Structural study of thin films prepared from tungstate glass matrix by Raman and X-ray absorption spectroscopy

Thin films were prepared using glass precursors obtained in the ternary system NaPO(3)-BaF(2)-WO(3) and the binary system NaPO(3)-WO(3) with high concentrations of WO(3) (above 40% molar). Vitreous samples have been used as a target to prepare thin films. Such films were deposited using the electron beam evaporation method onto soda-lime glass substrates. Several structural characterizations were performed by Raman spectroscopy and X-ray Absorption Near Edge Spectroscopy (XANES) at the tungsten L(I) and L(III) absorption edges. XANES investigations showed that tungsten atoms are only sixfold coordinated (octahedral WO(6)) and that these films are free of tungstate tetrahedral units (WO(4)). In addition, Raman spectroscopy allowed identifying a break in the linear phosphate chains as the amount of WO(3) increases and the formation of P-O-W bonds in the films network indicating the intermediary behavior of WO(6) octahedra in the film network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed identifying the presence of W-O and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO(3) concentrated samples (above 40% molar) attributed to the formation of WO(6) clusters. (C) 2008 Elsevier B.V. All rights reserved.

Structural study of tungstate fluorophosphate glasses by Raman and X-ray absorption spectroscopy

Transparent glasses were synthesized in the NaPO3-BaF2 WO3 tertiary system and several structural characterizations were performed by X-ray absorption spectroscopy (XANES) at the tungsten L-I and L-III absorption edges and by Raman spectroscopy. Special attention was paid to the coordination state of tungsten atoms in the vitreous network.XANES investigations showed that tungsten atoms are only six-fold coordinated (octahedra WO6) and that these glasses are free of tungstate tetrahedra (WO4).In addition, Raman spectroscopy allowed to identify a break in the linear phosphate chains as the amount of WO3 increases and the formation of P-O-W bonds in the vitreous network indicating the modifier behavior of WO6 octahedra in the glass network. Based on XANES data, we suggested a new attribution of several Raman absorption bands which allowed to identify the presence of W-O- and W=O terminal bonds and a progressive apparition of W-O-W bridging bonds for the most WO3 concentrated samples (≥ 30% molar) due to the formation of WO6 clusters. © 2004 Elsevier B.V. All rights reserved.

Mineral trioxide aggregate repair of lateral root perforations

This study was conducted to observe the healing process of intentional lateral root perforation repaired with mineral trioxide aggregate (MTA). Forty-eight root canals of dogs' teeth were instrumented and filled. After partial removal of the filling, an intentional perforation was made with a bur in the lateral area of the root. The perforations were repaired with MTA or Sealapex (control group). Histological analysis occurred 30 and 180 days after treatment. Results showed no inflammation and deposition of cementum over MTA in the majority of the specimens. In the 180-day period, Sealapex exhibited chronic inflammation in all the specimens and slight deposition of cementum over the material in only three cases. In conclusion, MTA exhibited better results than the control group. Copyright © 2001 by The American Association of Endodontists.

Calcium silicate and organic mineral fertilizer applications reduce phytophagy by Thrips palmi Karny (Thysanoptera: Thripidae) on eggplants (Solanum melongena L.)

Thrips palmi Karny (Thysanoptera: Thripidae) is a phytophagous insect associated with the reduction of eggplant productivity. The aim of this study was to evaluate the effect of calcium silicate and/or an organic mineral fertilizer, together or separately, in increasing the resistance of eggplants to T. palmi. The treatments were calcium silicate, organic mineral fertilizer, calcium silicate associated with this fertilizer and the control. Mortality and number of lesions caused by nymphs of this insect on eggplant leaves were evaluated after 3, 6, 9 and 12 leaf applications of these products. The calcium silicate and the organic mineral fertilizer reduced both the population of T. palmi and the damage caused by its nymphs, suggesting a possible increase in eggplant resistance to this pest as a result of the treatments.

