Mössbauer spectroscopic study of the early crystallization stage of iron(III) hydroxide particles

Mössbauer spectroscopy was used to investigate the early aging stage of iron(III) hydroxide sols prepared by oxidation of Fe(CO)5 in ethanolic solution, followed by vacuum drying at room temperature. One sample was composed of amorphous particles, while two other samples were partially crystallized, either as a result of solvent change or of spontaneous aging. The main results of Mössbauer measurements in the 80-320 K temperature range are: (a) partially crystallized particles exhibit a strong, S-shaped temperature dependence of the quadrupole splitting, in contrast to a weak and linear variation for amorphous particles; (b) the recoilless fraction temperature dependence is affected by vibration of the particles as a whole, with an effective force constant which is smaller for crystallized particles than for amorphous ones. Furthermore, the former exhibit anf-factor discontinuity near 0°C, which is attributed to melting of a surface layer built up during the crystallization process. © 1986.

Middle Proterozoic vein-hosted gold deposits in the Pontes e Lacerda region, southwestern Amazonian craton, Brazil

Structural, geochemical, and isotope studies were carried out on the gold deposits of the Pontes e Lacerda region (Mato Grosso state, Brazil), where rocks of the Aguapei and Rondoniano mobile belts (southwestern Amazonian craton) occur. The orebodies are hosted in metavolcanic, gneiss-granite, quartzite, tonalite, and granite units. Tectonics involve oblique overthrusting (from northeast to southwest), which led to the formation of recumbent folds and thrusts (pathways for the mineralizing fluids), upright folds, and faults with dominant strike-slip component. These unconformities represent potential sites for mineralization. During geological mapping, it was observed that the orebodies consist of quartz, pyrite, and gold, and that the hydrothermal alteration zone contains quartz, sericite, pyrite (altered to limonite), and magnetite (altered to hematite). Chalcopyrite, galena, and sphalerite occur only in the Onça deposit. Chemical analysis of sulfides indicates high contents of Bi, Se, and Te in sulfides and gold, suggesting plutonic involvement in the origin of hydrothermal solutions. K-Ar dating of hydrothermal sericites from gold veins yielded ages in the range from 960 to 840 Ma, which may indicate the age of original crystallization of sericite. Pb-Pb dating in galenas yielded model ages in the range from 1000 to 800 Ma for the Onça deposit, which is in agreement with K-Ar ages. Pb-isotopic ratios indicate high U/Pb and low Th/Pb for the upper-crustal Pb source before incorporation in galena crystals. The Pontes e Lacerda gold deposits yielded ages correlated to the Aguapei event and probably were formed during a Proterozoic contractional tectonic period in the southwestern part of the Amazon craton, which may characterize an important metallogenic epoch in the Pontes e Lacerda region.

Crystallization of ZrF4-LaF3-AlF3 glasses

0.7125ZrF4-0.2375(1 - xLaF3 • xLnF3)-0.05AIF3 with x = 0.01, 0.02 and 0.03 for Ln = Er and x = 0.03 for Ln = Pr, Nd glasses were studied by differential thermal analysis (DTA), X-ray diffraction and optical spectroscopy. Avrami parameters (Ec and n) were obtained from DTA curves. With La3+ substitution a decrease in the stability against crystallization was observed. This decrease follows the order Er3+ > Nd3+ ≈ Pr3+ for 3% molar substitution. n values suggest an interface controlled growth mechanism with grain edge nucleation abler saturation. Two crystalline polymorphs of the LaZr3F15 phase were identified. With the substitution of 3 mol% of Pr3+, Nd3+ or Er3+ for La3+ only the crystallization of the rhombohedral α-LnZr3F15 phase was observed. An increase in Ω6 Judd's intensity parameter occurs with crystallization and also an increase in the 1.04 μm peak emission cross-section for Nd3+ 4I3/2 state suggesting the potential application of these glass ceramics in optical amplification devices. © 1997 Elsevier Science B.V.

Crystallization of fluorindate and fluorogallate glasses

Crystallization of binary InF3-MF2 and GaF3-MF2 (where M = Ba, Sr and Ca) glasses was studied. Characteristic temperatures and kinetic parameters E (activation energy) and n (Avrami exponent) were obtained. Stability against devitrification is discussed in terms of the above cited parameters and also of some others parameters proposed in literature. Optical properties (IR and upconversion emissions) are reported in different crystallized samples containing Nd3+. The main observation is that up conversion emission presents an enhanced sensibility to crystallization when compared to conventional emission. © 1997 Published by Elsevier Science B.V.

Short Range Order Evolution in the Preparation of SnO2 Based Materials

The evolution of Eu3+ doped SnO2 xerogels to the cassiterite structure observed during sintering was studied by means of Eu3+ spectroscopy, XRD and EXAFS at the Sn K-edge. Eu3+ ions adsorbed at the surface of colloidal particles present a broad distribution of sites, typical of oxide glasses. With sintering at 300°C, this distribution is still broadened. Crystallization is clearly observed by the three techniques with increasing sintering temperature. It is found that the addition of Eu3+ limits the crystallite growth.

