31P Magic Angle Spinning Nuclear Magnetic Resonance Research Articles

Revealing the Local Structure and Dynamics of the Solid Li Ion Conductor Li3P5O14.

The development of fast Li ion-conducting materials for use as solid electrolytes that provide sufficient electrochemical stability against electrode materials is paramount for the future of all-solid-state batteries. Advances on these fast ionic materials are dependent on building structure-ionic mobility-function relationships. Here, we exploit a series of multinuclear and multidimensional nuclear magnetic resonance (NMR) approaches, including 6Li and 31P magic angle spinning (MAS), in conjunction with density functional theory (DFT) to provide a detailed understanding of the local structure of the ultraphosphate Li3P5O14, a promising candidate for an oxide-based Li ion conductor that has been shown to be a highly conductive, energetically favorable, and electrochemically stable potential solid electrolyte. We have reported a comprehensive assignment of the ultraphosphate layer and layered Li6O16 26- chains through 31P and 6Li MAS NMR, respectively, in conjunction with DFT. The chemical shift anisotropy of the eight resonances with the lowest 31P chemical shift is significantly lower than that of the 12 remaining resonances, suggesting the phosphate bonding nature of these P sites being one that bridges to three other phosphate groups. We employed a number of complementary 6,7Li NMR techniques, including MAS variable-temperature line narrowing spectra, spin-alignment echo (SAE) NMR, and relaxometry, to quantify the lithium ion dynamics in Li3P5O14. Detailed analysis of the diffusion-induced spin-lattice relaxation data allowed for experimental verification of the three-dimensional Li diffusion previously proposed computationally. The 6Li NMR relaxation rates suggest sites Li1 and Li5 (the only five-coordinate Li site) are the most mobile and are adjacent to one another, both in the a-b plane (intralayer) and on the c-axis (interlayer). As shown in the 6Li-6Li exchange spectroscopy NMR spectra, sites Li1 and Li5 likely exchange with one another both between adjacent layered Li6O16 26- chains and through the center of the P12O36 12- rings forming the three-dimensional pathway. The understanding of the Li ion mobility pathways in high-performing solid electrolytes outlines a route for further development of such materials to improve their performance.

Phosphorylated and carbamylated Kraft lignin for improving fire- and biological-resistance of Scots pine wood

In this study, Kraft lignin was modified by ammonium dihydrogen phosphate (ADP) and urea for achieving phosphorylation and carbamylation, aiming to protect wood against biological and fire attack. Scots pine (Pinus sylvestris L.) sapwood was impregnated with a water solution containing Kraft lignin, ADP, and urea, followed by heat treatment at 150 °C, resulting in changes in the properties of the Kraft lignin as well as the wood matrix. Infrared spectroscopy, 13C cross-polarisation magic-angle-spinning (MAS) nuclear magnetic resonance (NMR), and direct excitation single-pulse 31P MAS NMR analyses suggested the grafting reaction of phosphate and carbamylate groups onto the hydroxyl groups of Kraft lignin. Scanning electron microscopy with energy dispersive X-ray spectroscopy indicated that the condensed Kraft lignin filled the lumen as well as partially penetrating the wood cell wall. The modified Kraft lignin imparted fire-retardancy and increased char residue to the wood at elevated temperature, as confirmed by limiting oxygen index, microscale combustion calorimetry, and thermogravimetric analysis. The modified wood exhibited superior resistance against mold and decay fungi attack under laboratory conditions. The modified wood had a similar modulus of elasticity to the unmodified wood, while experiencing a reduction in the modulus of rupture.

Characterization of chemical reactions of silver diammine fluoride and hydroxyapatite under remineralization conditions.

