Microstructural investigation of Bi-Sr-Ca-Cu-oxide thick films on alumina substrates

The microstructure of Bi-Sr-Ca-Cu-oxide (BSCCO) thick films on alumina substrates has been characterized using a combination of X-ray diffractometry, scanning electron microscopy, transmission electron microscopy of sections across the film/substrate interface and energy-dispersive X-ray spectrometry. A reaction layer formed between the BSCCO films and the alumina substrates. This chemical interaction is largely responsible for off-stoichiometry of the films and is more significant after partial melting of the films. A new phase with fee structure, lattice parameter a = 2.45 nm and approximate composition Al3Sr2CaBi2CuOx has been identified as reaction product between BSCCO and Al2O3.

Elemental characterisation and detection of heavy metals in house dusts collected from sites in South-East Queensland, Australia

Knowledge of the elements present in house dusts is important in understanding potential health effects on humans. In this study, dust samples collected from 10 houses in south-east Queensland have been analysed by scanning electron microscopy and X-ray microanalysis to measure the inorganic element compositions and to investigate the form of heavy metals in the dusts. The overall analytical results were then used to discriminate between different localities using chemometric techniques. The relative amounts of elements, particularly of Si, Ca, and Fe, varied between size fractions and between different locations for the same size fraction. By analysing individual small particles, many other constituents were identified including Ti, Cr, Mn, Ni, Cu, Zn, Ba, Ag, W, Au, Hg, Pb, Bi, La and Ce. The heavy metals were mostly concentrated in small particles in the smaller size fractions, which allowed detection by particle analysis, though their average concentrations were very low.

Vibrational spectroscopic characterization of the phosphate mineral ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O – a mineral found in lithium bearing pegmatites

The objective of this work is to analyze ludlamite (Fe,Mn,Mg)3(PO4)2⋅4H2O from Boa Vista mine, Galiléia, Brazil and to assess the molecular structure of the mineral. The phosphate mineral ludlamite has been characterized by EMP-WDS, Raman and infrared spectroscopic measurements. The mineral is shown to be a ferrous phosphate with some minor substitution of Mg and Mn. Raman bands at 917 and 950 cm−1 are assigned to the symmetric stretching mode of and units. Raman bands at 548, 564, 599 and 634 cm−1 are assigned to the ν4 bending modes. Raman bands at 2605, 2730, 2896 and 3190 cm−1 and infrared bands at 2623, 2838, 3136 and 3185 cm−1 are attributed to water stretching vibrations. By using a Libowitzky empirical function, hydrogen bond distances are calculated from the OH stretching wavenumbers. Strong hydrogen bonds in the structure of ludlamite are observed as determined by their hydrogen bond distances. The application of infrared and Raman spectroscopy to the study of ludlamite enables the molecular structure of the pegmatite mineral ludlamite to be assessed.

Vibrational spectroscopic characterization of the phosphate mineral hureaulite – (Mn, Fe)5(PO4)2(HPO4)2·4(H2O)

This research was done on hureaulite samples from the Cigana claim, a lithium bearing pegmatite with triphylite and spodumene. The mine is located in Conselheiro Pena, east of Minas Gerais. Chemical analysis was carried out by Electron Microprobe analysis and indicated a manganese rich phase with partial substitution of iron. The calculated chemical formula of the studied sample is: (Mn3.23, Fe1.04, Ca0.19, Mg0.13)(PO4)2.7(HPO4)2.6(OH)4.78. The Raman spectrum of hureaulite is dominated by an intense sharp band at 959 cm−1 assigned to PO stretching vibrations of HPO42− units. The Raman band at 989 cm−1 is assigned to the PO43− stretching vibration. Raman bands at 1007, 1024, 1047, and 1083 cm−1 are attributed to both the HOP and PO antisymmetric stretching vibrations of HPO42− and PO43− units. A set of Raman bands at 531, 543, 564 and 582 cm−1 are assigned to the ν4 bending modes of the HPO42− and PO43− units. Raman bands observed at 414, and 455 cm−1 are attributed to the ν2 HPO42− and PO43− units. The intense A series of Raman and infrared bands in the OH stretching region are assigned to water stretching vibrations. Based upon the position of these bands hydrogen bond distances are calculated. Hydrogen bond distances are short indicating very strong hydrogen bonding in the hureaulite structure. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral hureaulite to be understood.