Crystallization and preliminary X-ray analysis of SIII-SPIII, a ahospholipase A2 isolated from the venom of Bothrops jararacussu

Large single crystals have been obtained of SIII-SPIII, a phospholipase A2 from the venom of Bothrops jararacussu. The crystals belong to the orthorhombic system space group C222, and diffract X-rays to a resolution of 1.9 Å. Preliminary analysis reveals the presence of one molecule in the crystallographic asymmetric unit. The crystal structure is currently being determined using molecular replacement techniques.

The influence of crystallization route on the SrBi2Nb2O9 thin films

Polycrystalline SrBi2Nb2O9-layered ferroelectric thin films were synthesized on Pt/Ti/SiO2/Si substrate using the polymeric precursors solution. The dip-coated films were specular and crack-free and crystallized during firing at 700 °C. Single-, double-, and triple-layered films were obtained by several dips in the deposition solution, and the influence of crystallization between each dip was studied. Microstructure and morphological evaluation were followed by grazing incident x-ray diffraction (GIXRD), scanning electron microscopy (SEM), and atomic force microscopy (AFM). Multilayered films obtained using the intermediate-crystallized layer route present a dense microstructure with spherical grains, with a preferential orientation in the 〈215〉 direction; films obtained using the intermediate-amorphous layer route are polycrystalline and present elongated grains around 250 nm in size.

Crystallization mechanism and properties of a blast furnace slag glass

The complex crystallization process of a Brazilian blast-furnace slag glass was investigated using differential scanning calorimetry (DSC), X-ray diffraction, optical microscopy, transmission electron microscopy (TEM), selected area diffraction (SAD), energy dispersive spectroscopy (EDS) and micro-Raman spectroscopy. Three crystalline phases (merwinite, melilite and larnite) were identified after heat treatment between Tg (742°C) and the DSC crystallization peak (T = 1000°C). Merwinite was identified as a metastable phase. A small amount (0.004 wt%) of metallic platinum was found in the glass composition. Particles of Pt3Fe, detected by EDS and SAD-TEM, were the starting points of crystallization acting, therefore, as heterogeneous nucleating sites. Only melilite and larnite precipitated in a glass sample heat-treated at 1000°C for 1 h. The flexural strength of this crystallized sample was less than that of the glass, probably due the allotropic phase transformation of larnite. © 2000 Published by Elsevier Science B.V. All rights reserved.

Assignment of the bisulfide bridges in bothropstoxin-I, a Myonecrotic Lys49 PLA2 homolog from bothrops jararacussu snake venom

Bothropstoxin-I (BthTX-I), a Lys49 phospholipase A2 homolog with no apparent catalytic activity, was first isolated from Bothrops jararacussu snake venom and completely sequenced in this laboratory. It is a 121-amino-acid single polypeptide chain, highly myonecrotic, despite its inability to catalyze hydrolysis of egg yolk phospholipids, and has 14 half-cystine residues identified at positions 27, 29, 44, 45, 50, 51, 61, 84, 91, 96, 98, 105, 123, and 131 (numbering according to the conventional alignment including gaps, so that the last residue is Cys 131). In order to access its seven disulfide bridges, two strategies were followed: (1) Sequencing of isolated peptides from (tryptic + SV8) and chymotryptic digests by Edman-dansyl degradation; (2) crystallization of the protein and determination of the crystal structure so that at least two additional disulfide bridges could be identified in the final electron density map. Identification of the disulfide-containing peptides from the enzymatic digests was achieved following the disappearance of the original peptides from the HPLC profile after reduction and carboxymethylation of the digest. Following this procedure, four bridges were initially identified from the tryptic and SV8 digests: Cys50-Cysl31, Cys51-Cys98, Cys61-Cys91, and Cys84-Cys96. From the chymotryptic digest other peptides were isolated either containing some of the above bridges, therefore confirming the results from the tryptic digest, or presenting a new bond between Cys27 and Cys 123. The two remaining bridges were identified as Cys29-Cys45 and Cys44-Cysl05 by determination of the crystal structure, showing that BthTX-I disulfide bonds follow the normal pattern of group II PLA2s. © 2001 Plenum Publishing Corporation.

Crystallization of amorphous GaAs films prepared onto different substrates

This work reports changes in structural properties produced by thermal annealing of flash evaporated amorphous GaAs films using the micro-Raman scattering and the X-ray diffraction (XRD) techniques. Films of about 1 μm were grown on c-Si and glass substrates. The crystallization process is less effective for samples deposited on c-Si. This could be due to the ordering in the first layers of the film imposed by the oriented Si substrates. We propose that this ordering makes the growth of crystallites in these films more restrained than the growth occurring in the completely amorphous films on glass substrates. © 2002 Elsevier Science B.V. All rights reserved.

