Disorder and Oxide Ion Diffusion Mechanism in La1.54Sr0.46Ga3O7.27 Melilite from Nuclear Magnetic Resonance.

Layered tetrahedral network melilite is a promising structural family of fast ion conductors that exhibits the flexibility required to accommodate interstitial oxide anions, leading to excellent ionic transport properties at moderate temperatures. Here, we present a combined experimental and computational magic angle spinning (MAS) nuclear magnetic resonance (NMR) approach which aims at elucidating the local configurational disorder and oxide ion diffusion mechanism in a key member of this structural family possessing the La1.54Sr0.46Ga3O7.27 composition. 17O and 71Ga MAS NMR spectra display complex spectral line shapes that could be accurately predicted using a computational ensemble-based approach to model site disorder across multiple cationic and anionic sites, thereby enabling the assignment of bridging/nonbridging oxygens and the identification of distinct gallium coordination environments. The 17O and 71Ga MAS NMR spectra of La1.54Sr0.46Ga3O7.27 display additional features not observed for the parent LaSrGa3O7 phase which are attributed to interstitial oxide ions incorporated upon cation doping and stabilized by the formation of five-coordinate Ga centers conferring framework flexibility. 17O high-temperature (HT) MAS NMR experiments capture exchange within the bridging oxygens at 130 °C and reveal coalescence of all oxygen signals in La1.54Sr0.46Ga3O7.27 at approximately 300 °C, indicative of the participation of both interstitial and framework oxide ions in the transport process. These results further supported by the coalescence of the 71Ga resonances in the 71Ga HT MAS NMR spectra of La1.54Sr0.46Ga3O7.27 unequivocally provide evidence of the conduction mechanism in this melilite phase and highlight the potential of MAS NMR spectroscopy to enhance the understanding of ionic motion in solid electrolytes.

Cryogen-free 400 MHz (9.4 T) solid state MAS NMR system with liquid state NMR potential.

We show that the temporal magnetic field distortion generated by the Cold Head operation can be removed and high quality Solid-State Magic Angle Spinning NMR results can be obtained with a cryogen-free magnet. The compact design of the cryogen-free magnets allows for the probe to be inserted either from the bottom (as in most NMR systems) or, more conveniently, from the top. The magnetic field settling time can be made as short as an hour after a field ramp. Therefore, a single cryogen-free magnet can be used at different fixed fields. The magnetic field can be changed every day without compromising the measurement resolution.

Modulation of Uptake and Reactivity of Nitrogen Dioxide in Metal-Organic Framework Materials.

We report the modulation of reactivity of nitrogen dioxide (NO2 ) in a charged metal-organic framework (MOF) material, MFM-305-CH3 in which unbound N-centres are methylated and the cationic charge counter-balanced by Cl- ions in the pores. Uptake of NO2 into MFM-305-CH3 leads to reaction between NO2 and Cl- to give nitrosyl chloride (NOCl) and NO3 - anions. A high dynamic uptake of 6.58 mmol g-1 at 298 K is observed for MFM-305-CH3 as measured using a flow of 500 ppm NO2 in He. In contrast, the analogous neutral material, MFM-305, shows a much lower uptake of 2.38 mmol g-1 . The binding domains and reactivity of adsorbed NO2 molecules within MFM-305-CH3 and MFM-305 have been probed using in situ synchrotron X-ray diffraction, inelastic neutron scattering and by electron paramagnetic resonance, high-field solid-state nuclear magnetic resonance and UV/Vis spectroscopies. The design of charged porous sorbents provides a new platform to control the reactivity of corrosive air pollutants.

Bimetallic Aluminum- and Niobium-Doped MCM-41 for Efficient Conversion of Biomass-Derived 2-Methyltetrahydrofuran to Pentadienes.

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of AlIII and NbV sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed NbV sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.

Labeling and Probing the Silica Surface Using Mechanochemistry and 17 O†NMR Spectroscopy*.

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly 17 O enrichment protocols to help to understand the structure and reactivity of materials by using 17 O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision 17 O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution 17 O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si-O-Si) and silanols (Si-OH), while DNP analyses, performed by using direct 17 O polarization and indirect 17 O{1 H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si-OH environments at the surface was obtained from 2D 1 H-17 O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using 17 O DNP, their common interface was probed and Si-O-Ti bonds identified.