Vibrational spectroscopic characterization of the phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O)

The phosphate mineral series eosphorite–childrenite–(Mn,Fe)Al(PO4)(OH)2·(H2O) has been studied using a combination of electron probe analysis and vibrational spectroscopy. Eosphorite is the manganese rich mineral with lower iron content in comparison with the childrenite which has higher iron and lower manganese content. The determined formulae of the two studied minerals are: (Mn0.72,Fe0.13,Ca0.01)(Al)1.04(PO4, OHPO3)1.07(OH1.89,F0.02)·0.94(H2O) for SAA-090 and (Fe0.49,Mn0.35,Mg0.06,Ca0.04)(Al)1.03(PO4, OHPO3)1.05(OH)1.90·0.95(H2O) for SAA-072. Raman spectroscopy enabled the observation of bands at 970 cm−1 and 1011 cm−1 assigned to monohydrogen phosphate, phosphate and dihydrogen phosphate units. Differences are observed in the area of the peaks between the two eosphorite minerals. Raman bands at 562 cm−1, 595 cm−1, and 608 cm−1 are assigned to the �4 bending modes of the PO4, HPO4 and H2PO4 units; Raman bands at 405 cm−1, 427 cm−1 and 466 cm−1 are attributed to the �2 modes of these units. Raman bands of the hydroxyl and water stretching modes are observed. Vibrational spectroscopy enabled details of the molecular structure of the eosphorite mineral series to be determined.

Vibrational spectroscopy of the phosphate mineral lazulite – (Mg, Fe)Al2(PO4)2·(OH)2 found in the Minas Gerais, Brazil

This research was done on lazulite samples from the Gentil mine, a lithium bearing pegmatite located in the municipality of Mendes Pimentel, Minas Gerais, Brazil. Chemical analysis was carried out by electron microprobe analysis and indicated a magnesium rich phase with partial substitution of iron. Traces of Ca and Mn, (which partially replaced Mg) were found. The calculated chemical formula of the studied sample is: (Mg0.88, Fe0.11)Al1.87(PO4)2.08(OH)2.02. The Raman spectrum of lazulite is dominated by an intense sharp band at 1060 cm-1 assigned to PO stretching vibrations of of tetrahedral [PO4] clusters presents into the HPO2/4- units. Two Raman bands at 1102 and 1137 cm-1 are attributed to both the HOP and PO antisymmetric stretching vibrations. The two infrared bands at 997 and 1007 cm-1 are attributed to the m1 PO3/4- symmetric stretching modes. The intense bands at 1035, 1054, 1081, 1118 and 1154 cm-1 are assigned to the v3PO3/4- antisymmetric stretching modes from both the HOP and tetrahedral [PO4] clusters. A set of Raman bands at 605, 613, 633 and 648 cm-1 are assigned to the m4 out of plane bending modes of the PO4, HPO4 and H2PO4 units. Raman bands observed at 414, 425, 460, and 479 cm-1 are attributed to the m2 tetrahedral PO4 clusters, HPO4 and H2PO4 bending modes. The intense Raman band at 3402 and the infrared band at 3403 cm-1 are assigned to the stretching vibration of the OH units. A combination of Raman and infrared spectroscopy enabled aspects of the molecular structure of the mineral lazulite to be understood.

