The molecular structure of the phosphate mineral kidwellite NaFe93+(PO4)6(OH)11⋅3H2O – a vibrational spectroscopic study

The mineral kidwellite, a hydrated hydroxy phosphate of ferric iron and sodium of approximate formula NaFe93+(PO4)6(OH)11⋅3H2O, has been studied using a combination of electron microscopy with EDX and vibrational spectroscopic techniques. Raman spectroscopy identifies an intense band at 978 cm−1 and 1014 cm−1. These bands are attributed to the PO43− ν1 symmetric stretching mode. The ν3 antisymmetric stretching modes are observed by a large number of Raman bands. The series of Raman bands at 1034, 1050, 1063, 1082, 1129, 1144 and 1188 cm−1 are attributed to the ν3 antisymmetric stretching bands of the PO43− and HOPO32− units. The observation of these multiple Raman bands in the symmetric and antisymmetric stretching region gives credence to the concept that both phosphate and hydrogen phosphate units exist in the structure of kidwellite. The series of Raman bands at 557, 570, 588, 602, 631, 644 and 653 cm−1are assigned to the PO43− ν2 bending modes. The series of Raman bands at 405, 444, 453, 467, 490 and 500 cm−1 are attributed to the PO43− and HOPO32− ν4 bending modes. The spectrum is quite broad but Raman bands may be resolved at 3122, 3231, 3356, 3466 and 3580 cm−1. These bands are assigned to water stretching vibrational modes. The number and position of these bands suggests that water is in different molecular environments with differing hydrogen bond distances. Infrared bands at 3511 and 3359 cm−1 are ascribed to the OH stretching vibration of the OH units. Very broad bands at 3022 and 3299 cm−1 are attributed to the OH stretching vibrations of water. Vibrational spectroscopy offers insights into the molecular structure of the phosphate mineral kidwellite.

Stoichiometry, crystallinity, and nano-scale surface morphology of the graded calcium phosphate-based bio-ceramic interlayer on Ti-Al-V

A plasma-assisted concurrent Rf sputtering technique for fabrication of biocompatible, functionally graded CaP-based interlayer on Ti-6Al-4V orthopedic alloy is reported. Each layer in the coating is designed to meet a specific functionality. The adherent to the metal layer features elevated content of Ti and supports excellent ceramic-metal interfacial stability. The middle layer features nanocrystalline structure and mimics natural bone apatites. The technique allows one to reproduce Ca/P ratios intrinsic to major natural calcium phosphates. Surface morphology of the outer, a few to few tens of nanometers thick, layer, has been tailored to fit the requirements for the bio-molecule/protein attachment factors. Various material and surface characterization techniques confirm that the optimal surface morphology of the outer layer is achieved for the process conditions yielding nanocrystalline structure of the middle layer. Preliminary cell culturing tests confirm the link between the tailored nano-scale surface morphology, parameters of the middle nanostructured layer, and overall biocompatibility of the coating.

Reactive species in RF plasma sputtering deposition of nanocrystalline calcium phosphate bio-active films

Optical emission of reactive plasma species during the synthesis of functionally graded calcium phosphate-based bioactive films has been investigated. The coatings have been deposited on Ti-6Al-4V orthopedic alloy by co-sputtering of hydroxyapatite (HA) and titanium targets in reactive plasmas of Ar + H2O gas mixtures. The species, responsible for the Ca-P-Ti film growth have been non-intrusively monitored in situ by a high-resolution optical emission spectroscopy (OES). It is revealed that the optical emission originating from CaO species dominates throughout the deposition process. The intensities of CaO, PO and CaPO species are strongly affected by variations of the operating pressure, applied RF power, and DC substrate bias. The optical emission intensity (OEI) of reaction species can efficiently be controlled by addition of H2O reactant.

A Raman and infrared spectroscopic characterisation of the phosphate mineral phosphohedyphane Ca2Pb3(PO4)3Cl from the Roote mine, Nevada, USA

Phosphohedyphane Ca2Pb3(PO4)3Cl is rare Ca and Pb phosphate mineral that belongs to the apatite supergroup. We have analysed phosphohedyphane using SEM with EDX, and Raman and infrared spectroscopy. The chemical analysis shows the presence of Pb, Ca, P and Cl and the chemical formula is expressed as Ca2Pb3(PO4)3Cl. The very sharp Raman band at 975 cm−1 is assigned to the PO43-ν1 symmetric stretching mode. Raman bands noted at 1073, 1188 and 1226 cm−1 are to the attributed to the PO43-ν3 antisymmetric stretching modes. The two Raman bands at 835 and 812 cm−1 assigned to the AsO43-ν1 symmetric stretching vibration and AsO43-ν3 antisymmetric stretching modes prove the substitution of As for P in the structure of phosphohedyphane. A series of bands at 557, 577 and 595 cm−1 are attributed to the ν4 out of plane bending modes of the PO4 units. The multiplicity of bands in the ν2, ν3 and ν4 spectral regions provides evidence for the loss of symmetry of the phosphate anion in the phosphohedyphane structure. Observed bands were assigned to the stretching and bending vibrations of phosphate tetrahedra. Some Raman bands attributable to OH stretching bands were observed, indicating the presence of water and/or OH units in the structure.

