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Scaffolds are needed that can act as temporary templates for bone regeneration and actively stimulate vascularized bone growth so that bone grafting is no longer necessary. To achieve this, the scaffold must have a suitable interconnected pore network and be made of an osteogenic material. Bioactive glass is an ideal material because it rapidly bonds to bone and degrades over time, releasing soluble silica and calcium ions that are thought to stimulate osteoprogenitor cells. Melt-derived bioactive glasses, such as the original Bioglass composition, are available commercially, but porous scaffolds have been difficult to produce because Bioglass and similar compositions crystallize on sintering. Sol-gel foam scaffolds have been developed that avoid this problem. They have a hierarchical pore structure comprising interconnected macropores, with interconnect diameters in excess of the 100 microm that is thought to be needed for vascularized bone ingrowth, and an inherent nanoporosity of interconnected mesopores (2-50 nm) which is beneficial for the attachment of osteoprogenitor cells. They also have a compressive strength in the range of cancellous bone. This paper describes the optimized sol-gel foaming process and illustrates the importance of optimizing the hierarchical structure from the atomic through nano, to the macro scale with respect to biological response. [ABSTRACT FROM AUTHOR]

Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 (LAGP) is a promising oxide solid electrolyte for all-solid-state batteries due to its excellent air stability, acceptable electrochemical stability window, and cost-effective precursor materials. However, further improvement in the ionic conductivity performance of oxide solid-state electrolytes is hindered by the presence of grain boundaries and their associated morphologies and composition. These key factors thus represent a major obstacle to the improved design of modern oxide based solid-state electrolytes. This study establishes a correlation between the influence of the grain boundary phases, their 3D morphology, and compositions formed under different sintering conditions on the overall LAGP ionic conductivity. Spark plasma sintering has been employed to sinter oxide solid electrolyte material at different temperatures with high compacity values, whereas a combined potentiostatic electrochemical impedance spectroscopy, 3D FIB-SEM tomography, XRD, and solid-state NMR/materials modeling approach provides an in-depth analysis of the influence of the morphology, structure, and composition of the grain boundary phases that impact the total ionic conductivity. This work establishes the first 3D FIB-SEM tomography analysis of the LAGP morphology and the secondary phases formed in the grain boundaries at the nanoscale level, whereas the associated 31 P and 27 Al MAS NMR study coupled with materials modeling reveals that the grain boundary material is composed of Li 4 P 2 O 7 and disordered Li 9 Al 3 (P 2 O 7 ) 3 (PO 4 ) 2 phases. Quantitative 31 P MAS NMR measurements demonstrate that optimal ionic conductivity for the LAGP system is achieved for the 680 °C SPS preparation when the disordered Li 9 Al 3 (P 2 O 7 ) 3 (PO 4 ) 2 phase dominates the grain boundary composition with reduced contributions from the highly ordered Li 4 P 2 O 7 phases, whereas the 27 Al MAS NMR data reveal that minimal structural change is experienced by each phase throughout this suite of sintering temperatures.

Introduction: Hybrids consist of inorganic and organic co-networks that are indistinguishable above the nanoscale, which can lead to unprecedented combinations of properties, such as high toughness and controlled degradation. Methods: We present 3D printed bioactive hybrid scaffolds for bone regeneration, produced by incorporating calcium into our "Bouncy Bioglass", using calcium methoxyethoxide (CME) as the calcium precursor. SiO 2 -CaO CME /PTHF/PCL-diCOOH hybrid "inks" for additive manufacturing (Direct Ink Writing) were optimised for synergy of mechanical properties and open interconnected pore channels. Results and Discussion: Adding calcium improved printability. Changing calcium content (5, 10, 20, 30, and 40 mol.%) of the SiO 2 -CaO CME /PTHF/PCL-diCOOH hybrids affected printability and mechanical properties of the lattice-like scaffolds. Hybrids containing 30 mol.% calcium in the inorganic network (70S30C CME -CL) printed with 500 µm channels and 100 µm strut size achieved the highest strength (0.90 ± 0.23 MPa) and modulus of toughness (0.22 ± 0.04 MPa). These values were higher than Ca-free SiO 2 /PTHF/PCL-diCOOH hybrids (0.36 ± 0.14 MPa strength and 0.06 ± 0.01 MPa toughness modulus). Over a period of 90 days of immersion in simulated body fluid (SBF), the 70S30C CME -CL hybrids also kept a stable strain to failure (~30 %) and formed hydroxycarbonate apatite within three days. The extracts released by the 70S30C CME -CL hybrids in growth medium did not cause cytotoxic effects on human bone marrow stromal cells over 24 h of culture., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Heyraud, Tallia, Sory, Ting, Tchorzewska, Liu, Pilsworth, Lee, Hanna, Rankin and Jones.)

Understanding and mastering the structural evolution of water oxidation electrocatalysts lays the foundation to finetune their catalytic activity. Herein, we demonstrate that surface reconstruction of spinel oxides originates from the metal-oxygen covalency polarity in the M T -O-M O backbone. A stronger M O -O covalency relative to M T -O covalency is found beneficial for a more thorough reconstruction towards oxyhydroxides. The structure-reconstruction relationship allows precise prediction of the reconstruction ability of spinel pre-catalysts, based on which the reconstruction degree towards the in situ generated oxyhydroxides can be controlled. The investigations of oxyhydroxides generated from spinel pre-catalysts with the same reconstruction ability provide guidelines to navigate the cation selection in spinel pre-catalysts design. This work reveals the fundamentals for manipulating the surface reconstruction of spinel pre-catalysts for water oxidation., (© 2023. The Author(s).)