Changes in the surface of four calcium silicate-containing endodontic materials and an epoxy resin-based sealer after a solubility test

Aim To compare the changes in the surface structure and elemental distribution, as well as the percentage of ion release, of four calcium silicate-containing endodontic materials with a well-established epoxy resin-based sealer, submitted to a solubility test. Methodology Solubility of AH Plus, iRoot SP, MTA Fillapex, Sealapex and MTA-Angelus (MTA-A) was tested according to ANSI/ADA Specification 57. The deionized water used in the solubility test was submitted to atomic absorption spectrophotometry to determine and quantify Ca2+, Na+, K+, Zn2+, Ni2+ and Pb2+ ions release. In addition, the outer and inner surfaces of nonsubmitted and submitted samples of each material to the solubility test were analysed by means of scanning electron microscopy and energy-dispersive spectroscopy (SEM/EDX). Statistical analysis was performed by using one-way anova and Tukeys post hoc tests (a = 0.05). Results Solubility results, in percentage, sorted in an increasing order were -1.24 +/- 0.19 (MTA-A), 0.28 +/- 0.08 (AH Plus), 5.65 +/- 0.80 (Sealapex), 14.89 +/- 0.73 (MTA Fillapex) and 20.64 +/- 1.42 (iRoot SP). AH Plus and MTA-A were statistically similar (P > 0.05), but different from the other materials (P < 0.05). High levels of Ca2+ ion release were observed in all groups except AH Plus sealer. MTA-A also had the highest release of Na2+ and K+ ions. Zn+2 ion release was observed only with AH Plus and Sealapex sealers. After the solubility test, all surfaces had morphological changes. The loss of matrix was evident and the filler particles were more distinguishable. EDX analysis displayed high levels of calcium and carbon at the surface of Sealapex, MTA Fillapex and iRoot SP. Conclusions AH Plus and MTA-A were in accordance with ANSI/ADAs requirements regarding solubility whilst iRoot SP, MTA Fillapex and Sealapex did not fulfil ANSI/ADAs protocols. High levels of Ca2+ ion release were observed in all materials except AH Plus. SEM/EDX analysis revealed that all samples had morphological changes in both outer and inner surfaces after the solubility test. High levels of calcium and carbon were also observed at the surface of all materials except AH Plus and MTA-A.

Structural, Spectroscopic (NMR, IR, and Raman), and DFT Investigation of the Self-Assembled Nanostructure of Pravastatin-LDH (Layered Double Hydroxides) Systems

Layered double hydroxide (LDH) nanocontainers, suitable as carriers for anionic drugs, were intercalated with Pravastatin drug using magnesium-aluminum and zinc-aluminum in a M-II/Al molar ratio equal 2 and different Al3+/Pravastatin molar ratios. Postsynthesis treatments were used in order to increase the materials crystallinity. Hybrid materials were characterized by a set of physical chemical techniques: chemical elemental analysis, X-ray diffraction (XRD), mass coupled thermal analyses, vibrational infrared and Raman spectroscopies, and solid-state C-13 nuclear magnetic resonance (NMR). Results were interpreted in light of computational density functional theory (DFT) calculations performed for Sodium Pravastatin in order to assign the data obtained for the LDH intercalated materials. XRD peaks of LDH-Pravastatin material and the one-dimensional (1D) electron density map pointed out to a bilayer arrangement of Pravastatin in the interlayer region, where its associated carboxylate and vicinal hydroxyl groups are close to the positive LDH. The structural organization observed for the stacked assembly containing the unsymmetrical and bulky monoanion Pravastatin and LDH seems to be promoted by a self-assembling process, in which local interactions are maximized and chloride ion cointercalation is required. It is observed a high similarity among vibrational and C-13 NMR spectra of Na-Pravastatin and LDH-Pravastatin materials. Those features indicate that the intercalation preserves the drug structural integrity. Spectroscopic techniques corroborate the nature of the guest species and their arrangement between the inorganic layers. Changes related to carboxylate, alcohol, and olefinic moieties are observed in both vibrational Raman and C-13 NMR spectra after the drug intercalation. Thus, Pravastatin ions are forced to be arranged as head to tail through intermolecular hydrogen bonding between adjacent organic species. The thermal decomposition profile of the hybrid samples is distinct of that one observed for Na-Pravastatin salt, however, with no visible increase in the thermal behavior when the organic anion is sequestrated within LDH gap.

