High-Resolution 17O Solid-State NMR as a Unique Probe for Investigating Oxalate Binding Modes in Materials: The Case Study of Calcium Oxalate Biominerals.

Oxalate ligands are found in many classes of materials, including energy storage materials and biominerals. Determining their local environments at the atomic scale is thus paramount to establishing the structure and properties of numerous phases. Here, we show that high-resolution 17O solid-state NMR is a valuable asset for investigating the structure of crystalline oxalate systems. First, an efficient 17O-enrichment procedure of oxalate ligands is demonstrated using mechanochemistry. Then, 17O-enriched oxalates were used for the synthesis of the biologically relevant calcium oxalate monohydrate (COM) phase, enabling the analysis of its structure and heat-induced phase transitions by high-resolution 17O NMR. Studies of the low-temperature COM form (LT-COM), using magnetic fields from 9.4 to 35.2 T, as well as 13C-17O MQ/D-RINEPT and 17O{1H} MQ/REDOR experiments, enabled the 8 inequivalent oxygen sites of the oxalates to be resolved, and tentatively assigned. The structural changes upon heat treatment of COM were also followed by high-resolution 17O NMR, providing new insight into the structures of the high-temperature form (HT-COM) and anhydrous calcium oxalate α-phase (α-COA), including the presence of structural disorder in the latter case. Overall, this work highlights the ease associated with 17O-enrichment of oxalate oxygens, and how it enables high-resolution solid-state NMR, for "NMR crystallography" investigations.

17O solid state NMR as a valuable tool for deciphering reaction mechanisms in mechanochemistry: the case study on the 17O-enrichment of hydrated Ca-pyrophosphate biominerals.

The possibility of enriching in 17O the water molecules within hydrated biominerals belonging to the Ca-pyrophosphate family was investigated, using liquid assisted grinding (LAG) in the presence of 17O-labelled water. Two phases with different hydration levels, namely triclinic calcium pyrophosphate dihydrate (Ca2P2O7·2H2O, denoted t-CPPD) and monoclinic calcium pyrophosphate tetrahydrate (Ca2P2O7·4H2O, denoted m-CPPT ß) were enriched in 17O using a "post-enrichment" strategy, in which the non-labelled precursors were ground under gentle milling conditions in the presence of stoichiometric quantities of 17O-enriched water (introduced here in very small volumes ∼10 µL). Using high-resolution 17O solid-state NMR (ssNMR) analyses at multiple magnetic fields, and dynamic nuclear polarisation (DNP)-enhanced 17O NMR, it was possible to show that the labelled water molecules are mainly located at the core of the crystal structures, but that they can enter the lattice in different ways, namely by dissolution/recrystallisation or by diffusion. Overall, this work sheds light on the importance of high-resolution 17O NMR to help decipher the different roles that water can play as a liquid-assisted grinding agent and as a reagent for 17O-isotopic enrichment.

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.

17 O solid-state NMR at ultrahigh magnetic field of 35.2 T: Resolution of inequivalent oxygen sites in different phases of MOF MIL-53(Al).

MIL-53(Al) is a member of the most extensively studied metal-organic framework (MOF) families owing to its "flexible" framework and superior stability. 17 O solid-state NMR (SSNMR) spectroscopy is an ideal site-specific characterization tool as it probes local oxygen environments. Because oxygen local structure is often altered during phase change, 17 O SSNMR can be used to follow phase transitions. However, 17 O is a challenging nucleus to study via SSNMR due to its low sensitivity and resolution arising from the very low natural abundance of 17 O isotope and its quadrupolar nature. In this work, we describe that by using 17 O isotopic enrichment and performing 17 O SSNMR experiments at an ultrahigh magnetic field of 35.2 T, all chemically and crystallographically inequivalent oxygen sites in two representative MIL-53(Al) (as-made and water adsorbed) phases can be completely resolved. The number of signals in each phase is consistent with that predicted from the space group refined from powder X-ray diffraction data. The 17 O 1D magic-angle spinning (MAS) and 2D triple-quantum MAS (3QMAS) spectra at 35.2 T furnish fine information about the host-guest interactions and the structural changes associated with phase transition. The ability to completely resolve multiple chemically and crystallographically inequivalent oxygen sites in MOFs at very high magnetic field, as illustrated in this work, significantly enhances the potential for using the NMR crystallography approach to determine crystal structures of new MOFs and verify the structures of existing MOFs obtained from refining powder X-ray diffraction data.