Chemoenzymatic Synthesis of Fluorinated Cellodextrins Identifies a New Allomorph for Cellulose-Like Materials*.

Understanding the fine details of the self-assembly of building blocks into complex hierarchical structures represents a major challenge en route to the design and preparation of soft-matter materials with specific properties. Enzymatically synthesised cellodextrins are known to have limited water solubility beyond DP9, a point at which they self-assemble into particles resembling the antiparallel cellulose II crystalline packing. We have prepared and characterised a series of site-selectively fluorinated cellodextrins with different degrees of fluorination and substitution patterns by chemoenzymatic synthesis. Bearing in mind the potential disruption of the hydrogen-bond network of cellulose II, we have prepared and characterised a multiply 6-fluorinated cellodextrin. In addition, a series of single site-selectively fluorinated cellodextrins was synthesised to assess the structural impact upon the addition of one fluorine atom per chain. The structural characterisation of these materials at different length scales, combining advanced NMR spectroscopy and microscopy methods, showed that a 6-fluorinated donor substrate yielded multiply 6-fluorinated cellodextrin chains that assembled into particles presenting morphological and crystallinity features, and intermolecular interactions, that are unprecedented for cellulose-like materials.

Drug-Polymer Interactions in Acetaminophen/Hydroxypropylmethylcellulose Acetyl Succinate Amorphous Solid Dispersions Revealed by Multidimensional Multinuclear Solid-State NMR Spectroscopy.

The bioavailability of insoluble crystalline active pharmaceutical ingredients (APIs) can be enhanced by formulation as amorphous solid dispersions (ASDs). One of the key factors of ASD stabilization is the formation of drug-polymer interactions at the molecular level. Here, we used a range of multidimensional and multinuclear nuclear magnetic resonance (NMR) experiments to identify these interactions in amorphous acetaminophen (paracetamol)/hydroxypropylmethylcellulose acetyl succinate (HPMC-AS) ASDs at various drug loadings. At low drug loading (<20 wt %), we showed that 1H-13C through-space heteronuclear correlation experiments identify proximity between aromatic protons in acetaminophen with cellulose backbone protons in HPMC-AS. We also show that 14N-1H heteronuclear multiple quantum coherence (HMQC) experiments are a powerful approach in probing spatial interactions in amorphous materials and establish the presence of hydrogen bonds (H-bond) between the amide nitrogen of acetaminophen with the cellulose ring methyl protons in these ASDs. In contrast, at higher drug loading (40 wt %), no acetaminophen/HPMC-AS spatial proximity was identified and domains of recrystallization of amorphous acetaminophen into its crystalline form I, the most thermodynamically stable polymorph, and form II are identified. These results provide atomic scale understanding of the interactions in the acetaminophen/HPMC-AS ASD occurring via H-bond interactions.

Characterization of and Structural Insight into Struvite-K, MgKPO4·6H2O, an Analogue of Struvite.

Struvite-K (MgKPO4·6H2O) is a magnesium potassium phosphate mineral with naturally cementitious properties, which is finding increasing usage as an inorganic cement for niche applications including nuclear waste management and rapid road repair. Struvite-K is also of interest in sustainable phosphate recovery from wastewater and, as such, a detailed knowledge of the crystal chemistry and high-temperature behavior is required to support further laboratory investigations and industrial applications. In this study, the local chemical environments of synthetic struvite-K were investigated using high-field solid-state 25Mg and 39K MAS NMR techniques, alongside 31P MAS NMR and thermal analysis. A single resonance was present in each of the 25Mg and 39K MAS NMR spectra, reported here for the first time alongside the experimental and calculated isotropic chemical shifts, which were comparable to the available data for isostructural struvite (MgNH4PO4·6H2O). An in situ high-temperature XRD analysis of struvite-K revealed the presence of a crystalline-amorphous-crystalline transition that occurred between 30 and 350 °C, following the single dehydration step of struvite-K. Between 50 and 300 °C, struvite-K dehydration yielded a transient disordered (amorphous) phase identified here for the first time, denoted δ-MgKPO4. At 350 °C, recrystallization was observed, yielding ß-MgKPO4, commensurate with an endothermic DTA event. A subsequent phase transition to γ-MgKPO4 was observed on further heating, which reversed on cooling, resulting in the α-MgKPO4 structure stabilized at room temperature. This behavior was dissimilar from that of struvite exposed to high temperature, where NH4 liberation occurs at temperatures >50 °C, indicating that struvite-K could potentially withstand high temperatures via a transition to MgKPO4.