Alkali-activated materials (AAMs) have been known as an alternative cementitious binder in construction for more than 120 years. Several buildings utilizing AAMs were realized in Europe in the 1950s-1980s. During the last 30 years, the interest towards AAMs has been reinvigorated due to the potentially lower CO 2 footprint in comparison to Portland cement. However, one often-raised issue with AAMs is the lack of long-term studies concerning durability in realistic conditions. In the present study, we examined a roof tile, which was prepared from alkali-activated blast furnace slag mortar and exposed to harsh Northern Scandinavian weather conditions in Turku, Finland, for approximately 30 years. Characterization of this roof tile provides unique and crucial information about the changes occurring during AAM lifetime. The results obtained with a suite of analytical techniques indicate that the roof tile had maintained excellent durability properties with little sign of structural disintegration in real-life living lab conditions, and thus provide in part assurance that AAM-based binders can be safely adopted in harsh climates. The phase assemblage and nanostructural characterization results reported here further elucidate the long-term changes occurring in AAMs and provide reference points for accelerated durability tests and thermodynamic modelling., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Methylammonium (MA + ) lead halide perovskites (MAPbX 3 ) have been widely investigated for photovoltaic applications, with the addition of Cs improving structural and thermal stability. This study reports the complete A site miscibility of Cs + and MA + cations in the lead chloride and lead bromide perovskites with nominal stoichiometric formulae (Cs x MA 1- x )Pb(Cl/Br) 3 ( x = 0, 0.13, 0.25, 0.37, 0.50, 0.63, 0.75, 0.87, 1). These suites of materials were synthesized mechanochemically as a simple, cost-effective synthesis technique to produce highly ordered, single phase particles. In contrast to previous studies using conventional synthetic routes that have reported significant solubility gaps, this solvent-free approach induces complete miscibility within the dual cation Cs + /MA + system, with the resultant structures exhibiting high short-range and long-range atomic ordering across the entire compositional range that are devoid of solvent inclusions and disorder. The subtle structural evolution from cubic to orthorhombic symmetry reflecting PbX 6 octahedral tilting was studied using complementary high resolution TEM, powder XRD, multinuclear 133 Cs/ 207 Pb/ 1 H MAS NMR, DSC, XPS and UV/vis approaches. The phase purity and exceptional structural order were reflected in the very high resolution HRTEM images presented from particles with crystallite sizes in the ∼80-170 nm range, and the stability and long lifetimes of the Br series (10-20 min) and the Cl series (∼30 s-1 min) under the 200 kV/146 μA e - beam. Rietveld refinements associated with the room temperature PXRD study demonstrated that each system converged towards single phase compositions that were very close to the intended target stoichiometries, thus indicating the complete miscibility within these dual cation Cs + /MA + solid solution systems. The multinuclear MAS NMR data showed a distinct sensitivity to the changing solid solution compositions across the MAPbX 3 -CsPbX 3 partition. In particular, the 133 Cs shifts demonstrated a sensitivity to the cubic-orthorhombic phase transition while the 133 Cs T 1 s exhibited a pronounced sensitivity to the variable Cs + cation mobility across the compositional range. Variable temperature PXRD studies facilitated the production of phase diagrams mapping the Cs + /MA + compositional space for the (Cs x MA 1- x )PbCl 3 and (Cs x MA 1- x )PbBr 3 solid solution series, while Tauc plots of the UV/vis data exhibited reducing bandgaps with increasing MA + incorporation through ranges of cubic phases where octahedral tilting was absent.

Objectives: Antibiotic resistance is increasingly a growing global threat. This study aimed to investigate the potential use of newly developed scandium-doped phosphate-based glasses (Sc-PBGs) as an antibacterial and anticariogenic agent through controlled release of Sc 3+ ions., Methods: Sc-PBGs with various calcium and sodium oxide contents were produced and characterised using thermal and spectroscopic analysis. Degradation behaviour, ion release, antibacterial action against Streptococcus mutans, anti-matrix metalloproteinase-2 (MMP-2) activity, remineralisation potential and in vivo biocompatibility were also investigated., Results: The developed glass system showed linear Sc 3+ ions release over time. The released Sc 3+ shows statistically significant inhibition of S. mutans biofilm (1.2 log 10 CFU reduction at 6 h) and matrix metalloproteinase-2 (MMP-2) activity, compared with Sc-free glass and positive control. When Sc-PBGs were mounted alongside enamel sections, subjected to acidic challenges, alternating hyper- and hypomineralisation layers consistent with periods of re- and demineralisation were observed demonstrating their potential remineralising action. Furthermore, Sc-PBGs produced a non-toxic response when implanted subcutaneously for 2 weeks in Sprague Dawley rats., Significance: Since Sc 3+ ions might act on various enzymes essential to the biological mechanisms underlying caries, Sc-PBGs could be a promising therapeutic agent against cariogenic bacteria., (Copyright © 2021 The Academy of Dental Materials. Published by Elsevier Inc. All rights reserved.)

A combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1 J NC coupling measurements supported by periodic density functional theory (DFT) calculations is used to characterise the transition from an n-π* interaction to bond formation between a nucleophilic nitrogen atom and an electrophilic sp 2 carbon atom in a series of crystalline peri-substituted naphthalenes. As the N⋅⋅⋅C distance reduces there is a sharp decrease in the Laplacian derived from increasing charge density between the two groups at ca. N⋅⋅⋅C = 1.8 Å, with the periodic DFT calculations predicting, and heteronuclear spin-echo NMR measurements confirming, the 1 J NC couplings of ≈3-6 Hz for long C-N bonds (1.60-1.65 Å), and 1 J NC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å., (© 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

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 1 H , 13 C , 31 P and 31 P nuclei, with the 1 H and 13 C 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 1 H NMR spectra is presented for the three hydrates, based on the structure and local dynamics. The corresponding 31 P 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., Competing Interests: The authors declare that they have no conflict of interest., (Copyright: © 2021 César Leroy et al.)