Thermal stability and hot-stage Raman spectroscopic study of Ca-montmorillonite modified with different surfactants : a comparative study

Three long chain cationic surfactants were intercalated into Ca-montmorillonite through ion exchangeand the obtained organoclays were characterized by X-ray diffraction (XRD), high resolution thermo-gravimetric analysis (TG) and Raman spectroscopy. The intercalation of surfactants not only changes thesurface properties of clay from hydrophilic to hydrophobic but also greatly increases the basal spacing ofthe interlayers based on XRD analysis. The thermal stability of organoclays intercalated with three sur-factants (TTAB, DTAB and CTAB) and the different arrangements of the surfactant molecules intercalatedinto Ca-montmorillonite were determined by TG-DTG analysis. A Raman spectroscopic study on the Ca-montmorillonite modified by three surfactants prepared at different concentrations provided the detailedconformational ordering of different intercalated long-chain surfactants under different conditions. Thewavenumber of the antisymmetric stretching mode is more sensitive than that of the symmetric stretch-ing mode to the mobility of the tail of the amine chain. At room temperature, the conformational orderingis more easily affected by the packing density in the lateral model. With the increase of the temperature,the positions of both the antisymmetric and symmetric stretching bands shift to higher wavenumbers,which indicates a decrease of conformational ordering. This study offers new insights into the struc-ture and properties of Ca-montmorillonite modified with different long chain surfactants. Moreover, theexperimental results confirm the potential applications of organic Ca-montmorillonites for the removalof organic impurities from aqueous media.

Metal hexaborides with Sc, Ti or Mn

Comparison of well-determined single crystal data for stoichiometric, or near-stoichiometric, metal hexaborides con-firm previously identified lattice parameter trends using powder diffraction. Trends for both divalent and trivalent forms suggest that potential new forms for synthesis include Sc and Mn hexaborides. Density Functional Theory (DFT) calculations for KB6, CaB6, YB6, LaB6, boron octahedral clusters and Sc and Mn forms, show that the shapes of bonding orbitals are defined by the boron framework. Inclusion of metal into the boron framework induces a reduction in energy ranging from 1 eV to 6 eV increasing with ionic charge. For metals with d1 character, such a shift in energy brings a doubly degenerate band section along the G-M reciprocal space direction within the conduction bands tangential to the Fermi surface. ScB6 band structure and density of states calculations show directional and gap characteristics similar to those of YB6 and LaB6. These calculations for ScB6 suggest it may be possible to realize superconductivity in this compound if synthesized.

Mussel-inspired bioceramics with self-assembled Ca-P/polydopamine composite nanolayer : preparation, formation mechanism, improved cellular bioactivity and osteogenic differentiation of bone marrow stromal cells

The nanostructured surface of biomaterials plays an important role in improving their in vitro cellular bioactivity as well as stimulating in vivo tissue regeneration. Inspired by the mussel’s adhesive versatility, which is thought to be due to the plaque–substrate interface being rich in 3,4-dihydroxy-L-phenylalamine (DOPA) and lysine amino acids, in this study we developed a self-assembly method to prepare a uniform calcium phosphate (Ca-P)/polydopamine composite nanolayer on the surface of b-tricalcium phosphate (b-TCP) bioceramics by soaking b-TCP bioceramics in Tris–dopamine solution. It was found that the addition of dopamine, reaction temperature and reaction time are three key factors inducing the formation of a uniform Ca-P/polydopamine composite nanolayer. The formation mechanism of a Ca-P/polydopamine composite nanolayer involved two important steps: (i) the addition of dopamine to Tris–HCl solution decreases the pH value and accelerates Ca and P ionic dissolution from the crystal boundaries of b-TCP ceramics; (ii) dopamine is polymerized to form self-assembled polydopamine film and, at the same time, nanosized Ca-P particles are mineralized with the assistance of polydopamine, in which the formation of polydopamine occurs simultaneously with Ca-P mineralization (formation of nanosized microparticles composed of calcium phosphate-based materials), and finally a self-assembled Ca-P/polydopamine composite nanolayer forms on the surface of the b-TCP ceramics. Furthermore, the formed self-assembled Ca-P/polydopamine composite nanolayer significantly enhances the surface roughness and hydrophilicity of b-TCP ceramics, and stimulates the attachment, proliferation, alkaline phosphate (ALP) activity and bone-related gene expression (ALP, OCN, COL1 and Runx2) of human bone marrow stromal cells. Our results suggest that the preparation of self-assembled Ca-P/polydopamine composite nanolayers is a viable method to modify the surface of biomaterials by significantly improving their surface physicochemical properties and cellular bioactivity for bone regeneration application.