Silver Diammine Fluoride (SDF) is a clinically used topical agent to arrest dental caries. However, the kinetics of its chemical interactions with hydroxyapatite (HA), the principal inorganic component of dental enamel, are not known. The aim was to characterize the step-wise chemical interactions between SDF and HA powder during the clinically important process of remineralization. Two grams of HA powder were immersed in 10 ml acetic acid pH = 4.0 for 2 h to mimic carious demineralization. The powder was then washed and dried for 24 h and mixed with 1.5 ml SDF (Riva Star) for 1 min. The treated powder was then air-dried for 3 min, and 0.2 g was removed and stored in individual tubes each containing 10 ml remineralizing solution. Powder was taken from each tube at various times of exposure to remineralization solution (0 min, 10 min, 2 h, 4 h, 8 h, 24 h, and 10 days), and characterized using Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR) spectroscopy. 19F MAS-NMR spectra showed that calcium fluoride (CaF2) started to form almost immediately after HA was in contact with SDF. After 24 h, the peak shifted to -104.5 ppm suggesting that fluoride substituted hydroxyapatite (FSHA) was formed with time at the expense of CaF2. The 31P MAS-NMR spectra showed a single peak at 2.7 ppm at all time points showing that the only phosphate species present was crystalline apatite. The 35Cl MAS-NMR spectra showed formation of silver chloride (AgCl) at 24 h. It was observed that after the scan, the whitish HA powder changed to black color. In conclusion, this time sequence study showed that under remineralization conditions, SDF initially reacted with HA to form CaF2 which is then transformed to FSHA over time. In the presence of chloride, AgCl is formed which is subsequently photo-reduced to black metallic silver.

Nuclear magnetic resonance spectroscopy to quantify major extracellular matrix components in fibro-calcific aortic valve disease

AbstractFibro-calcific aortic valve disease (FCAVD) is a pathological condition marked by overt fibrous and calcific extracellular matrix (ECM) accumulation that leads to valvular dysfunction and left ventricular outflow obstruction. Costly valve implantation is the only approved therapy. Multiple pharmacological interventions are under clinical investigation, however, none has proven clinically beneficial. This failure of translational approaches indicates incomplete understanding of the underlying pathomechanisms and may result from a limited toolbox of scientific methods to assess the cornerstones of FCAVD: lipid deposition, fibrous and calcific ECM accumulation. In this study, we evaluated magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy to both, qualitatively and quantitatively assess these key elements of FCAVD pathogenesis. NMR spectra showed collagen, elastin, triacylglycerols, and phospholipids in human control and FCAVD tissue samples (n = 5). Calcification, measured by the hydroxyapatite content, was detectable in FCAVD tissues and in valve interstitial cells under procalcifying media conditions. Hydroxyapatite was significantly higher in FCAVD tissues than in controls (p < 0.05) as measured by 31P MAS NMR. The relative collagen content was lower in FCAVD tissues vs. controls (p < 0.05). Overall, we demonstrate the versatility of NMR spectroscopy as a diagnostic tool in preclinical FCAVD assessment.

Structure of amorphous materials in the NASICON system NaTi2Si x PO12

The structure of glasses in the sodium (Na) super-ionic conductor (NASICON) system NaTi2Si x PO12 with x = 0.8 and x = 1.0 was explored by combining neutron and high-energy x-ray diffraction with 29Si, 31P and 23Na solid-state nuclear magnetic resonance (NMR) spectroscopy. The 29Si magic angle spinning (MAS) NMR spectra reveal that the silica component remains fully polymerized in the form of Si4 units, i.e. the silicon atoms are bound to four bridging oxygen atoms. The 31P{23Na} rotational echo adiabatic passage double resonance (REAPDOR) NMR data suggest that the 31P MAS NMR line shape originates from four-coordinated P n units, where n = 1, 2 or 3 is the number of bridging oxygen atoms per phosphorus atom. These sites differ in their 31P-23Na dipolar coupling strengths. The results support an intermediate range order scenario of a phosphosilicate mixed network-former glass in which the phosphate groups selectively attract the Na+ modifier ions. Titanium takes a sub-octahedral coordination environment with a mean Ti–O coordination number of 5.17(4) for x = 0.8 and 4.86(4) for x = 1.0. A mismatch between the P–O and Si–O bond lengths of 8% is likely to inhibit the incorporation of silicon into the phosphorus sites of the NASICON crystal structure.