There has been a huge amount of interest in perovskites recently and new structures of hybrid perovskites are frequently reported. The classification of perovskites has been unambiguous in the discussion of 3D and layered 2D perovskites due to the dimensional constraints. However, in 1D perovskites, the additional degrees of freedom have resulted in a large number of possible structural configurations. The new proposed notation aims to classify these structures based on the connectivity of the octahedra of the perovskite, which has a periodic repeating pattern. However, the notation should be restricted to simple 1D perovskites and haloplumbate structures as the notation would become too cumbersome when applied to an exotic framework which has 3D characteristics, such as perovskite polytypes.

Inorganic/organic hybrids have co-networks of inorganic and organic components, with the aim of obtaining synergy of the properties of those components. Here, a silica-gelatin sol-gel hybrid "ink" was directly 3D printed to produce 3D grid-like scaffolds, using a coupling agent, 3-glycidyloxypropyl)trimethoxysilane (GPTMS), to form covalent bonds between the silicate and gelatin co-networks. Scaffolds were printed with 1 mm strut separation, but the drying method affected the final architecture and properties. Freeze drying produced <40 μm struts and large ~700 μm channels. Critical point drying enabled strut consolidation, with ~160 μm struts and ~200 μm channels, which improved mechanical properties. This architecture was critical to cellular response: when chondrocytes were seeded on the scaffolds with 200 μm wide pore channels in vitro, collagen Type II matrix was preferentially produced (negligible amount of Type I or X were observed), indicative of hyaline-like cartilaginous matrix formation, but when pore channels were 700 μm wide, Type I collagen was prevalent. This was supported by Sox9 and Aggrecan expression. The scaffolds have potential for regeneration of articular cartilage regeneration, particularly in sports medicine cases., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Struvite-K (MgKPO 4 ·6H 2 O) 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 25 Mg and 39 K MAS NMR techniques, alongside 31 P MAS NMR and thermal analysis. A single resonance was present in each of the 25 Mg and 39 K 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 (MgNH 4 PO 4 ·6H 2 O). 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-MgKPO 4 . At 350 °C, recrystallization was observed, yielding β-MgKPO 4 , commensurate with an endothermic DTA event. A subsequent phase transition to γ-MgKPO 4 was observed on further heating, which reversed on cooling, resulting in the α-MgKPO 4 structure stabilized at room temperature. This behavior was dissimilar from that of struvite exposed to high temperature, where NH 4 liberation occurs at temperatures >50 °C, indicating that struvite-K could potentially withstand high temperatures via a transition to MgKPO 4 .

Driven by the clinical need for a strong tissue adhesive with elastomeric material properties, a departure from legacy crosslinking chemistries was sought as a multipurpose platform for tissue mending. A fresh approach to bonding wet substrates has yielded a synthetic biomaterial that overcomes the drawbacks of free-radical and nature-inspired bioadhesives. A food-grade liquid polycaprolactone grafted with carbene precursors yields CaproGlu. The first-of-its-kind low-viscosity prepolymer is VOC-free and requires no photoinitiators. Grafted diazirine end-groups form carbene diradicals upon low energy UVA (365 nm) activation that immediately crosslink tissue surfaces; no pre-heating or animal-derived components are required. The hydrophobic polymeric environment enables metastable functional groups not possible in formulations requiring solvents or water. Activated diazirine within CaproGlu is uniquely capable of crosslinking all amino acids, even on wet tissue substrates. CaproGlu undergoes rapid liquid-to-biorubber transition within seconds of UVA exposure-features not found in any other bioadhesive. The exceptional shelf stability of CaproGlu allows gamma sterilization with no change in material properties. CaproGlu wet adhesiveness is challenged against current unmet clinical needs: anastomosis of spliced blood vessels, anesthetic muscle patches, and human platelet-mediating coatings. The versatility of CaproGlu enables both organic and inorganic composites for future bioadhesive platforms., (Copyright © 2020 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

A procedure to acquire two Multiple-Quantum Magic Angle Spinning (MQMAS) NMR experiments with the same instrument time is presented. A triply tuned probe is utilized with multiple receivers to collect data with staggered acquisitions and thus more efficiently use the instrument time. The data for one nucleus is collected during the recovery delay of the other nucleus, and vice versa. The instrument time is reduced to 60-80% of the time needed for the single acquisition collection Specifically our approach is presented for recording triple-quantum (3Q) 17 O and either 3Q or quintuple-quantum (5Q) 27 Al MAS NMR spectra of a 1.18Na 2 O•5SiO 2 •Al 2 O 3 glass gel., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier Inc. All rights reserved.)

Heavy water or deuterium oxide (D 2 O) comprises deuterium, a hydrogen isotope twice the mass of hydrogen. Contrary to the disadvantages of deuterated perovskites, such as shorter recombination lifetimes and lower/invariant efficiencies, the serendipitous effect of D 2 O as a beneficial solvent additive for enhancing the power conversion efficiency (PCE) of triple-A cation (cesium (Cs)/methylammonium (MA)/formaminidium (FA)) perovskite solar cells from ≈19.2% (reference) to 20.8% (using 1 vol% D 2 O) with higher stability is reported. Ultrafast optical spectroscopy confirms passivation of trap states, increased carrier recombination lifetimes, and enhanced charge carrier diffusion lengths in the deuterated samples. Fourier transform infrared spectroscopy and solid-state NMR spectroscopy validate the N-H 2 group as the preferential isotope exchange site. Furthermore, the NMR results reveal the induced alteration of the FA to MA ratio due to deuteration causes a widespread alteration to several dynamic processes that influence the photophysical properties. First-principles density functional theory calculations reveal a decrease in PbI 6 phonon frequencies in the deuterated perovskite lattice. This stabilizes the PbI 6 structures and weakens the electron-LO phonon (Fröhlich) coupling, yielding higher electron mobility. Importantly, these findings demonstrate that selective isotope exchange potentially opens new opportunities for tuning perovskite optoelectronic properties., (© 2020 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

