avenues for controlling the behavior through electrode additives and operation controls. Figure 1

Conformational Flexibility of p150Glued(1–191) Subunit of Dynactin Assembled with Microtubules

Microtubule (MT)-associated proteins perform diverse functions in cells. These functions are dependent on their interactions with MTs. Dynactin, a cofactor of dynein motor, assists the binding of dynein to various organelles and is crucial to the long-distance processivity of dynein-based complexes. The largest subunit of dynactin, the p150Glued, contains an N-terminus segment that is responsible for the MT-binding interactions and long-range processivity of dynactin. We employed solution and magic angle spinning NMR spectroscopy to characterize the structure and dynamics of the p150Glued N-terminal region, both free and in complex with polymerized MTs. This 191-residue region encompasses the cytoskeleton-associated protein glycine-rich domain, the basic domain, and serine/proline-rich (SP-rich) domain. We demonstrate that the basic and SP-rich domains are intrinsically disordered in solution and significantly enhance the binding affinity to MTs as these regions contain the second MT-binding site on the p150Glued subunit. The majority of the basic and SP-rich domains are predicted to be random coil, whereas the segments S111–I116, A124–R132, and K144–T146 in the basic domain contain short α-helical or β-sheet structures. These three segments possibly encompass the MT-binding site. Surprisingly, the protein retains a high degree of flexibility upon binding to MTs except for the regions that are directly involved in the binding interactions with MTs. This conformational flexibility may be essential for the biological functions of the p150Glued subunit.

Advanced solid-state 1H/31P NMR characterization of pyrophosphate-doped calcium phosphate cements for biomedical applications: The structural role of pyrophosphate

From a suite of advanced magic-angle spinning (MAS) NMR spectroscopy and powder X-ray diffraction (PXRD) experiments, we present a comprehensive structural analysis of pyrophosphate-bearing calcium ...

From 3D to 2D: Structural, Spectroscopic and Theoretical Investigations of the Dimensionality Reduction in the [PtAl2 ]δ- Polyanions of the Isotypic MPtAl2 Series (M=Ca-Ba, Eu).

Four new MPtAl2 (M=Ca, Sr, Ba, Eu) compounds, adopting the orthorhombic MgCuAl2 -type structure, have been synthesized from the elements using tantalum ampoules. All compounds are obtained as platelet-shaped crystallites and exhibit an increasing moisture sensitivity with increasing size of the formal M cation. Structural investigations indicate a pronounced elongation of the crystallographic b-axis, which results in a significant distortion of the [PtAl2 ]δ- polyanion. Within the polyanion, layer-like arrangements can be found with bonding Pt-Al interactions within the slab; the increase of the b-axis can be attributed to increasing Al-Al distances and therefore decreasing interactions between the slabs, caused by the differently-sized formal M cations. While the alkaline earth (M=Ca, Sr) representatives exhibit Pauli paramagnetism, BaPtAl2 shows diamagnetic behavior, finally EuPtAl2 is ferromagnetic with TC =54.0(5) K. The effective magnetic moment indicates that the Eu atoms are in a divalent oxidation state, which is confirmed by 151 Eu Mössbauer spectroscopic investigations. Measurements below the Curie-temperature show a full magnetic hyperfine field splitting with Bhf =21.7(1) T. 27 Al and 195 Pt magic-angle spinning NMR spectroscopy corroborates the presence of single crystallographic sites for the Pt and Al atoms. The large 27 Al nuclear electric quadrupolar coupling constants confirm unusually strong electric field gradients, in agreement with the structural distortions and the respective theoretical calculations. X-ray photoelectron spectroscopy has been utilized to investigate the charge transfer within the polyanion. The Pt 4f binding energy decreases with decreasing electronegativity / ionization energy of the alkaline earth elements, suggesting an increasing electron density at the Pt atoms. Theoretical investigations underline the platinide character of the investigated compounds by Bader charge calculations. The analysis of the integrated crystal orbital Hamilton population (ICOHP) values, electron localization function (ELF) and isosurface analyses lead to a consistent structural picture, indicating stable layer-like arrangements of the [PtAl2 ]δ- polyanion.