Probing oxide-based glass structures by solid-state NMR: Opportunities and limitations

This Primer critically reviews the possibilities and limitations of probing the short-range structure of an oxide-based glass by routine magic-angle spinning (MAS) or triple-quantum MAS (3QMAS) nuclear magnetic resonance (NMR) experiments. We briefly outline the structural features of oxide-based glasses and the basics of solid-state NMR. Besides suggesting guidelines for selecting favorable experimental conditions and important considerations for recording high-quality MAS NMR spectra amenable for subsequent analysis, we review options for extracting NMR observables and their distributions from spins-1/2 as well as half-integer spin quadrupolar nuclei. Considering that the isotropic chemical shift remains the primary probe of local structure by MAS NMR, we thoroughly review its dependence on the short-range oxide-based glass parameters from the viewpoint of a very simple and intuitive but qualitative model. The utility of deconvolutions of notably 29Si and 31P MAS NMR spectra are discussed critically. We also suggest alternative yet qualitative analysis options that are available whenever MAS NMR spectral deconvolutions are not warranted without additional information, which incidentally applies to a majority of modern multicomponent glasses.

Nuclear magnetic resonance (NMR) studies of sintering effects on the lithium ion dynamics in Li1.5Al0.5Ti1.5(PO4)3

Abstract Various nuclear magnetic resonance (NMR) methods are combined to study the structure and dynamics of Li1.5Al0.5Ti1.5(PO4)3 (LATP) samples, which were obtained from sintering at various temperatures between 650 and 900 °C. 6Li, 27Al, and 31P magic angle spinning (MAS) NMR spectra show that LATP crystallites are better defined for higher calcination temperatures. Analysis of 7Li spin-lattice relaxation and line-shape changes indicates the existence of two species of lithium ions with clearly distinguishable jump dynamics, which can be attributed to crystalline and amorphous sample regions, respectively. An increase of the sintering temperature leads to higher fractions of the fast lithium species with respect to the slow one, but hardly affects the jump dynamics in either of the phases. Specifically, the fast and slow lithium ions show jumps in the nanoseconds regime near 300 and 700 K, respectively. The activation energy of the hopping motion in the LATP crystallites amounts to ca. 0.26 eV. 7Li field-gradient diffusometry reveals that the long-range ion migration is limited by the sample regions featuring slow transport. The high spatial resolution available from the high static field gradients of our setup allows the observation of the lithium ion diffusion inside the small (<100 nm) LATP crystallites, yielding a high self-diffusion coefficient of D = 2 × 10−12 m2/s at room temperature.

Multiple templating strategy for the control of aluminum and phosphorus distributions in AFX zeolite

A multiple templating strategy using both bulky and small organic structure-directing agents (SDAs) was adapted for AFX zeolite synthesis in order to control the distribution of aluminum and phosphorus. An AFX zeolite with an Si/Al ratio of 4.8 was obtained in the presence of a bulky and rigid SDA, N,N,N',N'-tetraethylbicyclo[2.2.2]oct-7-ene-2,3:5,6-dipyrrolidinium cation (TEBOP2+), and co-existing Na+ cations. The use of a tetramethylammonium cation (Me4N+) as the SDA instead of Na+ provided AFX zeolite with a middle Si/Al ratio of 7.9. Elemental analysis and 13C and 29Si magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy suggested that TEBOP2+ existed in the wide aft cage in both AFX zeolites, while the higher Si/Al ratio was derived from the lower charge density of Me4N+ occupying the narrow gme cage. We also attempted to control the distribution of phosphorus in phosphorus-modified AFX zeolite. The large tetraethylphosphonium cation (Et4P+) and small tetramethylphosphonium cation (Me4P+) were selectively incorporated into aft and gme cages during the hydrothermal synthesis, respectively. As a result, phosphorus oxide with different polymerization degrees were formed by calcination treatment according to the size of the cage occupied by the phosphorus-modifying agents (P-MAs). This direct phosphorus modification using alkylphosphonium was characterized by elemental analysis and 13C, 27Al, and 31P MAS NMR and two-dimensional (2D) 31P–27Al heteronuclear correlation NMR spectroscopies.

Quantitative phase analyses of biomedical pyrophosphate-bearing monetite and brushite cements by solid-state NMR and powder XRD

We present a comprehensive composition analysis of calcium phosphate cements (CPCs) incorporating increasing amounts of bioactive pyrophosphate species (up to 17 wt% P2O7). These cements comprise primarily poorly ordered monetite (CaHPO4) or brushite (CaHPO4⋅2H2O) and are investigated for enhanced osteoinductive bone/tooth implants. The specimens were characterized by magic-angle spinning (MAS) 31P and 1H nuclear magnetic resonance (NMR) spectroscopy along with powder X-ray diffraction (PXRD). 31P MAS NMR was employed to quantify the major monetite/brushite constituents, the crystalline and amorphous pyrophosphates, as well as various minor orthophosphate by-products. The NMR-derived contents of the crystalline phases accorded well with those from Rietveld analyses of the corresponding PXRD data. The amounts of crystalline and amorphous pyrophosphate depended on the precise cement precursor mixture and preparation conditions, which together with their distinct structural roles may enable the design of cements with a tunable P2O74− release into aqueous solutions.