Electrochemically-induced TCNQ/Mn TCNQ 2 (H2O) 2 (TCNQ= 7, 7, 8, 8-Tetracyanoquinodimethane) solid-solid interconversion : two voltammetrically distinct processes that allow selective generation of nanofiber or nanorod network morphologies

Unlike the case with other divalent transition metal M\[TCNQ](2)(H(2)O)(2) (M = Fe, Co, Ni) analogues, the electrochemically induced solid-solid phase interconversion of TCNQ microcrystals (TCNQ = 7,7,8,8-tetracyanoquinodimethane) to Mn\[TCNQ](2)(H(2)O)(2) occurs via two voltammetrically distinct, time dependent processes that generate the coordination polymer in nanofiber or rod-like morphologies. Careful manipulation of the voltammetric scan rate, electrolysis time, Mn(2+)((aq)) concentration, and the method of electrode modification with solid TCNQ allows selective generation of either morphology. Detailed ex situ spectroscopic (IR, Raman), scanning electron microscopy (SEM), and X-ray powder diffraction (XRD) characterization clearly establish that differences in the electrochemically synthesized Mn-TCNQ material are confined to morphology. Generation of the nanofiber form is proposed to take place rapidly via formation and reduction of a Mn-stabilized anionic dimer intermediate, \[(Mn(2+))(TCNQ-TCNQ)(2)(*-)], formed as a result of radical-substrate coupling between TCNQ(*-) and neutral TCNQ, accompanied by ingress of Mn(2+) ions from the aqueous solution at the triple phase TCNQ/electrode/electrolyte boundary. In contrast, formation of the nanorod form is much slower and is postulated to arise from disproportionation of the \[(Mn(2+))(TCNQ-TCNQ)(*-)(2)] intermediate. Thus, identification of the time dependent pathways via the solid-solid state electrochemical approach allows the crystal size of the Mn\[TCNQ](2)(H(2)O)(2) material to be tuned and provides new mechanistic insights into the formation of different morphologies.

Removal of bisphenol A from wastewater by Ca-montmorillonite modified with selected surfactants

Organo Arizona SAz-2 Ca-montmorillonite was prepared with different surfactant (DDTMA and HDTMA) loadings through direct ion exchange. The structural properties of the prepared organoclays were characterized by XRD and BET instruments. Batch experiments were carried out on the adsorption of bisphenol A (BPA) under different experimental conditions of pH and temperature to determine the optimum adsorption conditions. The hydrophobic phase and positively charged surface created by the loaded surfactant molecules are responsible for the adsorption of BPA. The adsorption of BPA onto organoclays is well described by pseudo-second order kinetic model and the Langmuir isotherm. The maximum adsorption capacity of the organoclays for BPA obtained from a Langmuir isotherm was 151.52 mg/g at 297 K. This value is among the highest values for BPA adsorption compared with other adsorbents. In addition, the adsorption process was spontaneous and exothermic based on the adsorption thermodynamics study. The organoclays intercalated with longer chain surfactant molecules possessed a greater adsorption capacity for BPA even under alkaline conditions. This process provides a pathway for the removal of BPA from contaminated waters.

A vibrational spectroscopic study of the silicate mineral ardennite-(As)