Fluorination of Li‐Rich Lithium‐Ion‐Battery Cathode Materials by Fluorine Gas: Chemistry, Characterization, and Electrochemical Performance in Half Cells

AbstractMild fluorination of high‐energy nickel‐cobalt‐manganese (HE‐NCM) materials with low pressures of elementary fluorine gas (F2) at room temperature was systematically studied. The fluorinated HE‐NCM samples were analysed by ion chromatography, inductively coupled plasma mass spectrometry, FT‐IR spectroscopy, powder X‐ray diffraction, magic angle spinning NMR spectroscopy, scanning electron microscopy, thermo‐gravimetric analysis, differential thermal analysis, electrochemical testing, and X‐ray photoelectron spectroscopy. The treatment of the cathode materials with low pressures (a few hundred mbar) of elementary fluorine gas at room temperature led to the elimination of the basic surface film (LiOH, Li2CO3, Li2O, etc.), and the resulting thin amorphous LiF film led to increased capacity and long‐term stability of the battery. Impedance built‐up was greatly reduced for these systems throughout cycling. Fluorination with F2 only causes the formation of O−Me−F bonds (Me=Transition Metal), when treated with F2 at higher pressures. If O−Me−F bonds are formed, it may be detrimental to the electrode surface film resistance and cycle stability of the electrodes. However, it may be that the LiF surface content, which can expand as long as the LiMeO2 structure can be oxidized and Li+ can be extracted, has become too large and thus detrimental. Considering the evolution of differential capacity plots and taking into account the thermodynamic driving force of the F2 treatment, it is likely that the same activation processes that occur electrochemically in Li‐rich materials also occur chemically, when the material is exposed to F2. Differential capacity plots show enhanced Mn4+ reduction peaks upon lithiation, when the material was exposed to F2, only possible after activation of the Li2MnO3 phase. For this reason, we believe fluorination promotes to some extent an activation of this phase.

Introduction to Covalent Organic Frameworks: An Advanced Organic Chemistry Experiment

In order to introduce the concept of covalent organic frameworks (COFs), an important class of predictable crystalline porous polymers, an integrated laboratory experiment for advanced organic chemistry students is reported. The importance of these kind of polymers and their multiple applications are presented as a part of key concepts in polymer and organic chemistry, bridging these disciplines to materials science. Students carry out the synthesis and characterization of an imine-linked COF and its building blocks. The polymer is formed at room temperature by using solvent-assisted synthesis and mechanochemistry. Students are trained in solid state characterization techniques, including FTIR spectroscopy, thermogravimetric analysis (TGA), 13C NMR cross-polarization–magic angle spinning (CP-MAS) NMR spectroscopy, and powder X-ray diffraction (PXRD), which are essential in the important field of reticular chemistry. Therefore, this lab experience constitutes a practical introduction to COFs.

Measurement of ligand coverage on cadmium selenide nanocrystals and its influence on dielectric dependent photoluminescence intermittency

Photoluminescent quantum dots are used in a range of applications that exploit the unique size tuneable emission, light harvesting and quantum efficient properties of these semiconductor nanocrystals. However, optical instabilities such as photoluminescence intermittency, the stochastic switching between bright, emitting states and dark states, can hinder quantum dot performance. Correlations between this blinking of emission and the dielectric properties of the nanoenvironment between the quantum dot interface and host medium, suggest surface ligands play a role in modulating on-off switching rates. Here we elucidate the nature of the cadmium selenide nanocrystal surface, by combining magic angle spinning NMR and x-ray photoelectron spectroscopy to determine ligand surface densities, with molecular dynamics simulation to assess net ligand filling at the nanocrystal interface. Results support a high ligand coverage and are consistent with photoluminescence intermittency measurements that indicate a dominant contribution from surface ligand to the dielectric properties of the local quantum dot environment.

