3D printed hybrid scaffolds for bone regeneration using calcium methoxyethoxide as a calcium source.

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. SiO2-CaOCME/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 SiO2-CaOCME/PTHF/PCL-diCOOH hybrids affected printability and mechanical properties of the lattice-like scaffolds. Hybrids containing 30 mol.% calcium in the inorganic network (70S30CCME-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 SiO2/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 70S30CCME-CL hybrids also kept a stable strain to failure (~30 %) and formed hydroxycarbonate apatite within three days. The extracts released by the 70S30CCME-CL hybrids in growth medium did not cause cytotoxic effects on human bone marrow stromal cells over 24 h of culture.

The Impact of Intergrain Phases on the Ionic Conductivity of the LAGP Solid Electrolyte Material Prepared by Spark Plasma Sintering.

Li1.5Al0.5Ge1.5(PO4)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 31P and 27Al MAS NMR study coupled with materials modeling reveals that the grain boundary material is composed of Li4P2O7 and disordered Li9Al3(P2O7)3(PO4)2 phases. Quantitative 31P MAS NMR measurements demonstrate that optimal ionic conductivity for the LAGP system is achieved for the 680 °C SPS preparation when the disordered Li9Al3(P2O7)3(PO4)2 phase dominates the grain boundary composition with reduced contributions from the highly ordered Li4P2O7 phases, whereas the 27Al MAS NMR data reveal that minimal structural change is experienced by each phase throughout this suite of sintering temperatures.

Navigating surface reconstruction of spinel oxides for electrochemical water oxidation.

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 MT-O-MO backbone. A stronger MO-O covalency relative to MT-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.

Characterization of an aged alkali-activated slag roof tile after 30 years of exposure to Northern Scandinavian weather.

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 CO2 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.

A powder XRD, solid state NMR and calorimetric study of the phase evolution in mechanochemically synthesized dual cation (Csx(CH3NH3)1-x)PbX3 lead halide perovskite systems.

Methylammonium (MA+) lead halide perovskites (MAPbX3) 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 (CsxMA1-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 PbX6 octahedral tilting was studied using complementary high resolution TEM, powder XRD, multinuclear 133Cs/207Pb/1H 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 MAPbX3-CsPbX3 partition. In particular, the 133Cs shifts demonstrated a sensitivity to the cubic-orthorhombic phase transition while the 133Cs T1s 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 (CsxMA1-x)PbCl3 and (CsxMA1-x)PbBr3 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.

Antibacterial, remineralising and matrix metalloproteinase inhibiting scandium-doped phosphate glasses for treatment of dental caries.

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 Sc3+ 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 Sc3+ ions release over time. The released Sc3+ shows statistically significant inhibition of S. mutans biofilm (1.2 log10 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 Sc3+ ions might act on various enzymes essential to the biological mechanisms underlying caries, Sc-PBGs could be a promising therapeutic agent against cariogenic bacteria.

Mapping of N-C Bond Formation from a Series of Crystalline Peri-Substituted Naphthalenes by Charge Density and Solid-State NMR Methodologies.

A combination of charge density studies and solid state nuclear magnetic resonance (NMR) 1 JNC 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 sp2 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 JNC couplings of ≈3-6 Hz for long C-N bonds (1.60-1.65 Å), and 1 JNC couplings of <1 Hz for N⋅⋅⋅C >2.1 Å.

The classification of 1D `perovskites'.

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.

3D printed silica-gelatin hybrid scaffolds of specific channel sizes promote collagen Type II, Sox9 and Aggrecan production from chondrocytes.

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.

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

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

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

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

Simultaneous MQMAS NMR Experiments for Two Half-Integer Quadrupolar Nuclei.

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) 17O and either 3Q or quintuple-quantum (5Q) 27Al MAS NMR spectra of a 1.18Na2O•5SiO2•Al2O3 glass gel.

CaproGlu: Multifunctional tissue adhesive platform.

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.

Heavy Water Additive in Formamidinium: A Novel Approach to Enhance Perovskite Solar Cell Efficiency.

Heavy water or deuterium oxide (D2 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 D2 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% D2 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-H2 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 PbI6 phonon frequencies in the deuterated perovskite lattice. This stabilizes the PbI6 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.

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

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

Electrospinning 3D bioactive glasses for wound healing.

An electrospinning technique was used to produce three-dimensional (3D) bioactive glass fibrous scaffolds, in the SiO2-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 Ca2+ 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 Ca2+ 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 SiO2-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.

Interstitial Boron Atoms in the Palladium Lattice of an Industrial Type of Nanocatalyst: Properties and Structural Modifications.

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 11B magic-angle-spinning (MAS) and 105Pd 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-intB/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 105Pd 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.

Crystal Chemistry and Antibacterial Properties of Cupriferous Hydroxyapatite.

Copper-doped hydroxyapatite (HA) of nominal composition Ca10(PO4)6[Cux(OH)2-2xOx] (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 Å3 for copper-free HA to 533.31 Å3 for material of the putative composition Ca10(PO4)6[Cu0.8(OH)0.4O0.8] consistent with Cu+ insertion into the [001] hydroxyapatite channel. This was less pronounced (528.30 Å3 to 529.3 Å3) 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 Cu2+. 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 31P 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.

Effects of manganese incorporation on the morphology, structure and cytotoxicity of spherical bioactive glass nanoparticles.

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 ±â€¯10.8 nm and spherical morphology were obtained after MnO incorporation in the SiO2 - CaO system. X-ray photoelectron spectroscopy (XPS) indicated the presence of Mn2+ 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 29Si 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.

Compound-specific δ15N values express differences in amino acid metabolism in plants of varying lignin content.

Amino acid δ15N 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 δ15N values of glutamate (Glx) and phenylalanine (Phe) were found to differ significantly between woody and herbaceous plants, with mean Δ15NGlx-Phe (i.e. δ15NPhe - δ15NGlx) values of -9.3 ±â€¯1.6‰ and -5.8 ±â€¯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 Δ15NGlx-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 13C 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 Δ15NGlx-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 δ15N values will, to give one example, allow refinement of estimates of herbivore diet in present and past ecosystems, enabling more accurate environmental niche modelling.