Raman-spektroskopische Untersuchungen an Alkali- und Erdalkalisilicatgläsern bei hohen Temperaturen

In der vorliegenden Arbeit wird die Struktur von Alkali- und Erdalkalisilicatglaesern bei hohen Temperaturen (bis 1800 K) mit Hilfe der Raman-Spektroskopie untersucht. Ein wesentlicher Teil der vorliegenden Arbeit besteht in dem Aufbau einer Hochtemperatureinrichtung, die es erlaubt, Raman-Spektren von Silicatglaesern bei sehr hohen Temperaturen zu messen. Mit der Hochtemperatur-Raman-Spektroskopie an Silicatglaesern sind erhebliche experimentelle Schwierigkeiten verbunden: Die thermische Strahlung der Probe überlagert sich mit dem Raman-Spektrum.Die Temperaturbestimmung der Glasprobe, die einen Durchmesser von nur 0,8 mm hat, erfolgt durch den Vergleich der Stokes- und Anti-Stokes-Raman-Intensitaeten einer intensiven Linie einer Referenzprobe. Die Natriumsilicatglaeser werden detailliert untersucht und die Verteilung der Struktureinheiten in den Natriumsilicatglaesern wird zwischen Zimmertemperatur und 900 K bestimmt. Aus der Verteilung der Strukturelemente wird eine Gleichgewichtskonstante K berechnet, welche die Disproportionierungsreaktion zwischen den Struktureinheiten in den Glaesern beschreibt. Der Wert für die Reaktionsenthalpie liegt im untersuchten Konzentrationsbereich zwischen 0 und 28 kJ/mol und haengt systematisch von der Zusammensetzung ab. Die Reaktionsenthalpie nimmt mit zunehmendem Natriumoxid-Gehalt zu.Die quantitative Auswertung der Raman-Spektren der Kaliumsilicatglaeser und der Bariumsilicatglaeser ist auf Grund deren Kristallisation bei hohen Temperaturen mit Problemen behaftet.

The influence of heat treatment on the phase relations in mineral growth systems

ABSTRACT Corundum is one of the most famous gems materials. Different heat treatment methods for enhancement purposes are commonly applied and accepted in the gem market. With this reason, the identification of the natural, unheated corundum is intensively investigated. In this study, aluminium hydroxide minerals and zircon are focused to observe the crystallization and phase change of these minerals during heat treatment procedures. Aluminium hydroxide minerals can be transformed to alumina with the corundum structure by heating. The reaction history of aluminium hydroxide minerals containing corundum was investigated comparing it with diaspore, boehmite, gibbsite and bayerite by TG and DTA methods. These hydroxide minerals were entirely transformed to corundum after heating at 600°C. Zircon inclusions in corundums from Ilakaka, Madagascar, were investigated for the influence of different heat-treatment temperatures on the recovery of their crystalline structure and on possible reactions within and with the host crystals. The host corundum was heated at 500, 800, 1000, 1200, 1400, 1600 and 1800°C. The crystallinity, the trapped pressure, and the decomposition of the zircon inclusions within the host corundum have been investigated by Raman spectroscopy. Radiation-damaged zircon inclusions may be used as an indicator for unheated Ilakaka corundum crystals. They are fully recrystallized after heating at 1000°C influencing the lowering of the 3 Raman band shift, the decreasing of FWHM of the 3 Raman band and the decreasing of the trapped pressure between the inclusion and the host corundum. Under microscopic observation, surface alterations of the inclusions can be firstly seen from transparent into frosted-like appearance at 1400°C. Then, between 1600°C and 1800 °C, the inclusion becomes partly or even completely molten. The decomposition of the zircon inclusion to m-ZrO2 and SiO2-glass phases begins at the rim of the inclusion after heating from 1200°C to 1600°C which can be detected by the surface change, the increase of the 3 Raman band position and the trapped pressure. At 1800°C, the zircon inclusions entirely melt transforming to solid phases during cooling like m-ZrO2 and SiO2-glass accompanied by an increase of pressure between the transformed inclusion and its host.