Plutonismn in three orogenic pulses, Eastern Blue Ridge Province, southern Appalachians

The Eastern Blue Ridge Province of the southern Appalachians contains, in part, remnants of an Ordovician accretionary wedge complex formed during subduction of an oceanic tract before mid-Ordovician accretion with Laurentia. The Eastern Blue Ridge Province consists of metapelite and amphibolite intruded by low-K plutons, high-temperature (T >750 °C) Ordovician eclogite, and other high-pressure metamafic and meta-ultramafic rocks. Felsic plutons in the Eastern Blue Ridge Province are important time markers for regional-scale tectonics, deformation, and metamorphism. Plutons were thought to be related to either Taconian (Ordovician) or Acadian (Devonian-Silurian) tectonothermal events. We dated five plutonic or metaplutonic rocks to constrain pluton crystallization ages better and thus the timing of tectonism. The Persimmon Creek gneiss yielded a protolith crystallization age of 455.7 ± 2.1 Ma, Chalk Mountain 377.7 ± 2.5 Ma, Mt. Airy 334 ± 3Ma, Stone Mountain 335.6 ± 1.0 Ma, and Rabun 335.1 ± 2.8 Ma. The latter four plutons were thought to be part of the Acadian Spruce Pine Suite, but instead our new ages indicate that Alleghanian (Carboniferous-Permian) plutonism is widespread and voluminous in the Eastern Blue Ridge Province. The Chattahoochee fault, which was considered an Acadian structure, cuts the Rabun pluton and thus must have been active during the Alleghanian orogeny. The new ages indicate that Persimmon Creek crystallized less than 3 m.y. after zircon crystallization in Eastern Blue Ridge eclogite and is nearly synchronous with nearby high-grade metamorphism and migmatization. The three phases of plutonism in the Eastern Blue Ridge Province correspond with established metamorphic ages for each of the three major orogenic pulses along the western flank of the southern Appalachians. © 2006 Geological Society of America.

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd3+, Mn2+ and Cu2+ heat treated at different temperatures, ranging from the glass transition temperature (Tg) to the crystallization temperature (Tc), are investigated by electron paramagnetic resonance (EPR) and 19F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu2+ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba2ZnF6, which correspond to Cu2+ in a tetragonal compressed F- octahedron and to Cu2+ on interstitial sites with a square-planar F- co-ordination. The EPR spectra of the Mn2+ doped glasses exhibit a sextet structure due to the Mn2+ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn2+ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn2+ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn2+ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd3+ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd3+ ions in environment close to cubic symmetry. The 19F NMR spin-lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above Tc. For the glass samples (doped or undoped) the 19F magnetization recoveries were found to be adjusted by an exponential function and the spin-lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above Tc, the 19F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu2+, Mn2+, Gd3+ EPR spectra and NMR relaxation, are always observed for the samples annealed above Tc. © 2006 Elsevier B.V. All rights reserved.

Analytical model for heterogeneous crystallization kinetics of spherical glass particles

An analytical model developed to describe the crystallization kinetics of spherical glass particles has been derived in this work. A continuous phase transition from three-dimensional (3D)-like to 1D-like crystal growth has been considered and a procedure for the quantitative evaluation of the critical time for this 3D-1D transition is proposed. This model also allows straightforward determination of the density of surface nucleation sites on glass powders using differential scanning calorimetry data obtained under different thermal conditions. © 2009 The American Ceramic Society.

Structural insights into selectivity and cofactor binding in snake venom l-amino acid oxidases

l-Amino acid oxidases (LAAOs) are flavoenzymes that catalytically deaminate l-amino acids to corresponding α-keto acids with the concomitant production of ammonia (NH 3) and hydrogen peroxide (H 2O 2). Particularly, snake venom LAAOs have been attracted much attention due to their diverse clinical and biological effects, interfering on human coagulation factors and being cytotoxic against some pathogenic bacteria and Leishmania ssp. In this work, a new LAAO from Bothrops jararacussu venom (BjsuLAAO) was purified, functionally characterized and its structure determined by X-ray crystallography at 3.1å resolution. BjsuLAAO showed high catalytic specificity for aromatic and aliphatic large side-chain amino acids. Comparative structural analysis with prokaryotic LAAOs, which exhibit low specificity, indicates the importance of the active-site volume in modulating enzyme selectivity. Surprisingly, the flavin adenine dinucleotide (FAD) cofactor was found in a different orientation canonically described for both prokaryotic and eukaryotic LAAOs. In this new conformational state, the adenosyl group is flipped towards the 62-71 loop, being stabilized by several hydrogen-bond interactions, which is equally stable to the classical binding mode. © 2012 Elsevier Inc.

Crystallization and optical properties of CCTO thin films under pressure influence

CCTO thin films were deposited on Pt(111)/Ti/SiO 2/Si substrates using a chemical (polymeric precursor) and pressure method. The pressure effects on the CCTO thin films were evaluated by XRD, FEG-SEM and optical properties. Pressure films were found to be more homogeneous and dense than chemical deposition films. Pressure also leaded to an increase in the photoluminescence emission; it is suggested that the displacement of Ti in the titanate clusters, favors the charge transference from TiO 6 to [TiO 5V o z], TiO 5V o z] to [CaO 11V o z] and [TiO 5V o z] to [CuO 4] x. The low synthesis temperature used in the pressure method allows the deposition of films on less expensive substrates (i.e. glass, aluminum, polymer and others).