A vibrational spectroscopic study of the anhydrous phosphate mineral sidorenkite Na3Mn(PO4)(CO3)

Sidorenkite is a very rare low-temperature hydrothermal mineral, formed very late in the crystallization of hyperagpaitic pegmatites in a differentiated alkalic massif (Mt. Alluaiv, Kola Peninsula, Russia). Sidorenkite Na3Mn(PO4)(CO3) is a phosphate–carbonate of sodium and manganese. Such a formula with two oxyanions lends itself to vibrational spectroscopy. The sharp Raman band at 959 cm−1 and 1012 cm−1 are assigned to the PO43− stretching modes, whilst the Raman bands at 1044 cm−1 and 1074 cm−1 are attributed to the CO32− stretching modes. It is noted that no Raman bands at around 800 cm−1 for sidorenkite were observed. The infrared spectrum of sidorenkite shows a quite intense band at 868 cm−1 with other resolved component bands at 850 and 862 cm−1. These bands are ascribed to the CO32− out-of-plane bend (ν2) bending mode. The series of Raman bands at 622, 635, 645 and 704 cm−1 are assigned to the ν4 phosphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the carbonate anion from D3h or even C2v.

The effectiveness of education or behavioral interventions on adherence to phosphate control in adults receiving hemodialysis: A systematic review protocol

The objective of this review is to identify the effectiveness of education or behavioral interventions on adherence to phosphate control in adults with end stage kidney disease (ESKD) receiving hemodialysis (HD).

Different correlation of Sphingosine-1-Phosphate receptor 1 with receptor activator of nuclear factor kappa B ligand and regulatory T cells in rat periapical lesions

Introduction Sphingosine-1-phosphate receptor 1 (S1P1) is crucial for regulation of immunity and bone metabolism. This study aimed to investigate the expression of S1P1 in rat periapical lesions and its relationship with receptor activator of nuclear factor kappa B ligand (RANKL) and regulatory T (Treg) cells. Methods Periapical lesions were induced by pulp exposure in the first lower molars of 55 Wistar rats. Thirty rats were killed on days 0, 7, 14, 21, 28, and 35, and their mandibles were harvested for x-ray imaging, micro–computed tomography scanning, histologic observation, immunohistochemistry, enzyme histochemistry, and double immunofluorescence analysis. The remaining 25 rats were killed on days 0, 14, 21, 28, and 35, and mandibles were harvested for flow cytometry. Results The volume and area of the periapical lesions increased from day 0 to day 21 and then remained comparably stable after day 28. S1P1-positive cells were observed in the inflammatory periapical regions; the number of S1P1-positive cells peaked at day 14 and then decreased from day 21 to day 35. The distribution of S1P1-positive cells was positively correlated with the dynamics of RANKL-positive cells but was negatively correlated with that of Treg cells. Conclusions S1P1 expression was differentially correlated with RANKL and Treg cell infiltration in the periapical lesions and is therefore a contributing factor to the pathogenesis of such lesions.

SEM, EDX and vibrational spectroscopic study of the phosphate mineral ushkovite MgFe3+2(PO4)2(OH)2·8H2O: Implications of the molecular structure

The mineral ushkovite has been analyzed using a combination of electron microscopy with EDX and vibrational spectroscopy. Chemical analysis shows the mineral contains P, Mg with very minor Fe. Thus, the formula of the studied ushkovite is Mg32+(PO4)2·8H2O. The Raman spectrum shows an intense band at 953 cm−1 assigned to the ν1 symmetric stretching mode. In the infrared spectra complexity exists with multiple antisymmetric stretching vibrations observed, due to the reduced tetrahedral symmetry. This loss of degeneracy is also reflected in the bending modes. Strong infrared bands around 827 cm−1 are attributed to water librational modes. The Raman spectra of the hydroxyl-stretching region are complex with overlapping broad bands. Hydroxyl stretching vibrations are identified at 2881, 2998, 3107, 3203, 3284 and 3457 cm−1. The wavenumber band at 3457 cm−1 is attributed to the presence of FeOH groups. This complexity is reflected in the water HOH bending modes where a strong infrared band centered around 1653 cm−1 is found. Such a band reflects the strong hydrogen bonding of the water molecules to the phosphate anions in adjacent layers. Spectra show three distinct OH bending bands from strongly hydrogen-bonded, weakly hydrogen bonded water and non-hydrogen bonded water. Vibrational spectroscopy enhances our knowledge of the molecular structure of ushkovite.