35 Cl-1 H Heteronuclear correlation magic-angle spinning nuclear magnetic resonance experiments for probing pharmaceutical salts.

Heteronuclear multiple-quantum coherence (HMQC) pulse sequences for establishing heteronuclear correlation in solid-state nuclear magnetic resonance (NMR) between 35 Cl and 1 H nuclei in chloride salts under fast (60 kHz) magic-angle spinning (MAS) and at high magnetic field (a 1 H Larmor frequency of 850 MHz) are investigated. Specifically, recoupling of the 35 Cl-1 H dipolar interaction using rotary resonance recoupling with phase inversion every rotor period or the symmetry-based SR42 1 pulse sequences are compared. In our implementation of the population transfer (PT) dipolar (D) HMQC experiment, the satellite transitions of the 35 Cl nuclei are saturated with an off-resonance WURST sweep, at a low nutation frequency, over the second spinning sideband, whereby the WURST pulse must be of the same duration as the recoupling time. Numerical simulations of the 35 Cl-1 H MAS D-HMQC experiment performed separately for each crystallite orientation in a powder provide insight into the orientation dependence of changes in the second-order quadrupolar-broadened 35 Cl MAS NMR lineshape under the application of dipolar recoupling. Two-dimensional 35 Cl-1 H PT-D-HMQC MAS NMR spectra are presented for the amino acids glycine·HCl and l-tyrosine·HCl and the pharmaceuticals cimetidine·HCl, amitriptyline·HCl and lidocaine·HCl·H2 O. Experimentally observed 35 Cl lineshapes are compared with those simulated for 35 Cl chemical shift and quadrupolar parameters as calculated using the gauge-including projector-augmented wave (GIPAW) method: the calculated quadrupolar product (PQ ) values exceed those measured experimentally by a factor of between 1.3 and 1.9.

A 43 Ca nuclear magnetic resonance perspective on octacalcium phosphate and its hybrid derivatives.

43 Ca nuclear magnetic resonance (NMR) spectroscopy has been extensively applied to the detailed study of octacalcium phosphate (OCP), Ca8 (HPO4 )2 (PO4 )4 .5H2 O, and hybrid derivatives involving intercalated metabolic acids (viz., citrate, succinate, formate, and adipate). Such phases are of importance in the development of a better understanding of bone structure. High-resolution 43 Ca magic angle spinning (MAS) experiments, including double-rotation (DOR) 43 Ca NMR, as well as 43 Ca{1 H} rotational echo DOR (REDOR) and 31 P{43 Ca} REAPDOR NMR spectra, were recorded on a 43 Ca-labeled OCP phase at very high magnetic field (20 T), and complemented by ab initio calculations of NMR parameters using the Gauge-Including Projector Augmented Wave-density functional theory (GIPAW-DFT) method. This enabled a partial assignment of the eight inequivalent Ca2+ sites of OCP. Natural-abundance 43 Ca MAS NMR spectra were then recorded for the hybrid organic-inorganic derivatives, revealing changes in the 43 Ca lineshape. In the case of the citrate derivative, these could be interpreted on the basis of computational models of the structure. Overall, this study highlights the advantages of combining high-resolution 43 Ca NMR experiments and computational modeling for studying complex hybrid biomaterials.

Measuring multiple 17O-13C J-couplings in naphthalaldehydic acid: a combined solid state NMR and density functional theory approach.