An electrospinning technique was used to produce three-dimensional (3D) bioactive glass fibrous scaffolds, in the SiO 2 -CaO sol-gel system, for wound healing applications. Previously, it was thought that 3D cotton wool-like structures could only be produced from sol-gel when the sol contained calcium nitrate, implying that the Ca 2+ and its electronic charge had a significant effect on the structure produced. Here, fibres with a 3D appearance were also electrospun from compositions containing only silica. A polymer binding agent was added to inorganic sol-gel solutions, enabling electrospinning prior to bioactive glass network formation and the polymer was removed by calcination. While the addition of Ca 2+ contributes to the 3D morphology, here we show that other factors, such as relative humidity, play an important role in producing the 3D cotton-wool-like macrostructure of the fibres. A human dermal fibroblast cell line (CD-18CO) was exposed to dissolution products of the samples. Cell proliferation and metabolic activity tests were carried out and a VEGF ELISA showed a significant increase in VEGF production in cells exposed to the bioactive glass samples compared to control in DMEM. A novel SiO 2 -CaO nanofibrous scaffold was created that showed tailorable physical and dissolution properties, the control and composition of these release products are important for directing desirable wound healing interactions.

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.

It is well-established that the inclusion of small atomic species such as boron (B) in powder metal catalysts can subtly modify catalytic properties, and the associated changes in the metal lattice imply that the B atoms are located in the interstitial sites. However, there is no compelling evidence for the occurrence of interstitial B atoms, and there is a concomitant lack of detailed structural information describing the nature of this occupancy and its effects on the metal host. In this work, we use an innovative combination of high-resolution 11 B magic-angle-spinning (MAS) and 105 Pd static solid-state NMR nuclear magnetic resonance (NMR), synchrotron X-ray diffraction (SXRD), in situ X-ray pair distribution function (XPDF), scanning transmission electron microscopy-annular dark field imaging (STEM-ADF), electron ptychography, and electron energy loss spectroscopy (EELS) to investigate the B atom positions, properties, and structural modifications to the palladium lattice of an industrial type interstitial boron doped palladium nanoparticle catalyst system (Pd- int B/C NPs). In this study, we report that upon B incorporation into the Pd lattice, the overall face centered cubic (FCC) lattice is maintained; however, short-range disorder is introduced. The 105 Pd static solid-state NMR illustrates how different types (and levels) of structural strain and disorder are introduced in the nanoparticle history. These structural distortions can lead to the appearance of small amounts of local hexagonal close packed (HCP) structured material in localized regions. The short-range lattice tailoring of the Pd framework to accommodate interstitial B dopants in the octahedral sites of the distorted FCC structure can be imaged by electron ptychography. This study describes new toolsets that enable the characterization of industrial metal nanocatalysts across length scales from macro- to microanalysis, which gives important guidance to the structure-activity relationship of the system.

Calcium phosphate glasses are a promising new generation of biomaterials that can simultaneously induce tissue regeneration and controlled release of therapeutic molecules. In this work, novel calcium phosphate glasses containing 0, 2, 4, and 6 mol % Cu 2+ were synthesized via room temperature precipitation reaction in aqueous solution. The effect of Cu 2+ addition on the glass properties and structure was investigated using thermal analysis, 31 P solid-state MAS NMR, Raman spectroscopy, and X-ray diffraction. All glasses crystallize at temperature >500 °C and are mainly formed by Q 1 groups. The release of P, Ca, and Cu in solution over time was monitored via inductively coupled plasma-optical emission spectroscopy. It was found that with increasing Cu content, the amount of P and Ca released decreases whereas the amount of Cu released increases. The effect of Cu 2+ release on the antibacterial activity against S. aureus , a bacterial strain commonly found in postsurgery infections, has been investigated. The addition of copper has been shown to infer the glasses antibacterial properties. As expected, the antibacterial activity of the glasses increases with increasing Cu 2+ content. Cytocompatibility was assessed by seeding human osteoblast-like osteosarcoma cells Saos-2 (HTB85) on the glass particles. A significant increase in cell number was observed in all the glasses investigated. The copper-doped calcium phosphate glasses have proven to be multifunctional, as they combine bone regenerative properties with antibacterial activity. Therefore, they have great potential as antibacterial bioresorbable materials for hard tissue regeneration.

Bioactive glass nanoparticles (BGNPs) are of great interest in tissue engineering as they possess high dissolution rate and capability of being internalized by cells, releasing their dissolution products with therapeutic benefits intracellularly. A modified Stöber process can be applied to obtain different BGNPs compositions containing therapeutic ions while maintaining controllable particle morphology, monodispersity and reduce agglomeration. Here, BGNPs containing Mn, an ion that has been shown to influence the osteoblast proliferation and bone mineralization, were evaluated. Particles with up to 142.3 ± 10.8 nm and spherical morphology were obtained after MnO incorporation in the SiO 2 - CaO system. X-ray photoelectron spectroscopy (XPS) indicated the presence of Mn 2+ species and also a reduction in the number of bridging oxygen bonds due to the Ca and Mn. The Ca and Mn network modifier role on the silica network was also confirmed by magic-angle spinning 29 Si solid-state nuclear magnetic resonance (MAS NMR). MTT evaluation showed no reduction in the mitochondrial metabolic activity of human mesenchymal stem cells exposed to the glass ionic products. Thus, evaluation showed that Mn could be incorporated into BGNPs by the modified Stöber method while maintaining their spherical morphology and features as a promising strategy for tissue regeneration., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Copper-doped hydroxyapatite (HA) of nominal composition Ca 10 (PO 4 ) 6 [Cu x (OH) 2-2x O x ] (0.0 ≤ x ≤ 0.8) was prepared by solid-state and wet chemical processing to explore the impact of the synthesis route and mode of crystal chemical incorporation of copper on the antibacterial efficacy against Escherichia coli ( E. coli ) and Staphylococcus aureus ( S. aureus ) strains. Apatites prepared by solid-state reaction showed unit cell volume dilation from 527.17 Å 3 for copper-free HA to 533.31 Å 3 for material of the putative composition Ca 10 (PO 4 ) 6 [Cu 0.8 (OH) 0.4 O 0.8 ] consistent with Cu + insertion into the [001] hydroxyapatite channel. This was less pronounced (528.30 Å 3 to 529.3 Å 3 ) in the corresponding wet chemical synthesised products, suggesting less complete Cu tunnel incorporation and partial tenancy of Cu in place of calcium. X-ray absorption spectroscopy suggests fast quenching is necessary to prevent oxidation of Cu + to Cu 2+ . Raman spectroscopy revealed an absorption band at 630 cm -1 characteristic of symmetric O-Cu + -O units tenanted in the apatite channel while solid-state 31 P magic-angle-spinning nuclear magnetic resonance (MAS NMR) supported a vacancy-Cu + substitution model within the apatite channel. The copper doping strategy increases antibacterial efficiency by 25% to 55% compared to undoped HA, with the finer particle sizes and greater specific surface areas of the wet chemical material demonstrating superior efficacy.