Higher Magnetic Fields, Finer MOF Structural Information: 17O Solid-State NMR at 35.2 T.

The spectroscopic study of oxygen, a vital element in materials, physical, and life sciences, is of tremendous fundamental and practical importance. 17O solid-state NMR (SSNMR) spectroscopy has evolved into an ideal site-specific characterization tool, furnishing valuable information on the local geometric and bonding environments about chemically distinct and, in some favorable cases, crystallographically inequivalent oxygen sites. However, 17O is a challenging nucleus to study via SSNMR, as it suffers from low sensitivity and resolution, owing to the quadrupolar interaction and low 17O natural abundance. Herein, we report a significant advance in 17O SSNMR spectroscopy. 17O isotopic enrichment and the use of an ultrahigh 35.2 T magnetic field have unlocked the identification of many inequivalent carboxylate oxygen sites in the as-made and activated phases of the metal-organic framework (MOF) α-Mg3(HCOO)6. The subtle 17O spectral differences between the as-made and activated phases yield detailed information about host-guest interactions, including insight into nonconventional O···H-C hydrogen bonding. Such weak interactions often play key roles in the applications of MOFs, such as gas adsorption and biomedicine, and are usually difficult to study via other characterization routes. The power of performing 17O SSNMR experiments at an ultrahigh magnetic field of 35.2 T for MOF characterization is further demonstrated by examining activation of the MIL-53(Al) MOF. The sensitivity and resolution enhanced at 35.2 T allows partially and fully activated MIL-53(Al) to be unambiguously distinguished and also permits several oxygen environments in the partially activated phase to be tentatively identified. This demonstration of the very high resolution of 17O SSNMR recorded at the highest magnetic field accessible to chemists to date illustrates how a broad variety of scientists can now study oxygen-containing materials and obtain previously inaccessible fine structural information.

Direct 17O Isotopic Labeling of Oxides Using Mechanochemistry.

While 17O NMR is increasingly being used for elucidating the structure and reactivity of complex molecular and materials systems, much effort is still required for it to become a routine analytical technique. One of the main difficulties for its development comes from the very low natural abundance of 17O (0.04%), which implies that isotopic labeling is generally needed prior to NMR analyses. However, 17O-enrichment protocols are often unattractive in terms of cost, safety, and/or practicality, even for compounds as simple as metal oxides. Here, we demonstrate how mechanochemistry can be used in a highly efficient way for the direct 17O isotopic labeling of a variety of s-, p-, and d-block oxides, which are of major interest for the preparation of functional ceramics and glasses: Li2O, CaO, Al2O3, SiO2, TiO2, and ZrO2. For each oxide, the enrichment step was performed under ambient conditions in less than 1 h and at low cost, which makes these synthetic approaches highly appealing in comparison to the existing literature. Using high-resolution solid-state 17O NMR and dynamic nuclear polarization, atomic-level insight into the enrichment process is achieved, especially for titania and alumina. Indeed, it was possible to demonstrate that enriched oxygen sites are present not only at the surface but also within the oxide particles. Moreover, information on the actual reactions occurring during the milling step could be obtained by 17O NMR, in terms of both their kinetics and the nature of the reactive species. Finally, it was demonstrated how high-resolution 17O NMR can be used for studying the reactivity at the interfaces between different oxide particles during ball-milling, especially in cases when X-ray diffraction techniques are uninformative. More generally, such investigations will be useful not only for producing 17O-enriched precursors efficiently but also for understanding better mechanisms of mechanochemical processes themselves.

Recent directions in the solid-state NMR study of synthetic and natural calcium phosphates.

Materials containing a calcium phosphate component have been the subject of much interest to NMR spectroscopists, especially in view of understanding the structure and properties of mineralized tissues like bone and teeth, and of developing synthetic biomaterials for bone regeneration. Here, we present a selection of recent developments in their structural characterization using advanced solid state NMR experiments, highlighting the level of insight which can now be accessed.

Hydroxyapatites: Key Structural Questions and Answers from Dynamic Nuclear Polarization.