A combined multinuclear solid state NMR and gauge included projected augmented wave, density functional theory (GIPAW DFT) computational approach is evaluated to determine the four heteronuclear 1J(13C,17O) couplings in solid 17O enriched naphthalaldehydic acid. Direct multi-field 17O magic angle spinning (MAS), triple quantum MAS (3QMAS) and double rotation (DOR) experiments are initially utilised to evaluate the accuracy of the DFT approximations used in the calculation of the isotropic chemical shifts (δiso), quadrupole coupling constants (CQ) and asymmetry (ηQ) parameters. These combined approaches give δiso values of 313, 200 and 66 ppm for the carbonyl (C[double bond, length as m-dash]O), ether (-O-) and hydroxyl (-OH) environments, respectively, with the corresponding measured quadrupole products (PQ) being 8.2, 9.0 and 10.6 MHz. The geometry optimised DFT structure derived using the CASTEP code gives firm agreement with the shifts observed for the ether (δiso = 223, PQ = 9.4 MHz) and hydroxyl (δiso = 62, PQ = 10.5 MHz) environments but the unoptimised experimental XRD structure has better agreement for the carbonyl group (δiso = 320, PQ = 8.3 MHz). The determined δiso and ηQ values are shown to be consistent with bond lengths closer to 1.222 Å (experimental length) rather than the geometry optimised length of 1.238 Å. The geometry optimised DFT 1J(13C,17O) coupling to the hydroxyl is calculated as 20 Hz and the couplings to the ether were calculated to be 37 (O-C[double bond, length as m-dash]O) and 32 (O-C-OH) Hz. The scalar coupling parameters for the unoptimised experimental carbonyl group predict a 1J(13C,17O) value of 28 Hz, whilst optimisation gives a value of 27 Hz. These calculated 1J(13C,17O) couplings, together with estimations of the probability of each O environment being isotopically labelled (determined by electrospray ionisation mass spectrometry) and the measured refocussable transverse dephasing (T2') behaviour, are combined to simulate the experimental decay behaviour. Good agreement between the measured and calculated decay behaviour is observed.

High Molecular Weight Mixed-Linkage Glucan as a Mechanical and Hydration Modulator of Bacterial Cellulose: Characterization by Advanced NMR Spectroscopy.

Bacterial cellulose (BC) consists of a complex three-dimensional organization of ultrafine fibers which provide unique material properties such as softness, biocompatibility, and water-retention ability, of key importance for biomedical applications. However, there is a poor understanding of the molecular features modulating the macroscopic properties of BC gels. We have examined chemically pure BC hydrogels and composites with arabinoxylan (BC-AX), xyloglucan (BC-XG), and high molecular weight mixed-linkage glucan (BC-MLG). Atomic force microscopy showed that MLG greatly reduced the mechanical stiffness of BC gels, while XG and AX did not exert a significant effect. A combination of advanced solid-state NMR methods allowed us to characterize the structure of BC ribbons at ultra-high resolution and to monitor local mobility and water interactions. This has enabled us to unravel the effect of AX, XG, and MLG on the short-range order, mobility, and hydration of BC fibers. Results show that BC-XG hydrogels present BC fibrils of increased surface area, which allows BC-XG gels to hold higher amounts of bound water. We report for the first time that the presence of high molecular weight MLG reduces the density of clusters of BC fibrils and dramatically increases water interactions with BC. Our data supports two key molecular features determining the reduced stiffness of BC-MLG hydrogels, that is, (i) the adsorption of MLG on the surface of BC fibrils precluding the formation of a dense network and (ii) the preorganization of bound water by MLG. Hence, we have produced and fully characterized BC-MLG hydrogels with novel properties which could be potentially employed as renewable materials for applications requiring high water retention capacity (e.g. personal hygiene products).

Exploiting in-situ solid-state NMR spectroscopy to probe the early stages of hydration of calcium aluminate cement.

We report a high-field in-situ solid-state NMR study of the hydration of CaAl2O4 (the most important hydraulic phase in calcium aluminate cement), based on time-resolved measurements of solid-state 27Al NMR spectra during the early stages of the reaction. A variant of the CLASSIC NMR methodology, involving alternate recording of direct-excitation and MQMAS 27Al NMR spectra, was used to monitor the 27Al species present in both the solid and liquid phases as a function of time. Our results provide quantitative information on the changes in the relative amounts of 27Al sites with tetrahedral coordination (the anhydrous reactant phase) and octahedral coordination (the hydrated product phases) as a function of time, and reveal significantly different kinetic and mechanistic behaviour of the hydration reaction at the different temperatures (20 °C and 60 °C) studied.

A Combined 25 Mg Solid-State NMR and Ab Initio DFT Approach to Probe the Local Structural Differences in Magnesium Acetate Phases Mg(CH3 COO)2 ⋠nH2 O (n=0, 1, 4).