A comparative evaluation of ion release characteristics of three different dental varnishes containing fluoride either with CPP-ACP or bioactive glass

ObjectiveTo compare ion release characteristics of three different dental varnishes either containing CPP-ACP and fluoride (CPP-ACPF, MI Varnish GC, Japan), bioactive glass and fluoride (BGAF, Dentsply Sirona USA) or fluoride alone (NUPRO White, Dentsply Sirona USA) using fluoride-Ion Selective Electrode (F-ISE), Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES), X-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), 19F and 31P Magic Angle Spinning-Nuclear Magnetic Resonance (MAS-NMR). MethodsA thin layer (0.0674±0.0005g) of each varnish (20×25mm in area) was spread on a roughened glass slide (n=7). They were separately immersed in 10ml Tris buffer (0.06M, pH=7.30), and changed after 1, 2, 4, 6, 24 and 48h. Fluoride-ion concentration at each time using the F-ISE, whilst calcium and phosphate release were investigated using ICP-OES. XRD, FTIR. MAS-NMR analyses were also performed before and after immersion. ResultsThe cumulative F-ion release was significantly higher in CPP-ACPF (1.113mmol/g)>BGAF(0.638)>F(0.112) (p<0.001). The cumulative calcium and phosphorus were higher in the CPP-ACPF (0.137mmol/g, 0.119) than BGAF (0.067, 0.015) (p<0.001) respectively. The XRD and 19F MAS-NMR confirmed the presence of NaF peaks in all cases before immersion. There were less prominent signal and appearance of fluorapatite crystals after immersion. 19F MAS-NMR revealed CaF2 formation after immersion in both CPP-ACPF and BGAF. 31P MAS-NMR showed phosphate signals in both CPP-ACPF and BGAF before immersion. FTIR failed to show any signs of apatite formation. SignificanceBoth CPP-ACP and bioactive glass enhanced ion release without compromising the bioavailability of fluoride. The CPP-ACPF varnish had the most promising ion release.

Surface Modification of Layered Perovskite Nanosheets with a Phosphorus Coupling Reagent in a Biphasic System.

Oleyl phosphate-modified HLaNb2O7· xH2O nanosheets (OP_HLaNb nanosheets) were prepared via phase transfer from an aqueous phase, comprising a dispersion of HLaNb2O7· xH2O (HLaNb) nanosheets, formed through the intercalation of tetrabutylammonium ion (TBA+) in the interlayer space of HLaNb and subsequent delamination, to a cyclohexane phase containing oleyl phosphate (OP, a mixture of monoester and diester). The modification of HLaNb nanosheets with OP was essentially completed within 3 days at a pH value of 2 or 4. Both infrared and solid-state 13C cross-polarization and magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectra of the OP_HLaNb nanosheets showed the presence of OP and/or related species and TBA+ on the HLaNb nanosheet surface. The solid-state 31P MAS NMR spectra of OP_HLaNb nanosheets exhibited new signals at -2 and 0 ppm, the former of which indicates the formation of Nb-O-P bonds. These whole data set obtained by complementary techniques clearly point out the modification of the HLaNb nanosheet surface by OP moieties causing a phase transfer. OP_HLaNb nanosheets showed higher dispersibility in cyclohexane than the OP_HLaNb_interlayer nanosheets, which were prepared via stepwise substitution reactions in the interlayers of HLaNb to achieve surface modification with OP and subsequent exfoliation in cyclohexane. The presence of TBA+ on the HLaNb nanosheets and the use of a liquid-liquid biphasic system were likely to improve the dispersibility. These results show that the preparation of OP-modified HLaNb nanosheets which could be well-dispersed in the cyclohexane phase was successful because of the use of a liquid-liquid biphasic system.