We demonstrate that NMR/DNP (Dynamic Nuclear Polarization) allows an unprecedented description of carbonate substituted hydroxyapatite (CHAp). Key structural questions related to order/disorder and clustering of carbonates are tackled using distance sensitive DNP experiments using 13C-13C recoupling. Such experiments are easily implemented due to unprecedented DNP gain (orders of magnitude). DNP is efficiently mediated by quasi one-dimensional spin diffusion through the hydroxyl columns present in the CHAp structure (thought of as "highways" for spin diffusion). For spherical nanoparticles and ϕ < 100 nm, it is numerically shown that spin diffusion allows their study as a whole. Most importantly, we demonstrate also that the DNP study at 100 K leads to data which are comparable to data obtained at room temperature (in terms of spin dynamics and line shape resolution). Finally, all 2D DNP experiments can be interpreted in terms of domains exhibiting well identified types of substitution: local order and carbonate clustering are clearly favored.

Unleashing the Potential of 17 O†NMR Spectroscopy Using Mechanochemistry.

17 O NMR spectroscopy has been the subject of vivid interest in recent years, because there is increasing evidence that it can provide unique insight into the structure and reactivity of many molecules and materials. However, due to the very poor natural abundance of oxygen-17, 17 O labeling is generally a prerequisite. This is a real obstacle for most research groups, because of the high costs and/or strong experimental constraints of the most frequently used 17 O-labeling schemes. Here, we show for the first time that mechanosynthesis offers unique opportunities for enriching in 17 O a variety of organic and inorganic precursors of synthetic interest. The protocols are fast, user-friendly, and low-cost, which makes them highly attractive for a broad research community, and their suitability for 17 O solid-state NMR applications is demonstrated.

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).

Exploring the molecular structure of imidazolium-silica-based nanoparticle networks by combining solid-state NMR spectroscopy and first-principles calculations.

A DFT-based molecular model for imidazolium-silica-based nanoparticle networks (INNs) is presented. The INNs were synthesized and characterized by using small-angle X-ray scattering (SAXS), NMR spectroscopy, and theoretical ab initio calculations. (11)B and (31)P HETCOR CP MAS experiments were recorded. Calculated (19)F NMR spectroscopy results, combined with the calculated anion-imidazolium (IM) distances, predicted the IM chain density in the INN, which was also confirmed from thermogravimetric analysis/mass spectrometry results. The presence of water molecules trapped between the nanoparticles is also suggested. First considerations on possible π-π stacking between the IM rings are presented. The predicted electronic properties confirm the photoluminescence emissions in the correct spectral domain.

Denoising NMR time-domain signal by singular-value decomposition accelerated by graphics processing units.

We present a post-processing method that decreases the NMR spectrum noise without line shape distortion. As a result the signal-to-noise (S/N) ratio of a spectrum increases. This method is called Cadzow enhancement procedure that is based on the singular-value decomposition of time-domain signal. We also provide software whose execution duration is a few seconds for typical data when it is executed in modern graphic-processing unit. We tested this procedure not only on low sensitive nucleus (29)Si in hybrid materials but also on low gyromagnetic ratio, quadrupole nucleus (87)Sr in reference sample Sr(NO3)2. Improving the spectrum S/N ratio facilitates the determination of T/Q ratio of hybrid materials. It is also applicable to simulated spectrum, resulting shorter simulation duration for powder averaging. An estimation of the number of singular values needed for denoising is also provided.

Confining calcium oxalate crystal growth in a carbonated apatite-coated microfluidic channel to better understand the role of Randall's plaque in kidney stone formation.

Effective prevention of recurrent kidney stone disease requires the understanding of the mechanisms of its formation. Numerous in vivo observations have demonstrated that a large number of pathological calcium oxalate kidney stones develop on an apatitic calcium phosphate deposit, known as Randall's plaque. In an attempt to understand the role of the inorganic hydroxyapatite phase in the formation and habits of calcium oxalates, we confined their growth under dynamic physicochemical and flow conditions in a reversible microfluidic channel coated with hydroxyapatite. Using multi-scale characterization techniques including scanning electron and Raman microscopy, we showed the successful formation of carbonated hydroxyapatite as found in Randall's plaque. This was possible due to a new two-step flow seed-mediated growth strategy which allowed us to coat the channel with carbonated hydroxyapatite. Precipitation of calcium oxalates under laminar flow from supersaturated solutions of oxalate and calcium ions showed that the formation of crystals is a substrate and time dependent complex process where diffusion of oxalate ions to the surface of carbonated hydroxyapatite and the solubility of the latter are among the most important steps for the formation of calcium oxalate crystals. Indeed when an oxalate solution was flushed for 24 h, dissolution of the apatite layer and formation of calcium carbonate calcite crystals occurred which seems to promote calcium oxalate crystal formation. Such a growth route has never been observed in vivo in the context of kidney stones. Under our experimental conditions, our results do not show any direct promoting role of carbonated hydroxyapatite in the formation of calcium oxalate crystals, consolidating therefore the important role that macromolecules can play in the process of nucleation and growth of calcium oxalate crystals on Randall's plaque.