Multinuclear (1 H, 13 C, 25 Mg) solid-state NMR data is reported for a series of magnesium acetate phases Mg(CH3 COO)2 ⋅ nH2 O (n=0 (two polymorphs), 1, 4). The central focus here is 25 Mg as this set of compounds provides an expanded range of local magnesium coordinations compared to what has previously been reported in the literature using NMR. These four compounds provide 10 distinct magnesium sites with varying NMR interaction parameters. One of the anhydrous crystal structures (α) has an MgO7 site which is reported, to the best of our knowledge, for the first time. For those phases with a single crystal structure, a combination of magic angle spinning (MAS) NMR at high magnetic field (20 T) and first principles density functional theory (DFT) calculations demonstrates the value of including 25 Mg in NMR crystallography approaches. For the second anhydrate phase (ß), where no single crystal structure exists, the multinuclear NMR data clearly show the multiplicity of sites for the different elements, with 25 Mg satellite transition (ST) MAS NMR revealing four inequivalent magnesium environments, which is new information constraining future refinement of the structure. This study highlights the sensitivity of 25 Mg NMR to the local environment, an observation important for several sub-disciplines of chemistry where the structural chemistry of magnesium is likely to be crucial.

Mediation mechanism of tyrosine 185 on the retinal isomerization equilibrium and the proton release channel in the seven-transmembrane receptor bacteriorhodopsin.

Electrostatic coupling leading to conformational changes in proteins is challenging to demonstrate directly, it requires that both the local, discrete electronic details and dynamic information relevant to the functional descriptions are probed. Here, as a novel study to address this challenge, the roles of an aromatic residue in influencing the functional conformational changes of a membrane receptor in its natural membrane environment are reported. Previously intractable discrete electronic details have been obtained using 2D solid-state NMR of specifically labelled receptor, reinforced with molecular dynamic simulations, mutational analysis and functional assays, supported by and compared with rigid-atom crystal structural models. Hydrogen bonding and hydrophobic interactions are identified as the mechanistic origin for direct electromechanical coupling to the dynamics of conformational changes within the receptor.

Characterization of Protein-Protein Interfaces in Large Complexes by Solid-State NMR Solvent Paramagnetic Relaxation Enhancements.

Solid-state NMR is becoming a viable alternative for obtaining information about structures and dynamics of large biomolecular complexes, including ones that are not accessible to other high-resolution biophysical techniques. In this context, methods for probing protein-protein interfaces at atomic resolution are highly desirable. Solvent paramagnetic relaxation enhancements (sPREs) proved to be a powerful method for probing protein-protein interfaces in large complexes in solution but have not been employed toward this goal in the solid state. We demonstrate that 1H and 15N relaxation-based sPREs provide a powerful tool for characterizing intermolecular interactions in large assemblies in the solid state. We present approaches for measuring sPREs in practically the entire range of magic angle spinning frequencies used for biomolecular studies and discuss their benefits and limitations. We validate the approach on crystalline GB1, with our experimental results in good agreement with theoretical predictions. Finally, we use sPREs to characterize protein-protein interfaces in the GB1 complex with immunoglobulin G (IgG). Our results suggest the potential existence of an additional binding site and provide new insights into GB1:IgG complex structure that amend and revise the current model available from studies with IgG fragments. We demonstrate sPREs as a practical, widely applicable, robust, and very sensitive technique for determining intermolecular interaction interfaces in large biomolecular complexes in the solid state.

Co-existence of Distinct Supramolecular Assemblies in Solution and in the Solid State.

The formation of distinct supramolecular assemblies, including a metastable species, is revealed for a lipophilic guanosine (G) derivative in solution and in the solid state. Structurally different G-quartet-based assemblies are formed in chloroform depending on the nature of the cation, anion and the salt concentration, as characterized by circular dichroism and time course diffusion-ordered NMR spectroscopy data. Intriguingly, even the presence of potassium ions that stabilize G-quartets in chloroform was insufficient to exclusively retain such assemblies in the solid state, leading to the formation of mixed quartet and ribbon-like assemblies as revealed by fast magic-angle spinning (MAS) NMR spectroscopy. Distinct N-H⋅⋅⋅N and N-H⋅⋅⋅O intermolecular hydrogen bonding interactions drive quartet and ribbon-like self-assembly resulting in markedly different 2D 1 H solid-state NMR spectra, thus facilitating a direct identification of mixed assemblies. A dissolution NMR experiment confirmed that the quartet and ribbon interconversion is reversible-further demonstrating the changes that occur in the self-assembly process of a lipophilic nucleoside upon a solid-state to solution-state transition and vice versa. A systematic study for complexation with different cations (K+ , Sr2+ ) and anions (picrate, ethanoate and iodide) emphasizes that the existence of a stable solution or solid-state structure may not reflect the stability of the same supramolecular entity in another phase.