Dynamic Nuclear Polarization Magic-Angle Spinning Nuclear Magnetic Resonance Combined with Molecular Dynamics Simulations Permits Detection of Order and Disorder in Viral Assemblies

We report dynamic nuclear polarization (DNP)-enhanced magic-angle spinning (MAS) NMR spectroscopy in viral capsids from HIV-1 and bacteriophage AP205. Viruses regulate their life cycles and infectivity through modulation of their structures and dynamics. While static structures of capsids from several viruses are now accessible with near-atomic-level resolution, atomic-level understanding of functionally important motions in assembled capsids is lacking. We observed up to 64-fold signal enhancements by DNP, which permitted in-depth analysis of these assemblies. For the HIV-1 CA assemblies, a remarkably high spectral resolution in the 3D and 2D heteronuclear data sets permitted the assignment of a significant fraction of backbone and side-chain resonances. Using an integrated DNP MAS NMR and molecular dynamics (MD) simulation approach, the conformational space sampled by the assembled capsid at cryogenic temperatures was mapped. Qualitatively, a remarkable agreement was observed for the experimental 13C/15N chemical shift distributions and those calculated from substructures along the MD trajectory. Residues that are mobile at physiological temperatures are frozen out in multiple conformers at cryogenic conditions, resulting in broad experimental and calculated chemical shift distributions. Overall, our results suggest that DNP MAS NMR measurements in combination with MD simulations facilitate a thorough understanding of the dynamic signatures of viral capsids.

Evidence of superdiffusive nanoscale motion in anionic polymeric hydrogels: Analysis of PGSE- NMR data and comparison with drug release properties

Polymeric hydrogels are promising candidates for drug delivery applications, thanks to their ability to encapsulate, transport and release a wide range of chemicals. The successful application of these materials requires a deep understanding of the mechanisms governing solute transport at the nanoscale and its impact on release kinetics. In this work, we investigate the translational diffusion of ibuprofen loaded in anionic agarose-carbomer (AC) hydrogels by 1H high resolution magic angle spinning (HR-MAS) NMR spectroscopy, and compare it to its macroscopic release kinetics. The analysis of the experimental NMR data provides the first evidence of superdiffusion for ibuprofen in AC hydrogels. Superdiffusive transport is observed in the majority of our samples, especially those with the smallest mesh size (7 nm) and highest ibuprofen concentrations (90–120 mg/mL). This outcome is rationalized in terms of heavy-tailed distributions of spatial displacements (Lèvy flights) and of waiting times, which depend on the nanoscopic structural heterogeneity of the gels and the strong but reversible association between ibuprofen and the agarose matrix.

Trapping at the Solid-Gas Interface: Selective Adsorption of Naphthalene by Montmorillonite Intercalated with a Fe(III)-Phenanthroline Complex.

In this study, stable hybrid materials (Mt–Fe(III)Phen), made by the μ-oxo Fe(III)–phenanthroline complex [(OH2)3(Phen)FeOFe(Phen)(OH2)3]4+ (Fe(III)Phen) intercalated in different amounts into montmorillonite (Mt), were used as a trap for immobilizing gaseous benzene and naphthalene and their mono chloro-derivatives at 25 and 50 °C. The entrapping process was studied through elemental analysis, magic angle spinning NMR spectroscopy, thermal analysis, and evolved gas mass spectrometry. Naphthalene and 1-chloronaphthalene were found to be immobilized in large amount at both temperatures. Molecular modeling allowed designing of the structure of the interlayer in the presence of the immobilized aromatic molecules. Adsorption is affected by the amount of the Fe complex hosted in the interlayer of the entrapping hybrid materials. On the contrary, under the same conditions, benzene and chlorobenzene were not adsorbed. Thermal desorption of naphthalenes was obtained under mild conditions, and immobilization was found to be reversible at least for 20 adsorption/desorption cycles.

Porous Crystalline Olefin-Linked Covalent Organic Frameworks.

The first unsubstituted olefin-linked covalent organic framework, termed COF-701, was made by linking 2,4,6-trimethyl-1,3,5-triazine (TMT) and 4,4'-biphenyldicarbaldehyde (BPDA) through Aldol condensation. Formation of the unsubstituted olefin (-CH═CH-) linkage upon reticulation is confirmed by Fourier transform infrared (FT-IR) spectroscopy and solid-state 13C cross-polarization magic angle spinning (CP-MAS) NMR spectroscopy of the framework and of its 13C-isotope-labeled analogue. COF-701 is found to be porous (1715 m2 g-1) and to retain its composition and crystallinity under both strongly acidic and basic conditions. The high chemical robustness is attributed to the unsubstituted olefin linkages. Immobilization of the strong Lewis acid BF3·OEt2 in the pores of the structure yields BF3⊂COF-701. In the material, the catalytic activity of the guest is retained, as evidenced in a benchmark Diels-Alder reaction.