Revealing long- and short-range structural modifications within phosphorus-treated HZSM-5 zeolites by atom probe tomography, nuclear magnetic resonance and powder X-ray diffraction.

The average and the local structure of phosphorus-treated HZSM-5 zeolites were investigated by means of atom probe tomography, powder X-ray diffraction (at ambient and cryogenic temperatures) and 1H, 29Si, 27Al, and 31P magic angle spinning (MAS) solid state nuclear magnetic resonance (NMR) spectroscopy. Phosphatation to yield a product with P/Al ≤ 1 followed by thermal treatment leads to breaking of the Si-OH-Al bridging groups, and subsequent partial dealumination of the zeolite framework, as shown by the contraction of the orthorhombic unit-cell volume and by the loss of tetrahedral framework Al, as observed in the 27Al Multiple Quantum (MQ) MAS NMR spectrum. Most of the framework Al is present in an electronic environment distorted by the presence of phosphorus and appears not to be involved in classic Si-OH-Al Brønsted acid sites. The 31P MAS NMR signals indicate that phosphorus interacts with the zeolitic framework to locally form silico-aluminophosphate (SAPO) domains and the presence of a new kind of acidic site was confirmed by the resonance at ∼8.6 ppm in the 1H MAS NMR spectra, attributed to P-OH groups. Increasing the phosphorus loading (P/Al ≫ 1) promotes further dealumination of the framework and cross-dehydroxylation between P-OH and Si-OH species, leading to the formation of a crystalline silicon orthophosphate phase. With decreasing Al content, the monoclinic HZSM-5 structure becomes preferred, especially at 85 K where the strain relaxation is higher. However, the presence of a higher amount of silicophosphate impurities hinders the low-temperature strain release of the framework, indicating that some of these species are localized in the zeolite pores and contribute to the strain build up.

Enhanced efficiency of solid-state NMR investigations of energy materials using an external automatic tuning/matching (eATM) robot

We have developed and explored an external automatic tuning/matching (eATM) robot that can be attached to commercial and/or home-built magic angle spinning (MAS) or static nuclear magnetic resonance (NMR) probeheads. Complete synchronization and automation with Bruker and Tecmag spectrometers is ensured via transistor-transistor-logic (TTL) signals. The eATM robot enables an automated “on-the-fly” re-calibration of the radio frequency (rf) carrier frequency, which is beneficial whenever tuning/matching of the resonance circuit is required, e.g. variable temperature (VT) NMR, spin-echo mapping (variable offset cumulative spectroscopy, VOCS) and/or in situ NMR experiments of batteries. This allows a significant increase in efficiency for NMR experiments outside regular working hours (e.g. overnight) and, furthermore, enables measurements of quadrupolar nuclei which would not be possible in reasonable timeframes due to excessively large spectral widths. Additionally, different tuning/matching capacitor (and/or coil) settings for desired frequencies (e.g.7Li and 31P at 117 and 122MHz, respectively, at 7.05 T) can be saved and made directly accessible before automatic tuning/matching, thus enabling automated measurements of multiple nuclei for one sample with no manual adjustment required by the user. We have applied this new eATM approach in static and MAS spin-echo mapping NMR experiments in different magnetic fields on four energy storage materials, namely: (1) paramagnetic 7Li and 31P MAS NMR (without manual recalibration) of the Li-ion battery cathode material LiFePO4; (2) paramagnetic 17O VT-NMR of the solid oxide fuel cell cathode material La2NiO4+δ; (3) broadband 93Nb static NMR of the Li-ion battery material BNb2O5; and (4) broadband static 127I NMR of a potential Li–air battery product LiIO3. In each case, insight into local atomic structure and dynamics arises primarily from the highly broadened (1–25MHz) NMR lineshapes that the eATM robot is uniquely suited to collect. These new developments in automation of NMR experiments are likely to advance the application of in and ex situ NMR investigations to an ever-increasing range of energy storage materials and systems.