1H CSA parameters by ultrafast MAS NMR: Measurement and applications to structure refinement.

A 1H anisotropic-isotropic chemical shift correlation experiment which employs symmetry-based recoupling sequences to reintroduce the chemical shift anisotropy in ν1 and ultrafast MAS to resolve 1H sites in ν2 is described. This experiment is used to measure 1H shift parameters for L-ascorbic acid, a compound with a relatively complex hydrogen-bonding network in the solid. The 1H CSAs of hydrogen-bonded sites with resolved isotropic shifts can be extracted directly from the recoupled lineshapes. In combination with DFT calculations, hydrogen positions in crystal structures obtained from X-ray and neutron diffraction are refined by comparison with simulations of the full two-dimensional NMR spectrum. The improved resolution afforded by the second dimension allows even unresolved hydrogen-bonded sites 1H to be assigned and their shift parameters to be obtained.

Amyloid Hydrogen Bonding Polymorphism Evaluated by (15)N{(17)O}REAPDOR Solid-State NMR and Ultra-High Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

A combined approach, using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) and solid-state NMR (Nuclear Magnetic Resonance), shows a high degree of polymorphism exhibited by Aß species in forming hydrogen-bonded networks. Two Alzheimer's Aß peptides, Ac-Aß(16-22)-NH2 and Aß(11-25), selectively labeled with (17)O and (15)N at specific amino acid residues were investigated. The total amount of peptides labeled with (17)O as measured by FTICR-MS enabled the interpretation of dephasing observed in (15)N{(17)O}REAPDOR solid-state NMR experiments. Specifically, about one-third of the Aß peptides were found to be involved in the formation of a specific >C═(17)O···H-(15)N hydrogen bond with their neighbor peptide molecules, and we hypothesize that the rest of the molecules undergo ± n off-registry shifts in their hydrogen bonding networks.

Multinuclear Solid-State NMR Investigation of Hexaniobate and Hexatantalate Compounds.

This work determines the potential of solid-state NMR techniques to probe proton, alkali, and niobium environments in Lindqvist salts. Na7HNb6O19·15H2O (1), K8Nb6O19·16H2O (2), and Na8Ta6O19·24.5H2O (3) have been studied by solid-state static and magic angle spinning (MAS) NMR at high and ultrahigh magnetic field (16.4 and 19.9 T). (1)H MAS NMR was found to be a convenient and straightforward tool to discriminate between protonated and nonprotonated clusters AxH8-xM6O19·nH2O (A = alkali ion; M = Nb, Ta). (93)Nb MAS NMR studies at different fields and MAS rotation frequencies have been performed on 1. For the first time, the contributions of NbO5Oµ2H sites were clearly distinguished from those assigned to NbO6 sites in the hexaniobate cluster. The strong broadening of the resonances obtained under MAS was interpreted by combining chemical shift anisotropy (CSA) with quadrupolar effects and by using extensive fitting of the line shapes. In order to obtain the highest accuracy for all NMR parameters (CSA and quadrupolar), (93)Nb WURST QCPMG spectra in the static mode were recorded at 16.4 T for sample 1. The (93)Nb NMR spectra were interpreted in connection with the XRD data available in the literature (i.e., fractional occupancies of the NbO5Oµ2H sites). 1D (23)Na MAS and 2D (23)Na 3QMAS NMR studies of 1 revealed several distinct sodium sites. The multiplicity of the sites was again compared to structural details previously obtained by single-crystal X-ray diffraction (XRD) studies. The (23)Na MAS NMR study of 3 confirmed the presence of a much larger distribution of sodium sites in accordance with the 10 sodium sites predicted by XRD. Finally, the effect of Nb/Ta substitutions in 1 was also probed by multinuclear MAS NMR ((1)H, (23)Na, and (93)Nb).