Molecular orientation distribution of regenerated cellulose fibers investigated with rotor synchronized solid state NMR spectroscopy

A regenerated cellulose fiber is, in contrast to cotton, a man-made fiber. In the fiber production, the cellulose polymer is subject to various processing steps, affecting the underlying molecular orientation distribution, which is a determining factor for mechanical properties of the fiber. In this work, the molecular orientation distribution was determined in a 13C natural abundance Lyocell regenerated cellulose fiber bundle using rotor synchronized magic angle spinning NMR spectroscopy (ROSMAS) to investigate the chemical shift anisotropy (CSA). The recorded signal intensities were compared with an analytical model of the experiment to find the order parameters reflecting the orientation of the fiber. The CSA tensor was calculated using density functional theory for the crystalline cellulose II structure, commonly found in regenerated cellulose, and is required as an input parameter. The expected order parameter values were only found when approximating the glycosidic bond and its CSA tensor as being parallel to the molecular frame with the order parameter P_{2}=0.45 pm 0.02 compared to P_{2}=0.46 pm 0.02 obtained with wide angle X-ray scattering on a fiber bundle. To make this method accessible to the community, we distribute the Matlab script for the simulation of spectra obtained by the ROSMAS experiment at github.com/LeoSvenningsson/ROSMAS.

Natural abundance 17O MAS NMR and DFT simulations: New insights into the atomic structure of designed micas

Combining 17O Magic-Angle Spinning (MAS) NMR at natural abundance with DFT calculations is a promising methodology to shed light on the structure and disorder in tetrahedral sheets of designed micas with enhanced properties. Among brittle micas, synthetic mica is an important alternative to natural ones with a swelling sheet-like structure that results in many applications, by exploiting unique characteristics. Lowenstein's rule is one of the main chemical factor that determines the atomic structure of aluminosilicates and furthermore their properties. In the present article, 17O MAS NMR spectroscopy is used to validate (or not) the agreement of the Lowenstein's rule with the distribution of Si and Al sites in the tetrahedral sheets of synthetic micas. 17O MAS spectra of synthetic high-charged micas exhibit two regions of signals that revealed two distinguishable oxygen environments, namely Si-O-X (with X = Si, Altet, Mg) and Altet-O-Y (Y=Mg or Altet). DFT calculations were also conducted to obtain the 17O chemical shift and other NMR features like the quadrupolar coupling constant, CQ, for all of the oxygen environments encountered in the two model structures, one respecting the Lowenstein's rule and the other involving Altet-O-Altet and Si-O-Si environments. Our DFT calculations support the 17O assignment, by confirming that Altet-O-3Mg and Altet-O-Altet oxygen environments show chemical shifts under 30 ppm and more important, with quadrupolar coupling constants of about 1 MHz, in line with the spectral observation. By quantifying the 17O MAS NMR spectra at natural abundance, we demonstrate that one of the synthetic mica compositions does not meet the Lowenstein's rule.

19F Dynamic Nuclear Polarization at Fast Magic Angle Spinning for NMR of HIV-1 Capsid Protein Assemblies.

We report remarkably high, up to 100-fold, signal enhancements in 19F dynamic nuclear polarization (DNP) magic angle spinning (MAS) spectra at 14.1 T on HIV-1 capsid protein (CA) assemblies. These enhancements correspond to absolute sensitivity ratios of 12-29 and are of similar magnitude to those seen for 1H signals in the same samples. At MAS frequencies above 20 kHz, it was possible to record 2D 19F-13C HETCOR spectra, which contain long-range intra- and intermolecular correlations. Such correlations provide unique distance restraints, inaccessible in conventional experiments without DNP, for protein structure determination. Furthermore, systematic quantification of the DNP enhancements as a function of biradical concentration, MAS frequency, temperature, and microwave power is reported. Our work establishes the power of DNP-enhanced 19F MAS NMR spectroscopy for structural characterization of HIV-1 CA assemblies, and this approach is anticipated to be applicable to a wide range of large biomolecular systems.