Relationship between structure and mobility of proton carriers injected by electrochemical substitution of sodium ions with protons in 35NaO1/2-1 WO3-8NbO5/2-5LaO3/2-51PO5/2-based glasses

Using Raman and 31P magic-angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopies, we studied the structural changes in 35NaO1/2-1WO3-8NbO5/2-5LaO3/2-51PO5/2 glass upon introducing Al2O3 and/or Y2O3 in order to understand the reduced mobility of proton carriers in glasses with Al2O3 and/or Y2O3 in which proton carriers were injected by alkali-proton substitution (APS). The Raman and 31P MAS-NMR spectra showed that phosphate chains were shortened by the Al2O3 and/or Y2O3 introduced into 1W glass. This structural change increased the fraction of protons bound to oxygen atoms in the terminal PO4 (i.e., the Q1 unit) of the phosphate chains. Because the protons bound to terminal Q1 units in phosphate chains tightly bind to oxygen atoms, as opposed to the protons bound to inner Q2 units in phosphate chains, we attributed the reduced mobility of proton carriers upon introducing AlO3/2 and/or YO3/2 into 1W glass to the shortening of phosphate chains. From these results we propose that to obtain a highly proton-conducting glass after APS, the glass must have a composition of O/P <3.5 and thus a sufficiently high fraction of Q2 units.

From crystalline to amorphous calcium pyrophosphates: A solid state Nuclear Magnetic Resonance perspective

Hydrated calcium pyrophosphates (CPP, Ca2P2O7·nH2O) are a fundamental family of materials among osteoarticular pathologic calcifications. In this contribution, a comprehensive multinuclear NMR (Nuclear Magnetic Resonance) study of four crystalline and two amorphous phases of this family is presented. 1H, 31P and 43Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different 1H and 43Ca solid state NMR signatures were observed for the amorphous phases, depending on the synthetic procedure used. The NMR parameters of the crystalline phases were determined using the GIPAW (Gauge Including Projected Augmented Wave) DFT approach, based on first-principles calculations. In some cases, relaxed structures were found to improve the agreement between experimental and calculated values, demonstrating the importance of proton positions and pyrophosphate local geometry in this particular NMR crystallography approach. Such calculations serve as a basis for the future ab initio modeling of the amorphous CPP phases. Statement of significanceThe general concept of NMR crystallography is applied to the detailed study of calcium pyrophosphates (CPP), whether hydrated or not, and whether crystalline or amorphous. CPP are a fundamental family of materials among osteoarticular pathologic calcifications. Their prevalence increases with age, impacting on 17.5% of the population after the age of 80. They are frequently involved or associated with acute articular arthritis such as pseudogout. Current treatments are mainly directed at relieving the symptoms of joint inflammation but not at inhibiting CPP formation nor at dissolving these crystals. The combination of advanced NMR techniques, modeling and DFT based calculation of NMR parameters allows new original insights in the detailed structural description of this important class of biomaterials.

A study of the glass formation and crystallization in the mixed fluorozirconate–phosphate systems ZrF4–BaF2(SnF2)–NaPO3

Fluorozirconate–phosphate glasses in the ZrF4–BaF2(SnF2)–NaPO3 and 53ZrF4–30BaF2–(17−x)NaPO3–xMF3 systems (M=Ga, In, Bi; 1≤x≤5) have been prepared and characterized by differential thermal analysis (DTA), 19F nuclear magnetic resonance (NMR), 19F and 31P magic-angle spinning (MAS) NMR, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). It was shown that glasses consisted of fluorozirconate and phosphate subsystems, which coexisted independently. The additives of metal trifluorides MF3 do not virtually affect thermal characteristics of fluorozirconate subsystem but decrease gradually the crystallization temperature (Tc2) of phosphate subsystem According to the SAXS and TEM data, the fluorozirconate–phosphate glasses have the globular structure with the particles size of 50–560Å. Mixed fluorozirconate–phosphate glasses can be considered as precursors for obtaining new functional materials.