Amino acid δ 15 N values of foliage of various plant taxa, grown at the experimental farm stations of North Wyke, UK and Bad Lauchstädt, Germany were determined by GC-C-IRMS. The difference between δ 15 N values of glutamate (Glx) and phenylalanine (Phe) were found to differ significantly between woody and herbaceous plants, with mean Δ 15 N Glx-Phe (i.e. δ 15 N Phe - δ 15 N Glx ) values of -9.3 ± 1.6‰ and -5.8 ± 2.1‰, respectively. These differences in values are hypothesised to be due to the involvement of Phe in the phenylpropanoid pathway, by which lignin and other phenolic secondary metabolites are produced, leading to isotopic fractionation and enrichment of the remaining Phe pool available for protein biosynthesis. This results in the more negative Δ 15 N Glx-Phe values observed in woody plants relative to herbaceous plants, as the former are assumed to produce more lignin. To test this assumption, plant leaf tissue lignin concentrations were estimated by solid state 13 C cross-polarisation, magic-angle-spinning (CPMAS) NMR spectroscopy for a subset of plants, which showed that tree foliage has a higher concentration of lignin (12.6 wt%) than herbaceous foliage (6.3 wt%). The correlation of lignin concentration with Δ 15 N Glx-Phe values demonstrates that the difference in these values with plant type is indeed due to differential production of lignin. The ability to estimate the lignin content of plants from amino acid δ 15 N values will, to give one example, allow refinement of estimates of herbivore diet in present and past ecosystems, enabling more accurate environmental niche modelling., (Copyright © 2019. Published by Elsevier Ltd.)

We describe a new class of inorganic polymeric materials featuring a main chain consisting of P V -O bonds and aryl side groups, which was obtained with >70 repeat units by ring-opening polymerization of cyclic phosphonates. This monomer-polymer system was found to be dynamic in solution enabling selective depolymerization under dilute conditions, which can be tuned by varying the substituents. The polymers show high thermal stability to weight loss and can be easily fabricated into self-standing thin films. Structural characterizations of the cyclic 6- and 12-membered ring precursors are also described.

The ability to clearly relate local structure to function is desirable for many catalytically relevant Pd-containing systems. This report represents the first direct 105 Pd solid state NMR measurements of diamagnetic inorganic (K 2 Pd(iv)Cl 6 , (NH 4 ) 2 Pd(iv)Cl 6 and K 2 Pd(iv)Br 6 ) complexes, and micron- and nano-sized Pd metal particles at room temperature, thereby introducing effective 105 Pd chemical shift and Knight shift ranges in the solid state. The very large 105 Pd quadrupole moment (Q) makes the quadrupole parameters (C Q , η Q ) extremely sensitive to small structural distortions. Despite the well-defined high symmetry octahedral positions describing the immediate Pd coordination environment, 105 Pd NMR measurements can detect longer range disorder and anisotropic motion in the interstitial positions. The approach adopted here combines high resolution X-ray pair distribution function (PDF) analyses with 105 Pd, 39 K and 35 Cl MAS NMR, and shows solid state NMR to be a very sensitive probe of short range structural perturbations. Solid state 105 Pd NMR observations of ∼44-149 μm Pd sponge, ∼20-150 nm Pd black nanoparticles, highly monodisperse 16 ± 3 nm PVP-stabilised Pd nanoparticles, and highly polydisperse ∼2-1100 nm biomineralized Pd nanoparticles (bio-Pd) on pyrolysed amorphous carbon detect physical differences between these systems based on relative bulk:surface ratios and monodispersity/size homogeneity. This introduces the possibility of utilizing solid state NMR to help elucidate the structure-function properties of commercial Pd-based catalyst systems.