Graphene-oxide-modified β-tricalcium phosphate bioceramics stimulate in vitro and in vivo osteogenesis

Graphene oxide (GO) has attracted much interest for applications in bone tissue engineering; however, until now the interaction between GO and stem cells, and the in vivo bone-forming ability of GO has not been explored. The aim of this study was to produce a GO-modified β-tricalcium phosphate (β-TCP-GRA) biceramics and then explore the material’s osteogenic capacity in vitro and in vivo, as well as unravel some of the molecular mechanisms behind this. β-TCP-GRA disks and scaffolds were successfully prepared by a simple GO/water suspension soaking method in combination with heat treatment. These scaffolds were found to significantly enhance the proliferation, alkaline phosphatase activity and osteogenic gene expression of human bone marrow stromal cells (hBMSCs), when compared to β-TCP without GO modification (controls). Activation of the Wnt/β-catenin signaling pathway in hBMSCs appears to be the mechanism behind this osteogenic induction by β-TCP-GRA. β-TCP-GRA scaffolds led to an increased rate of in vivo new bone formation compared to β-TCP controls, indicative of the stimulatory effect of GO on in vivo osteogenesis, making GO modification of β-TCP a very promising method for applications in bone tissue engineering, in particular for the regeneration of large bone defects.

A vibrational spectroscopic study of the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O

We have studied the phosphate mineral vantasselite Al4(PO4)3(OH)3·9H2O using a combination of SEM with EDX and Raman and infrared spectroscopy. Qualitative chemical analysis shows Al, Fe and P. Raman bands at 1013 and 1027cm−1 are assigned to the PO43−ν1 symmetric stretching mode. The observation of two bands suggests the non-equivalence of the phosphate units in the vantasselite structure. Raman bands at 1051, 1076 and 1090cm−1 are attributed to the PO43−ν3 antisymmetric stretching vibration. A comparison is made with the spectroscopy of wardite. Strong infrared bands at 1044, 1078, 1092, 1112, 1133, 1180 and 1210cm−1 are attributed to the PO43−ν3 antisymmetric stretching mode. Some of these bands may be due to δAl2OH deformation modes. Vibrational spectroscopy offers a mechanism for the study of the molecular structure of vantasselite.

The effect of osteoimmunomodulation on the osteogenic effects of cobalt incorporated β-tricalcium phosphate

Osteoblast lineage cells are direct effectors of osteogenesis and are, therefore, commonly used to evaluate the in vitro osteogenic capacity of bone substitute materials. This method has served its purposes when testing novel bone biomaterials; however, inconsistent results between in vitro and in vivo studies suggest the mechanisms that govern a material's capacity to mediate osteogenesis are not well understood. The emerging field of osteoimmunology and immunomodulation has informed a paradigm shift in our view of bone biomaterials–from one of an inert to an osteoimmunomodulatory material–highlighting the importance of immune cells in materials-mediated osteogenesis. Neglecting the importance of the immune response during this process is a major shortcoming of the current evaluation protocol. In this study we evaluated a potential angiogenic bone substitute material cobalt incorporated with β-tricalcium phosphate (CCP), comparing the traditional “one cell type” approach with a “multiple cell types” approach to assess osteogenesis, the latter including the use of immune cells. We found that CCP extract by itself was sufficient to enhance osteogenic differentiation of bone marrow stem cells (BMSCs), whereas this effect was cancelled out when macrophages were involved. In response to CCP, the macrophage phenotype switched to the M1 extreme, releasing pro-inflammatory cytokines and bone catabolic factors. When the CCP materials were implanted into a rat femur condyle defect model, there was a significant increase of inflammatory markers and bone destruction, coupled with fibrous encapsulation rather than new bone formation. These findings demonstrated that the inclusion of immune cells (macrophages) in the in vitro assessment matched the in vivo tissue response, and that this method provides a more accurate indication of the essential role of immune cells when assessing materials-stimulated osteogenesis in vitro.