Characterisation of a remineralising Glass Carbomer® ionomer cement by MAS-NMR Spectroscopy

ObjectivesThe purpose of this study was to characterize commercial glass polyalkenoate cement (GPC) or glass ionomer cement (GIC), Glass Carbomer®, which is designed to promote remineralization to fluorapatite (FAp) in the mouth. The setting reaction of the cement was followed using magic angle spinning nuclear magnetic resonance (MAS-NMR) spectroscopy. MethodsGlass Carbomer® initial glass powder and cements were subjected to 27Al, 31P, 19F and 29Si MAS-NMR analysis. X-ray powder diffraction (XRD) was employed to determine the presence of crystalline phases. Results27Al MAS-NMR showed the Al to be predominantly four coordinate, Al(IV), and the presence of Al–O–P species in the glass. The proportion of Al(IV) was reduced with setting reaction of the cement and significant amount of six coordinate Al, Al(VI), was found in the cement. The 31P MAS-NMR spectra showed clearly a decrease of the orthophosphate peak of apatite on initial setting. 19F MAS-NMR showed only a small fraction of FAp. 29Si MAS-NMR demonstrated the presence of largely Q4(2Al) in the glass which changed only little in the aged cement. SignificanceThis study also demonstrated how the setting reaction in Glass Carbomer® cement and other GICs can be followed by 27Al MAS-NMR examining the conversion of Al(IV) to Al(VI). Our data revealed that the apatite in this cement was not FAp but largely hydroxyapatite, which was partially consumed during the cement formation.

Local structure around phosphorus and silicon in the CaO–SiO2–PO2.5 system

The local structure of phosphorus and silicon in the molten CaO–SiO2–PO2.5 slag system was investigated by magic angle spinning nuclear magnetic resonance (MAS-NMR). The 31P MAS-NMR spectra revealed that phosphorus was present primarily as the monophosphate complex ion PO43−, with a small amount of diphosphate ion also present. Their relative ratio to total phosphorus was independent of the phosphate concentration of the sample. In the case of the 29Si MAS-NMR, the mean number of the non-bridging oxygen atoms associated with tetrahedrally coordinated silicon decreased as the phosphate concentration increased at a fixed CaO/SiO2 ratio. This indicates that the nonbridging oxygen atoms around the silicon were replaced by bridging oxygen atoms around the phosphorus as the phosphate concentration in the samples increased.To elucidate the basicity dependence of the structure of slag, the relationship between the structure and optical basicity was also investigated. The relative ratio of Qn (Qn means the silicon atoms tetrahedrally bonded with “n” number of bridging oxygen atoms) strongly depends on the optical basicity. These optical basicity dependencies of the structures of phosphorus and silicon can be explained clearly by the basicity equalization concept (Duffy and Ingram, 1976) [12].

31P MAS NMR Spectroscopy of Hexachlorocyclotriphosphazene at Different Stages During Thermal Ring-Opening Polymerization

Thermal ring-opening polymerization of hexachlorocyclotriphosphazene was probed using 31 P magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The spectrum of unreacted hexa- chlorocyclotriphosphazene was compared with the spectra of a reaction mixture at 3, 8 and 17.5 h of polymerization. Signals from trimer, oligomer, polymer and hydrolysis products were identified in the spectra and used to observe changes in the mixture during polymerization. The signal of poly(dichlorophosphazene) exhibits a complex behavior where ten individual components were observed and ana- lyzed by deconvolution. These lines were preliminarily assigned to species with differing chain lengths based on their chemical shifts and relative intensities. This work shows that 31 P MAS NMR has the potential to provide quantitative information about the rates of chain propaga- tion and cross-linking during thermal ring-opening polymerization.

Solid‐state NMR spectroscopy of Pb‐rich apatite

Pb-containing hydroxylapatite phases synthesized under aqueous conditions were investigated by X-ray diffraction and solid-state nuclear magnetic resonance (NMR) techniques to determine the Pb, Ca distribution. 31P and 1H magic-angle spinning (MAS) NMR results indicate slight shifts of the isotropic chemical shift with increased Ca content and complex lineshapes at compositions with near equal amounts of Ca and Pb. 31P{207Pb} and 1H{207Pb} rotational-echo double resonance (REDOR) results for intermediate compositions show that resolved spectral features cannot be assigned simply in terms of local Ca, Pb configurations or coexisting phases. 207Pb MAS NMR spectra are easily obtained for these materials and contain well-resolved resonances for crystallographically unique A1 and A2 Pb sites. Splitting of the A1 and A2 207Pb resonances for pure hydroxyl-pyromorphite (Pb10(PO4)6(OH)2) compared to natural pyromorphite (Pb5(PO4)3Cl) suggests symmetry reduced from hexagonal. We find that 207Pb{1H} CP/MAS NMR is impractical in Pb-rich hydroxylapatites due to fast 207Pb relaxation.