Spectroscopic study of Bioceramics for Endodontic and Orthopaedics

This thesis was aimed at investigating the physical-chemical properties and the behaviour in physiological environment of two classes of bioceramics: calcium silicate-based dental cements and alumina-based femoral heads for hip joint prostheses. The material characterization was performed using spectroscopic techniques such as that allow to obtain information on the molecular structure of the species and phases present in the analyzed samples. Raman, infrared and fluorescence spectroscopy was principally used. Calcium silicate cements, such as MTA (Mineral Trioxide Aggregate), are hydraulic materials that can set in presence of water: this characteristic makes them suitable for oral surgery and in particular as root-end filling materials. With the aim to improve the properties of commercial MTA cements, several MTA-based experimental formulations have been tested with regard to bioactivity (i.e. apatite forming ability) upon ageing in simulated body fluids. The formation of a bone-like apatite layer may support the integration in bone tissue and represents an essential requirement for osteoconduction and osteoinduction. The spectroscopic studies demonstrated that the experimental materials under study had a good bioactivity and were able to remineralize demineralized dentin. . Bioceramics thanks to their excellent mechanical properties and chemical resistance, are widely used as alternative to polymer (UHMWPE) and metal alloys (Cr-Co) for hip-joint prostesis. In order to investigate the in vivo wear mechanisms of three different generations of commercial bioceramics femoral heads (Biolox®, Biolox® forte, and Biolox® delta), fluorescence and Raman spectroscopy were used to investigate the surface properties and residual stresses of retrieved implants. Spectroscopic results suggested different wear mechanisms in the three sets of retrievals. Since Biolox® delta is a relatively recent material, the Raman results on its retrievals has been reported for the first time allowing to validate the in vitro ageing protocols proposed in the literature to simulate the effects of the in vivo wear.

Zinc deposits and related mineralization of the Burketown mineral field, including the world-class Century Deposit, Northern Australia: Fluid inclusion and stable isotope evidence for basin fluid sources

The stratiform Century Zn-Pb deposit and the discordant Zn-Pb lode deposits of the Burketown mineral field, northern Australia, host ore and gangue minerals with primary fluid inclusions that have not been affected by the Isan orogeny, thus providing a unique opportunity to investigate the nature of the ore-forming brines. All of the deposits are hosted in shales and siltstones belonging to the Isa superbasin and comprise sphalerite, pyrite, carbonate, quartz, galena, minor chalcopyrite, and minor illite. According to Pb model ages, the main ore stage of mineralization at Century formed at I575 Ma, some 20 m.y. after deposition of the host shale sequence. Microthermometry on undeformed, primary fluid inclusions hosted in porous sphalerite shows that the Zn at Century was transported to the deposit by a homogeneous, Ca2+- and Na+-bearing brine with a salinity of 21.6 wt percent NaCl equiv. delta D-fluid of the fluid inclusion water ranges from -89 to -83 per mil, consistent with a basinal brine that evolved from meteoric water. Fluid inclusion homogenization temperatures range between 74 degrees and 125 degrees C, which are lower than the 120 degrees to 160 degrees C range calculated from vitrinite reflectance and illite crystallinity data from the deposit. This discrepancy indicates that mineralization likely formed at 50 to 85 Mpa, corresponding to a depth of 1,900 to 3,100 m. Transgressive galena-sphalerite veins that cut stratiform mineralization at Century and breccia-filled quartz-dolomite-sphalerite-galena veins in the discordant Zn-Pb lodes have Pb model ages between 1575 and 1485 Ma. Raman spectroscopy and microthermometry reveal that the primary fluid inclusions in these veins contain Ca2+, Na+. but they have lower salinities between 23 and 10 wt percent NaCl equiv and higher delta D-fluid values ranging from -89 to -61 per mil than fluid inclusions in porous sphalerite from Century. Fluid inclusion water from sphalerite in one of the lode deposits has delta O-18(fluid) values of 1.6 and 2.4 per mil, indistinguishable from delta O-18(fluid) values between -0.3 to +7.4 per mil calculated from the isotopic composition of coexisting quartz, dolomite, and illite. The trend toward lower salinities and higher delta D-fluid values relative to the earlier mineralizing fluids is attributed to mixing between the fluid that formed Century and a seawater-derived fluid from a different source. Based on seismic data from the Lawn Hill platform and paragenetic and geochemical results from the Leichhardt River fault trough to the south, diagenetic aquifers in the Underlying Calvert superbasin appear to have been the most likely sources for the fluids that formed Century and the discordant lode deposits. Paragenetically late sphalerite and calcite cut sphalerite, quartz, and dolomite in the lode deposits and contain Na+-dominated fluid inclusions with much lower salinities than their older counterparts. The isotopic composition of calcite also indicates delta O-18(fluid) from 3.3 to 10.7 per mil, which is larger than the range obtained from synmineralization minerals, supporting the idea that a unique fluid source was involved. The absolute timing of this event is unclear, but a plethora of Pb model, K-Ar, and Ar-40/Ar-39 ages between 1440 and 1300 Ma indicate that a significant volume of fluid was mobilized at this time. The deposition of the Roper superbasin from ca. 1492 +/- 4 Ma suggests that these late veins formed from fluids that may have been derived from aquifers in overlying sediments of the Roper superbasin. Clear, buck, and drusy quartz in veins unrelated to any form of Pb-Zn mineralization record the last major fluid event in the Burketown mineral field and form distinct outcrops and ridges in the district. Fluid inclusions in these veins indicate formation from a low-salinity, 300 degrees +/- 80 degrees C fluid. Temperatures approaching 300 degrees C recorded in organic matter adjacent to faults and at sequence boundaries correspond to K-Ar ages spanning 1300 to 1100 Ma, which coincides with regional hydrothermal activity in the northern Lawn Hill platform and the emplacement of the Lakeview Dolerite at the time of assemblage of the Rodinia supercontinent.