A surge in interest of oxide-based materials is testimony for their potential utility in a wide array of device applications and offers a fascinating landscape for tuning the functional properties through a variety of physical and chemical parameters. In particular, selective electronic/defect doping has been demonstrated to be vital in tailoring novel functionalities, not existing in the bulk host oxides. Here, an extraordinary interstitial doping effect is demonstrated centered around a light element, boron (B). The host matrix is a novel composite system, made from discrete bulk LaAlO 3 :LaBO 3 compounds. The findings show a spontaneous ordering of the interstitial B cations within the host LaAlO 3 lattices, and subsequent spin-polarized charge injection into the neighboring cations. This leads to a series of remarkable cation-dominated electrical switching and high-temperature ferromagnetism. Hence, the induced interstitial doping serves to transform a nonmagnetic insulating bulk oxide into a ferromagnetic ionic-electronic conductor. This unique interstitial B doping effect upon its control is proposed to be as a general route for extracting/modifying multifunctional properties in bulk oxides utilized in energy and spin-based applications., (© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The facile silane functionalization of graphene oxide (GO) was achieved yielding vinyltrimethoxysilane-reduced graphene oxide (VTMOS-rGO) nanospheres located in the inter-layer spacing between rGO sheets via an acid-base reaction using aqueous media. The successful grafting of the silane agent with pendant vinyl groups to rGO was confirmed by a combination of Fourier-transform infrared (FTIR), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The structure and speciation of the silane-graphene network (nanosphere) and, the presence of free vinyl groups was verified from solid-state magic angle spinning (MAS) and solution 13C and 29Si nuclear magnetic resonance (NMR) measurements. Evidence from Scanning Electron Microscopy (SEM), High-Resolution Transmission Electron Microscopy (HRTEM) and TEM-High-Angle Annular Dark-Field (TEM-HAADF) imaging showed that these silane networks aided the exfoliation of the rGO layers preventing agglomeration, the interlayer spacing increased by 10 Å. The thermal stability (TGA/DTA) of VTMOS-rGO was significantly improved relative to GO, displaying just one degradation process for the silane network some 300 °C higher than either VTMOS or GO alone. The reduction of GO to VTMOS-rGO induced sp2 hybridization and enhanced the electrical conductivity of GO by 105 S m-1.

Natural abundance 43Ca solid state NMR experiments are reported for the first time at ultra-high magnetic field (35.2 T) on a series of Ca-(pyro)phosphate and Ca-oxalate materials, which are of biological relevance in relation to biomineralization processes and the formation of pathological calcifications. The significant gain in both sensitivity and resolution at 35.2 T leads to unprecedented insight into the structure of both crystalline and amorphous phases.

Vanadate ellestadites Ca 10 (SiO 4 ) x (VO 4 ) 6-2 x (SO 4 ) x Cl 2 , serving as prototype crystalline matrices for the fixation of pentavalent toxic metals (V, Cr, As), were synthesized and characterized by powder X-ray and neutron diffraction (PXRD and PND), electron probe microanalysis (EPMA), Fourier transform infrared spectroscopy (FTIR), and solid-state nuclear magnetic resonance (SS-NMR). The ellestadites 0.19 < x < 3 adopt the P6 3 / m structure, while the vanadate endmember Ca 10 (VO 4 ) 6 Cl 2 is triclinic with space group P1̅. A miscibility gap exists for 0.77 < x < 2.44. The deficiency of Cl in the structure leads to short-range disorder in the tunnel. Toxicity characteristic leaching testing (TCLP) showed the incorporation of vanadium increases ellestadite solubility, and defined a waste loading limit that should not exceed 25 atom % V to ensure small release levels.

Multinuclear ( 1 H, 13 C, 25 Mg) solid-state NMR data is reported for a series of magnesium acetate phases Mg(CH 3 COO) 2  ⋅ nH 2 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 MgO 7 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 (β), 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., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We demonstrate that non-equilibrium nuclear spin order survives precipitation from solution and redissolution. The effect is demonstrated on 13 C- and 2 H-labeled sodium fumarate, with precipitation and dissolution achieved by altering the pH. The lifetime of the spin magnetization in the precipitate suspension is found to be much longer than in solution. Our preliminary results show an extension of the effective relaxation time T 1 for the metabolite fumarate by a factor of ≈6. We show that when the free radical agent TEMPO is present in the solution, it is not incorporated into the precipitate, suggesting that this procedure may provide a means to store and transport agents polarized by dynamic nuclear polarization. Although the relaxation time, T 1 , of the precipitate suspension is longer than that of the same molecules in solution, it is significantly shorter than that observed in the immobilized solid state., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Hydrated niobium oxides are used as strong solid acids with a wide variety of catalytic applications, yet the correlations between structure and acidity remain unclear. New insights into the structural features giving rise to Lewis and Brønsted acid sites are presently achieved. It appears that Lewis acid sites can arise from lower coordinate NbO 5 and in some cases NbO 4 sites, which are due to the formation of oxygen vacancies in thin and flexible NbO 6 systems. Such structural flexibility of Nb-O systems is particularly pronounced in high surface area nanostructured materials, including few-layer to monolayer or mesoporous Nb 2 O 5 ·nH 2 O synthesized in the presence of stabilizers. Bulk materials on the other hand only possess a few acid sites due to lower surface areas and structural rigidity: small numbers of Brønsted acid sites on HNb 3 O 8 arise from a protonic structure due to the water content, whereas no acid sites are detected for anhydrous crystalline H-Nb 2 O 5 .

This paper discusses the fluorination characteristics of phases related to FeSb 2 O 4 , by reporting the results of a detailed study of Mg 0.50 Fe 0.50 Sb 2 O 4 and Co 0.50 Fe 0.50 Sb 2 O 4 . Reaction with fluorine gas at low temperatures (typically 230 °C) results in topotactic insertion of fluorine into the channels, which are an inherent feature of the structure. Neutron powder diffraction and solid state NMR studies show that the interstitial fluoride ions are bonded to antimony within the channel walls to form Sb-F-Sb bridges. To date, these reactions have been observed only when Fe 2+ ions are present within the chains of edge-linked octahedra (FeO 6 in FeSb 2 O 4 ) that form the structural channels. Oxidation of Fe 2+ to Fe 3+ is primarily responsible for balancing the increased negative charge associated with the presence of the fluoride ions within the channels. For the two phases studied, the creation of Fe 3+ ions within the chains of octahedra modify the magnetic exchange interactions to change the ground-state magnetic symmetry to C-type magnetic order in contrast to the A-type order observed for the unfluorinated oxide parents.