Boronate ligands in materials: determining their local environment by using a combination of IR/solid-state NMR spectroscopies and DFT calculations.

Boronic acids (R-B(OH)(2)) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R-B(OH)(3)(-)) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C(4)H(9)-B(OH)(3)](2), which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid-state NMR spectroscopy ((1)H, (13)C, (11)B and (43)Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave--GIPAW--method). These data allow relationships between the geometry around the OH groups in boronates and the IR and (1)H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic-inorganic materials containing boronate building blocks.

87Sr solid-state NMR as a structurally sensitive tool for the investigation of materials: antiosteoporotic pharmaceuticals and bioactive glasses.

Strontium is an element of fundamental importance in biomedical science. Indeed, it has been demonstrated that Sr(2+) ions can promote bone growth and inhibit bone resorption. Thus, the oral administration of Sr-containing medications has been used clinically to prevent osteoporosis, and Sr-containing biomaterials have been developed for implant and tissue engineering applications. The bioavailability of strontium metal cations in the body and their kinetics of release from materials will depend on their local environment. It is thus crucial to be able to characterize, in detail, strontium environments in disordered phases such as bioactive glasses, to understand their structure and rationalize their properties. In this paper, we demonstrate that (87)Sr NMR spectroscopy can serve as a valuable tool of investigation. First, the implementation of high-sensitivity (87)Sr solid-state NMR experiments is presented using (87)Sr-labeled strontium malonate (with DFS (double field sweep), QCPMG (quadrupolar Carr-Purcell-Meiboom-Gill), and WURST (wideband, uniform rate, and smooth truncation) excitation). Then, it is shown that GIPAW DFT (gauge including projector augmented wave density functional theory) calculations can accurately compute (87)Sr NMR parameters. Last and most importantly, (87)Sr NMR is used for the study of a (Ca,Sr)-silicate bioactive glass of limited Sr content (only ~9 wt %). The spectrum is interpreted using structural models of the glass, which are generated through molecular dynamics (MD) simulations and relaxed by DFT, before performing GIPAW calculations of (87)Sr NMR parameters. Finally, changes in the (87)Sr NMR spectrum after immersion of the glass in simulated body fluid (SBF) are reported and discussed.

First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17O and 2H NMR Analyses.

Calcium oxalate minerals of the general formula CaC2O4 . xH2O are widely present in nature and usually associated with pathological calcifications, constituting up to 70-80% of the mineral component of renal calculi. The monohydrate phase (CaC2O4 .H2O, COM) is the most stable form, accounting for the majority of the hydrated calcium oxalates found. These mineral phases have been studied extensively via X-ray diffraction and IR spectroscopy and, to a lesser extent, using 1H, 13C, and 43Ca solid-state NMR spectroscopy. However, several aspects of their structure and reactivity are still unclear, such as the evolution from low- to high-temperature COM structures (LT-COM and HT-COM, respectively) and the involvement of water molecules in this phase transition. Here, we report for the first time a 17O and 2H solid-state NMR investigation of the local structure and dynamics of water in the COM phase. A new procedure for the selective 17O- and 2H-isotopic enrichment of water molecules within the COM mineral is presented using mechanochemistry, which employs only microliter quantities of enriched water and leads to exchange yields up to ∼30%. 17O NMR allows both crystallographically inequivalent water molecules in the LT-COM structure to be resolved, while 2H NMR studies provide unambiguous evidence that these water molecules are undergoing different types of motions at high temperatures without exchanging with one another. Dynamics appear to be essential for water molecules in these structures, which have not been accounted for in previous structural studies on the HT-COM structure due to lack of available tools, highlighting the importance of such NMR investigations for refining the overall knowledge on biologically relevant minerals like calcium oxalates.

Correction to "First Direct Insight into the Local Environment and Dynamics of Water Molecules in the Whewellite Mineral Phase: Mechanochemical Isotopic Enrichment and High-Resolution 17O and 2H NMR Analyses".

[This corrects the article DOI: 10.1021/acs.jpcc.2c02070.].

Investigation of the interface in silica-encapsulated liposomes by combining solid state NMR and first principles calculations.