Estudo por espectroscopia micro-Raman dos mecanismos de separação de fase em vidros fosfatos de metais de transição

Glass-ceramics are prepared by controlled separation of crystal phases in glasses, leading to uniform and dense grain structures. On the other hand, chemical leaching of soluble crystal phases yields porous glass-ceramics with important applications. Here, glass/ceramic interfaces of niobo-, vanado- and titano-phosphate glasses were studied by micro-Raman spectroscopy, whose spatial resolution revealed the multiphase structures. Phase-separation mechanisms were also determined by this technique, revealing that interface composition remained unchanged as the crystallization front advanced for niobo- and vanadophosphate glasses (interface-controlled crystallization). For titanophosphate glasses, phase composition changed continuously with time up to the equilibrium composition, indicating a spinodal-type phase separation.

Knoop microhardness and FT-Raman evaluation of composite resins: influence of opacity and photoactivation source

The aim of this study was to evaluate the degree of conversion by Knoop microhardness (KHN) and FT-Raman spectroscopy (FTIR) of one nanofilled (Filtek Supreme-3M-ESPE [FS]) and one microhybrid composite (Charisma-Heraeus-Kulzer [CH]), each with different opacities, namely enamel, dentin, and translucent, which were photo-activated by a quartz-tungsten-halogen lamp (QTH) and a light-emitting diode (LED). Resin was bulk inserted into a disc-shaped mold that was 2.0 mm thick and 4 mm in diameter, obtaining 10 samples per group. KHN and FTIR values were analyzed by two-way ANOVA and Tukey's tests (α = 0.05). Nanofilled resin activated by a LED presented higher microhardness values than samples activated by a QTH for dentin opacity (p < 0.05). The microhybrid resin showed no differences in KHN or FTIR values with different activation sources or opacity. The nanofilled dentin and enamel resins showed lower FTIR values than the translucent resin. The KHN values of the translucent resins were not influenced by the light source.