The structure of Ba 3 Nb 2 O 8 has been investigated using high resolution neutron powder diffraction. Our results show that, while the structure has some features in common with the 9R perovskite and palmierite structures, it is a new and distinct structure. It is shown to follow a (chh)(hhc)(chh) sequence with BaO 3-δ packing layers and is a cation- and anion-deficient 9H perovskite polytype. Nb atoms occupy octahedral sites with vacancies between hexagonal close-packed layers. Isolated, corner-sharing and face-sharing Nb-O octahedra all occur within the unit cell. The identification of purely octahedral Nb is supported by solid-state 93 Nb wideline NMR measurements. A two-component line shape was detected: a narrow featureless resonance with an isotropic chemical shift of δ iso -928 ± 5 ppm consistent with regular Nb octahedra, and a much broader featureless resonance with an approximate isotropic chemical shift in the range δ iso ∼ -944 to -937 ± 10 ppm consistent with Nb octahedra influenced by O vacancies. These are both characteristic of 6-fold oxo-coordinated Nb environments. The highly distorted octahedral environments in Ba 3 Nb 2 O 8 make it a potential candidate for dielectric and photocatalytic applications.

The structure of the mineral schafarzikite, FeSb 2 O 4 , has one-dimensional channels with walls comprising Sb 3+ cations; the channels are separated by edge-linked FeO 6 octahedra that form infinite chains parallel to the channels. Although this structure provides interest with respect to the magnetic and electrical properties associated with the chains and the possibility of chemistry that could occur within the channels, materials in this structural class have received very little attention. Here we show, for the first time, that heating selected phases in oxygen-rich atmospheres can result in relatively large oxygen uptakes (up to ∼2% by mass) at low temperatures (ca. 350 °C) while retaining the parent structure. Using a variety of structural and spectroscopic techniques, it is shown that oxygen is inserted into the channels to provide a structure with the potential to show high one-dimensional oxide ion conductivity. This is the first report of oxygen-excess phases derived from this structure. The oxygen insertion is accompanied not only by oxidation of Fe 2+ to Fe 3+ within the octahedral chains but also Sb 3+ to Sb 5+ in the channel walls. The formation of a defect cluster comprising one 5-coordinate Sb 5+ ion (which is very rare in an oxide environment), two interstitial O 2- ions, and two 4-coordinate Sb 3+ ions is suggested and is consistent with all experimental observations. To the best of our knowledge, this is the first example of an oxidation process where the local energetics of the product dictate that simultaneous oxidation of two different cations must occur. This reaction, together with a wide range of cation substitutions that are possible on the transition metal sites, presents opportunities to explore the schafarzikite structure more extensively for a range of catalytic and electrocatalytic applications.

Abstract: This work reports the synthesis of lithium-silicate glass, containing 10 mol% of Li 2 O by the sol-gel process, intended for the regeneration of cartilage. Lithium citrate and lithium nitrate were selected as lithium precursors. The effects of the lithium precursor on the sol-gel process, and the resulting glass structure, morphology, dissolution behaviour, chondrocyte viability and proliferation, were investigated. When lithium citrate was used, mesoporous glass containing lithium as a network modifier was obtained, whereas the use of lithium nitrate produced relatively dense glass-ceramic with the presence of lithium metasilicate, as shown by X-ray diffraction, 29 Si and 7 Li MAS NMR and nitrogen sorption data. Nitrate has a better affinity for lithium than citrate, leading to heterogeneous crystallisation from the mesopores, where lithium salts precipitated during drying. Citrate decomposed at a lower temperature, where the crystallisation of lithium-silicate crystal is not thermodynamically favourable. Upon decomposition of the citrate, a solid-state salt metathesis reaction between citrate and silanol occurred, followed by the diffusion of lithium within the structure of the glass. Both glass and glass-ceramic released silica and lithium ions in culture media, but release rate was lower for the glass-ceramic. Both samples did not affect chondrocyte viability and proliferation., (© The Author(s) 2016.)

New photoactive composites to efficiently remove organic dyes from water are reported. These consist of Cu2O/TiO2 nanoparticles in a novel inorganic geopolymer matrix modified by a large tertiary ammonium species (cetyltrimethylammonium bromide, CTAB) whose presence in the matrix is demonstrated by FTIR spectroscopy. The CTAB does not disrupt the tetrahedral geopolymer structural silica and alumina units as demonstrated by (29)Si and (27)Al MAS NMR spectroscopy. SEM/EDS, TEM and BET measurements suggest that the Cu2O/TiO2 nanoparticles are homogenously distributed on the surface and within the geopolymer pores. The mechanism of removal of methylene blue (MB) dye from solution consists of a combination of adsorption (under dark conditions) and photodegradation (under UV radiation). MB adsorption in the dark follows pseudo second-order kinetics and is described by Freundlich-Langmuir type isotherms. The performance of the CTAB-modified geopolymer based composites is superior to composites based on unmodified geopolymer hosts, the most effective composite containing 5wt% Cu2O/TiO2 in a CTAB-modified geopolymer host. These composites constitute a new class of materials with excellent potential in environmental protection applications., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Polycrystalline bis(dialkyldithiophosphato)Pt(II) complexes of the form [Pt{S 2 P(OR) 2 } 2 ] (R = ethyl, iso-propyl, iso-butyl, sec-butyl or cyclo-hexyl group) were studied using solid-state 31 P and 195 Pt NMR spectroscopy, to determine the influence of R to the structure of the central chromophore. The measured anisotropic chemical shift (CS) parameters for 31 P and 195 Pt afford more detailed chemical and structural information, as compared to isotropic CS and J couplings alone. Advanced theoretical modeling at the hybrid DFT level, including both crystal lattice and the important relativistic spin-orbit effects qualitatively reproduced the measured CS tensors, supported the experimental analysis, and provided extensive orientational information. A particular correction model for the non-negligible lattice effects was adopted, allowing one to avoid a severe deterioration of the 195 Pt anisotropic parameters due to the high requirements posed on the pseudopotential quality in such calculations. Though negligible differences were found between the 195 Pt CS tensors with different substituents R, the 31 P CS parameters differed significantly between the complexes, implying the potential to distinguish between them. The presented approach enables good resolution and a detailed analysis of heavy-element compounds by solid-state NMR, thus widening the understanding of such systems.