In the context of nanomedicine, liposils (liposomes and silica) have a strong potential for drug storage and release schemes: such materials combine the intrinsic properties of liposome (encapsulation) and silica (increased rigidity, protective coating, pH degradability). In this work, an original approach combining solid state NMR, molecular dynamics, first principles geometry optimization, and NMR parameters calculation allows the building of a precise representation of the organic/inorganic interface in liposils. {(1)H-(29)Si}(1)H and {(1)H-(31)P}(1)H Double Cross-Polarization (CP) MAS NMR experiments were implemented in order to explore the proton chemical environments around the silica and the phospholipids, respectively. Using VASP (Vienna Ab Initio Simulation Package), DFT calculations including molecular dynamics, and geometry optimization lead to the determination of energetically favorable configurations of a DPPC (dipalmitoylphosphatidylcholine) headgroup adsorbed onto a hydroxylated silica surface that corresponds to a realistic model of an amorphous silica slab. These data combined with first principles NMR parameters calculations by GIPAW (Gauge Included Projected Augmented Wave) show that the phosphate moieties are not directly interacting with silanols. The stabilization of the interface is achieved through the presence of water molecules located in-between the head groups of the phospholipids and the silica surface forming an interfacial H-bonded water layer. A detailed study of the (31)P chemical shift anisotropy (CSA) parameters allows us to interpret the local dynamics of DPPC in liposils. Finally, the VASP/solid state NMR/GIPAW combined approach can be extended to a large variety of organic-inorganic hybrid interfaces.

Synthesis and characterization of crystalline structures based on phenylboronate ligands bound to alkaline earth cations.

We describe the preparation of the first crystalline compounds based on arylboronate ligands PhB(OH)(3)(-) coordinated to metal cations: [Ca(PhB(OH)(3))(2)], [Sr(PhB(OH)(3))(2)]·H(2)O, and [Ba(PhB(OH)(3))(2)]. The calcium and strontium structures were solved using powder and single-crystal X-ray diffraction, respectively. In both cases, the structures are composed of chains of cations connected through phenylboronate ligands, which interact one with each other to form a 2D lamellar structure. The temperature and pH conditions necessary for the formation of phase-pure compounds were investigated: changes in temperature were found to mainly affect the morphology of the crystallites, whereas strong variations in pH were found to affect the formation of pure phases. All three compounds were characterized using a wide range of analytical techniques (TGA, IR, Raman, XRD, and high resolution (1)H, (11)B, and (13)C solid-state NMR), and the different coordination modes of phenylboronate ligands were analyzed. Two different kinds of hydroxyl groups were identified in the structures: those involved in hydrogen bonds, and those that are effectively "free" and not involved in hydrogen bonds of any significant strength. To position precisely the OH protons within the structures, an NMR-crystallography approach was used: the comparison of experimental and calculated NMR parameters (determined using the Gauge Including Projector Augmented Wave method, GIPAW) allowed the most accurate positions to be identified. In the case of the calcium compound, it was found that it is the (43)Ca NMR data that are critical to help identify the best model of the structure.

A novel multinuclear solid-state NMR approach for the characterization of kidney stones.

The spectroscopic study of pathological calcifications (including kidney stones) is extremely rich and helps to improve the understanding of the physical and chemical processes associated with their formation. While Fourier transform infrared (FTIR) imaging and optical/electron microscopies are routine techniques in hospitals, there has been a dearth of solid-state NMR studies introduced into this area of medical research, probably due to the scarcity of this analytical technique in hospital facilities. This work introduces effective multinuclear and multidimensional solid-state NMR methodologies to study the complex chemical and structural properties characterizing kidney stone composition. As a basis for comparison, three hydrates (n=1, 2 and 3) of calcium oxalate are examined along with nine representative kidney stones. The multinuclear magic angle spinning (MAS) NMR approach adopted investigates the 1H, 13C, 31P and 31P nuclei, with the 1H and 13C MAS NMR data able to be readily deconvoluted into the constituent elements associated with the different oxalates and organics present. For the first time, the full interpretation of highly resolved 1H NMR spectra is presented for the three hydrates, based on the structure and local dynamics. The corresponding 31P MAS NMR data indicates the presence of low-level inorganic phosphate species; however, the complexity of these data make the precise identification of the phases difficult to assign. This work provides physicians, urologists and nephrologists with additional avenues of spectroscopic investigation to interrogate this complex medical dilemma that requires real, multitechnique approaches to generate effective outcomes.