Análise colorimétrica e espectroscópica do muco de caracóis terrestres Achatina sp alimentados com ração diferenciada

Foram estudados os efeitos da adição de plantas medicinais de princípios cicatrizantes (Centelha asiática, Papaína e Confrei) na ração controle de caracóis terrestres, para se avaliar a interferência destas plantas na composição do muco glicoprotéico. Foram utilizados 80 caracóis terrestres Achatina sp, baseados em um peso homogêneo (49 e 40 g e idade média de 10 e 19 meses para Achatina fulica e Achatina monochromatica, respectivamente). Os animais foram distribuídos aleatoriamente em oito grupos experimentais: controle Achatina fulica (FC) e Achatina monochromatica (MC), centelha asiática Achatina fulica (FCe) e Achatina monochromatica (MCe), papaína Achatina fulica (FPa) e Achatina monochromatica (MPa) e confrei Achatina fulica (FCo) e Achatina monochromatica (MCo). Água e ração foram fornecidos ad libitum. Ao final de 150 dias de tratamento, os animais foram submetidos à técnica de extração do muco glicoprotéico, por meio do estímulo manual da glândula podal, responsável pela secreção deste muco. Esta metodologia considerou o bem-estar dos animais, uma vez que os mesmos não foram sacrificados e retornaram ao seu sistema de criação. Os mucos foram analisados por meio de testes colorimétricos e espectroscópicos, que constataram alterações semelhantes, porém apresentaram variação significativa em sua composição glicoprotéica.

Spectral Region Optimization for Raman-Based Optical Biopsy of Inflammatory Lesions

Objective: The biochemical alterations between inflammatory fibrous hyperplasia (IFH) and normal tissues of buccal mucosa were probed by using the FT-Raman spectroscopy technique. The aim was to find the minimal set of Raman bands that would furnish the best discrimination. Background: Raman-based optical biopsy is a widely recognized potential technique for noninvasive real-time diagnosis. However, few studies had been devoted to the discrimination of very common subtle or early pathologic states as inflammatory processes that are always present on, for example, cancer lesion borders. Methods: Seventy spectra of IFH from 14 patients were compared with 30 spectra of normal tissues from six patients. The statistical analysis was performed with principal components analysis and soft independent modeling class analogy cross-validated, leave-one-out methods. Results: Bands close to 574, 1,100, 1,250 to 1,350, and 1,500 cm(-1) (mainly amino acids and collagen bands) showed the main intragroup variations that are due to the acanthosis process in the IFH epithelium. The 1,200 (C-C aromatic/DNA), 1,350 (CH(2) bending/collagen 1), and 1,730 cm(-1) (collagen III) regions presented the main intergroup variations. This finding was interpreted as originating in an extracellular matrix-degeneration process occurring in the inflammatory tissues. The statistical analysis results indicated that the best discrimination capability (sensitivity of 95% and specificity of 100%) was found by using the 530-580 cm(-1) spectral region. Conclusions: The existence of this narrow spectral window enabling normal and inflammatory diagnosis also had useful implications for an in vivo dispersive Raman setup for clinical applications.

Fluorescence and reflectance spectroscopy for identification of atherosclerosis in human carotid arteries using principal components analysis

Objectives: The aim of this work was to verify the differentiation between normal and pathological human carotid artery tissues by using fluorescence and reflectance spectroscopy in the 400- to 700-nm range and the spectral characterization by means of principal components analysis. Background Data: Atherosclerosis is the most common and serious pathology of the cardiovascular system. Principal components represent the main spectral characteristics that occur within the spectral data and could be used for tissue classification. Materials and Methods: Sixty postmortem carotid artery fragments (26 non-atherosclerotic and 34 atherosclerotic with non-calcified plaques) were studied. The excitation radiation consisted of a 488-nm argon laser. Two 600-mu m core optical fibers were used, one for excitation and one to collect the fluorescence radiation from the samples. The reflectance system was composed of a halogen lamp coupled to an excitation fiber positioned in one of the ports of an integrating sphere that delivered 5 mW to the sample. The photo-reflectance signal was coupled to a 1/4-m spectrograph via an optical fiber. Euclidean distance was then used to classify each principal component score into one of two classes, normal and atherosclerotic tissue, for both fluorescence and reflectance. Results: The principal components analysis allowed classification of the samples with 81% sensitivity and 88% specificity for fluorescence, and 81% sensitivity and 91% specificity for reflectance. Conclusions: Our results showed that principal components analysis could be applied to differentiate between normal and atherosclerotic tissue with high sensitivity and specificity.