Bayerite was treated under hydrothermal conditions (120, 130, 140, and 150 °C) to prepare a series of layered double hydroxides (LDHs) with an ideal composition of ZnAl4(OH)12(SO4)0.5·nH2O (ZnAl4-LDHs). These products were investigated by both bulk techniques (powder X-ray diffraction (PXRD), transmission electron microscopy, and elemental analysis) and atomic-level techniques ((1)H and (27)Al solid-state NMR, IR, and Raman spectroscopy) to gain a detailed insight into the structure of ZnAl4-LDHs and sample composition. Four structural models (one stoichiometric and three different defect models) were investigated by Rietveld refinement of the PXRD data. These were assessed using the information obtained from other characterization techniques, which favored the ideal (nondefect) structural model for ZnAl4-LDH, as, for example, (27)Al magic-angle spinning NMR showed that excess Al was present as amorphous bayerite (Al(OH)3) and pseudoboehmite (AlOOH). Moreover, no evidence of cation mixing, that is, partial substitution of Zn(II) onto any of four Al sites, was observed. Altogether this study highlights the challenges involved to synthesize pure ZnAl4-LDHs and the necessity to use complementary techniques such as PXRD, elemental analysis, and solid-state NMR for the characterization of the local and extended structure of ZnAl4-LDHs.

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).

The Stӧber process is commonly used for synthesising spherical silica particles. This article reports the first comprehensive study of how the process variables can be used to obtain monodispersed particles of specific size. The modal particle size could be selected within in the range 20-500 nm. There is great therapeutic potential for bioactive glass nanoparticles, as they can be internalised within cells and perform sustained delivery of active ions. Biodegradable bioactive glass nanoparticles are also used in nanocomposites. Modification of the Stӧber process so that the particles can contain cations such as calcium, whilst maintaining monodispersity, is desirable. Here, whilst calcium incorporation is achieved, with a homogenous distribution, careful characterisation shows that much of the calcium is not incorporated. A maximum of 10 mol% CaO can be achieved and previous reports are likely to have overestimated the amount of calcium incorporated., (Copyright © 2016 Elsevier Inc. All rights reserved.)

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. (1)H, (31)P and (43)Ca MAS (Magic Angle Spinning) NMR spectra were recorded, leading to informative fingerprints characterizing each compound. In particular, different (1)H and (43)Ca 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 Significance: The 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., (Copyright © 2016. Published by Elsevier Ltd.)

Apatite silicates are attracting significant interest as potential SOFC electrolyte materials. They are non-conventional oxide ion conductors in the sense that oxide ion interstitials, rather than vacancies, are the key defects. In this work we compare the structures of La9.6Si6O26.4 and La8Sr2Si6O26, both before and after hydration in order to gather information about the location of the interstitial oxide ion site. Neutron diffraction structural studies suggest that in the as-prepared La8Sr2Si6O26 and hydrated La8Sr2Si6O26, the interstitial oxide ion sites are close to the apatite channel centre. For La9.6Si6O26.4, a similar site close to the channel centre is observed, but on hydration of this particular sample, the interstitial site is shown to be significantly displaced away from the channel centre towards the SiO4 units. This can be explained by the need for additional displacement from the channel centre to accommodate the large amount of interstitial anions in this hydrated phase. The solid state (29)Si MAS NMR spectra are shown to be very sensitive to the different speciation exhibited by the La8Sr2Si6O26 and La9.6Si6O26.4 systems, with the former being dominated by regular SiO4 framework species and the latter being dominated by interruptions to this network caused by cation vacancies and interstitials. The corresponding (17)O MAS NMR study identifies a strong signal from the O atoms of the SiO4 groups, thus demonstrating that all of the O species in these systems are exchangeable O under heterogeneous gas phase conditions. In addition, interstitial O species attributed to pendant OH linkages on the Si positions are clearly identified and resolved, and these are removed on dehydration. This observation and assignment is corroborated by corresponding (1)H MAS NMR measurements. Overall the neutron diffraction work indicates that the interstitial site location in these apatite silicates depends on the anion content with progressive displacement towards the SiO4 tetrahedra on increasing anion content, while the observation of exchangeable O on the SiO4 groups is consistent with prior modelling predictions as to the importance on the silicate units in the conduction process.

Sol-gel hybrids are inorganic/organic co-networks with nanoscale interactions between the components leading to unique synergistic mechanical properties, which can be tailored, via a selection of the organic moiety. Methacrylate based polymers present several benefits for class II hybrids (which exhibit formal covalent bonding between the networks) as they introduce great versatility and can be designed with a variety of chemical side-groups, structures and morphologies. In this study, the effect of high cross-linking density polymers on the structure-property relationships of hybrids generated using poly(3-trimethoxysilylpropyl methacrylate) (pTMSPMA) and tetraethyl orthosilicate (TEOS) was investigated. The complexity and fine scale of the co-network interactions requires the development of new analytical methods to understand how network evolution dictates the wide-ranging mechanical properties. Within this work we developed data manipulation techniques of acoustic-AFM and solid state NMR output that provide new approaches to understand the influence of the network structure on the macroscopic elasticity. The concentration of pTMSPMA in the silica sol affected the gelation time, ranging from 2 h for a hybrid made with 75 wt% inorganic with pTMSPMA at 2.5 kDa, to 1 minute for pTMSPMA with molecular weight of 30 kDa without any TEOS. A new mechanism of gelation was proposed based on the different morphologies derived by AC-AFM observations. We established that the volumetric density of bridging oxygen bonds is an important parameter in structure/property relationships in SiO2 hybrids and developed a method for determining it from solid state NMR data. The variation in the elasticity of pTMSPMA/SiO2 hybrids originated from pTMSPMA acting as a molecular spacer, thus decreasing the volumetric density of bridging oxygen bonds as the inorganic to organic ratio decreased.