Comparison of silicate-substituted calcium phosphate (Actifuse®) with rhBMP-2 (Infuse®) in posterolateral instrumented lumbar fusion

Study Design This was a randomised controlled trial in patients with degenerative disc disease (DDD) who underwent instrumented posterolateral lumbar fusion (PLF) surgery. Objective The aim of this study was to assess the efficacy of the bone grafting substitute, silicate-substituted calcium phosphate (SiCaP) compared with bone morphogenetic protein (rhBMP-2) and to evaluate clinical outcomes over a period of two years. Methods Patients undergoing PLF surgery for DDD at a single centre were recruited and randomised to one of two groups; SiCaP (n=9) or rhBMP-2 (n=10). One patient withdrew prior to randomisation and another from the rhBMP-2 group after randomisation. The radiological and clinical outcomes were examined and compared. Fusion was assessed at 12 months with computed tomography (CT) and plain radiographs. Clinical outcomes were evaluated by recording measures of pain, quality of life, disability and neurological status from six weeks to two years postoperatively. Results In the SiCaP and rhBMP-2 groups, fusion was observed in 9/9 and 8/9 patients respectively. Pain and disability scores were reduced and quality of life increased in both groups. Leg pain, disability and satisfaction scores were similar between the groups at each postoperative time point, however, back pain was less at six weeks and quality of life was higher at six months in the SiCaP group than the rhBMP-2 group. Conclusions SiCaP and rhBMP-2 were comparable in terms of achieving successful bone growth and fusion. Both groups similarly alleviated pain and improved quality of life, neurological, satisfaction and return to work outcomes following PLF surgery.

Co-and Ca-phosphate-based catalysts for the depolymerization of organosolv eucalytpus lignin

Depolymerization of purified organosolv eucalyptus wood lignin by the heterogeneous catalysts, cobalt polyphosphate (CoP2O6) and calcium phosphate (β-CaP2O6) was investigated. A total syringol yield of 16.7% was achieved with β-CaP2O6 in a methanol/water (50/50, wt/wt) solvent system after depolymerization at 300 ºC for 1 h, showing selectivity of the catalyst.

Calcium phosphate flocs and the clarification of sugar cane juice from whole of crop harvesting

Sugar cane biomass is one of the most viable feedstocks for the production of renewable fuels and chemicals. Therefore, processing the whole of crop (WC) (i.e., stalk and trash, instead of stalk only) will increase the amount of available biomass for this purpose. However, effective clarification of juice expressed from WC for raw sugar manufacture is a major challenge because of the amounts and types of non-sucrose impurities (e.g., polysaccharides, inorganics, proteins, etc.) present. Calcium phosphate flocs are important during sugar cane juice clarification because they are responsible for the removal of impurities. Therefore, to gain a better understanding of the role of calcium phosphate flocs during the juice clarification process,the effects of impurities on the physicochemical properties of calcium phosphate flocs were examined using small-angle laser light scattering technique, attenuated total reflectance Fourier transformed infrared spectroscopy, and X-ray powder diffraction. Results on synthetic sugar juice solutions showed that the presence of SiO2 and Na+ ions affected floc size and floc structure. Starch and phosphate ions did not affect the floc structure; however, the former reduced the floc size, whereas the latter increased the floc size. The study revealed that high levels of Na+ ions would negatively affect the clarification process the most, as they would reduce the amount of suspended particles trapped by the flocs. A complementary study on prepared WC juice using cold and cold/intermediate liming techniques was conducted. The study demonstrated that, in comparison to the one-stage (i.e., conventional) clarification process, a two-stage clarification process using cold liming removed more polysaccharides (≤19%),proteins (≤82%), phosphorus (≤53%), and SiO2 (≤23%) in WC juice but increased Ca2+ (≤136%) and sulfur (≤200%)

Measuring load of phosphate in the environment by passive sampling techniques: An introduction

Phosphorus has a number of indispensable biochemical roles, but its natural deposition and the low solubility of phosphates as well as their rapid transformation to insoluble forms make the element commonly the growth-limiting nutrient, particularly in aquatic ecosystems. Famously, phosphorus that reaches water bodies is commonly the main cause of eutrophication. This undesirable process can severely affect many aquatic biotas in the world. More management practices are proposed but long-term monitoring of phosphorus level is necessary to ensure that the eutrophication won't occur. Passive sampling techniques, which have been developed over the last decades, could provide several advantages to the conventional sampling methods including simpler sampling devices, more cost-effective sampling campaign, providing flow proportional load as well as representative average of concentrations of phosphorus in the environment. Although some types of passive samplers are commercially available, their uses are still scarcely reported in the literature. In Japan, there is limited application of passive sampling technique to monitor phosphorus even in the field of agricultural environment. This paper aims to introduce the relatively new P-sampling techniques and their potential to use in environmental monitoring studies.