We have used a combination of scanning electron microscopy with EDX and vibrational spectroscopy to study the mineral ardennite-(As). The mineral ardennite-(As) of accepted formula Mn2þ 4 (Al,Mg)6(Si3O10)(SiO4)2(AsO4,VO4)(OH)6 is a silicate mineral which may contain arsenate and/or vanadates anions. Because of the oxyanions present, the mineral lends itself to analysis by Raman and infrared spectroscopy. Qualitative chemical analysis shows a homogeneous phase, composed by Si, Mn, Al and As. Ca and V were also observed in partial substitution for Mn and As. Raman bands at 1197, 1225, 1287 and 1394 cm-1 are assigned to SiO stretching vibrations. The strong Raman bands at 779 and 877 cm-1 are assigned to the AsO3- 4 antisymmetric and symmetric stretching vibrations. The Raman band at 352 cm-1 is assigned to the m2 symmetric bending vibration. The series of Raman bands between 414 and 471 cm-1 are assigned to the m4 out of plane bending modes of the AsO3-4 units. Intense Raman bands observed at 301 and 314 cm-1 are attributed to the MnO stretching and bending vibrations. Raman bands at 3041, 3149, 3211 and 3298 cm-1 are attributed to the stretching vibrations of OH units. There is vibrational spectroscopic evidence for the presence of water adsorbed on the ardennite-(As) surfaces.

Raman spectroscopy of the arsenate minerals maxwellite and in comparison with tilasite

Maxwellite NaFe3+(AsO4)F is an arsenate mineral containing fluoride and forms a continuous series with tilasite CaMg(AsO4)F. Both maxwellite and tilasite form a continuous series with durangite NaAl3+(AsO4)-F. We have used the combination of scanning electron microscopy with EDS and vibrational spectroscopy to chemically analyse the mineral maxwellite and make an assessment of the molecular structure. Chemical analysis shows that maxwellite is composed of Fe, Na and Ca with minor amounts of Mn and Al. Raman bands for tilasite at 851 and 831 cm�1 are assigned to the Raman active m1 symmetric stretching vibration (A1) and the Raman active triply degenerate m3 antisymmetric stretching vibration (F2). The Raman band of maxwellite at 871 cm�1 is assigned to the m1 symmetric stretching vibration and the Raman band at 812 cm�1 is assigned to the m3 antisymmetric stretching vibration. The intense Raman band of tilasite at 467 cm�1 is assigned to the Raman active triply degenerate m4 bending vibration (F2). Raman band at 331 cm�1 for tilasite is assigned to the Raman active doubly degenerate m2 symmetric bending vibration (E). Both Raman and infrared spectroscopy do not identify any bands in the hydroxyl stretching region as is expected.

Remodeling of purinergic receptor-mediated Ca 2+ signaling as a consequence of EGF-induced epithelial-mesenchymal transition in breast cancer cells

Background The microenvironment plays a pivotal role in tumor cell proliferation, survival and migration. Invasive cancer cells face a new set of environmental challenges as they breach the basement membrane and colonize distant organs during the process of metastasis. Phenotypic switching, such as that which occurs during epithelial-mesenchymal transition (EMT), may be associated with a remodeling of cell surface receptors and thus altered responses to signals from the tumor microenvironment. Methodology/Principal Findings We assessed changes in intracellular Ca 2+ in cells loaded with Fluo-4 AM using a fluorometric imaging plate reader (FLIPR TETRA) and observed significant changes in the potency of ATP (EC 50 0.175 μM (-EGF) versus 1.731 μM (+EGF), P<0.05), and the nature of the ATP-induced Ca 2+ transient, corresponding with a 10-fold increase in the mesenchymal marker vimentin (P<0.05). We observed no change in the sensitivity to PAR2-mediated Ca 2+ signaling, indicating that these alterations are not simply a consequence of changes in global Ca 2+ homeostasis. To determine whether changes in ATP-mediated Ca 2+ signaling are preceded by alterations in the transcriptional profile of purinergic receptors, we analyzed the expression of a panel of P2X ionotropic and P2Y metabotropic purinergic receptors using real-time RT-PCR and found significant and specific alterations in the suite of ATP-activated purinergic receptors during EGF-induced EMT in breast cancer cells. Our studies are the first to show that P2X 5 ionotropic receptors are enriched in the mesenchymal phenotype and that silencing of P2X 5 leads to a significant reduction (25%, P<0.05) in EGF-induced vimentin protein expression. Conclusions The acquisition of a new suite of cell surface purinergic receptors is a feature of EGF-mediated EMT in MDA-MB-468 breast cancer cells. Such changes may impart advantageous phenotypic traits and represent a novel mechanism for the targeting of cancer metastasis.