Time-Resolved X-Ray Powder Diffraction Study of Photoinduced Phase Transitions in Ti3 O5 Nanoparticles.

Nanoparticles of Ti3 O5 have been reported to show a permanent photoinduced phase transition at room temperature. This suggests that light-induced phase transformations of Ti3 O5 nanoparticles may be promising for technological applications. Here, we report a photoinduced semiconductor-to-metal phase transition from ß-Ti3 O5 to λ-Ti3 O5 nanoparticles at room temperature observed directly by time-resolved X-ray powder diffraction in a pump-probe setup. The results show a partial structural change, limited by differences between pumped and probed volumes, which persists a few microseconds after excitation. The first step in the relaxation back to the ground state can be described by a single exponential decay with time constant within microsecond timescales. Analysis of the change in lattice constants enables us to estimate an average temperature increase across the phase transition, consistent with a thermally driven process.

Comparing two tetraalkylammonium ionic liquids. I. Liquid phase structure.

X-ray scattering experiments at room temperature were performed for the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2]. The peak in the diffraction data characteristic of charge ordering in [N1444][NTf2] is shifted to longer distances in comparison to [N1114][NTf2], but the peak characteristic of short-range correlations is shifted in [N1444][NTf2] to shorter distances. Molecular dynamics (MD) simulations were performed for these ionic liquids using force fields available from the literature, although with new sets of partial charges for [N1114](+) and [N1444](+) proposed in this work. The shifting of charge and adjacency peaks to opposite directions in these ionic liquids was found in the static structure factor, S(k), calculated by MD simulations. Despite differences in cation sizes, the MD simulations unravel that anions are allowed as close to [N1444](+) as to [N1114](+) because anions are located in between the angle formed by the butyl chains. The more asymmetric molecular structure of the [N1114](+) cation implies differences in partial structure factors calculated for atoms belonging to polar or non-polar parts of [N1114][NTf2], whereas polar and non-polar structure factors are essentially the same in [N1444][NTf2]. Results of this work shed light on controversies in the literature on the liquid structure of tetraalkylammonium based ionic liquids.

Comparing two tetraalkylammonium ionic liquids. II. Phase transitions.

Phase transitions of the ionic liquids n-butyl-trimethylammonium bis(trifluoromethanesulfonyl)imide, [N1114][NTf2], and methyl-tributylammonium bis(trifluoromethanesulfonyl)imide, [N1444][NTf2], were investigated by differential scanning calorimetry (DSC), X-ray diffraction (XRD) measurements, and Raman spectroscopy. XRD and Raman spectra were obtained as a function of temperature at atmospheric pressure, and also under high pressure at room temperature using a diamond anvil cell (DAC). [N1444][NTf2] experiences glass transition at low temperature, whereas [N1114][NTf2] crystallizes or not depending on the cooling rate. Both the ionic liquids exhibit glass transition under high pressure. XRD and low-frequency Raman spectra provide a consistent physical picture of structural ordering-disordering accompanying the thermal events of crystallization, glass transition, cold crystallization, pre-melting, and melting. Raman spectra in the high-frequency range of some specific cation and anion normal modes reveal conformational changes of the molecular structures along phase transitions.

A versatile x-ray microtomography station for biomedical imaging and materials research.

An x-ray microtomography station implemented at the X-ray Applied Crystallography Laboratory of the State University of Campinas is described. The station is based on a propagation based phase contrast imaging setup with a microfocus source and digital x-ray area detectors. Due to its simplicity, this setup is ideal for fast, high resolution imaging and microtomography of small biological specimens and materials research samples. It can also be coupled to gratings to use and develop new techniques as the harmonic spatial coherent imaging, which allow scattering contrast imaging. Details of the experimental setup, equipment, and software integration are described. Test microtomography for setup commissioning and characterization is shown. We conclude that phase contrast enhanced x-ray imaging and microtomography with resolution below 5 µm voxel size are possible and data sets as wide as 2000 × 2000 × 2000 voxels are obtained with this instrumentation.

Iron insertion and hematite segregation on Fe-doped TiO2 nanoparticles obtained from sol-gel and hydrothermal methods.

Iron-doped TiO(2) (Fe:TiO(2)) nanoparticles were synthesized by the sol-gel method (with Fe/Ti molar ratio corresponding to 1, 3, and 5%), followed by hydrothermal treatment, drying, and annealing. A similar methodology was used to synthesize TiO(2) and α-Fe(2)O(3) nanoparticles. For comparison, a mixture hematite/titania, with Fe/Ti = 4% was also investigated. Characterization of the samples using Rietveld refinement of X-ray diffraction data revealed that TiO(2) consisted of 82% anatase and 18% brookite; for Fe:TiO(2), brookite increased to 30% and hematite was also identified (0.5, 1.0, and 1.2 wt % for samples prepared with 1, 3, and 5% of Fe/Ti). For hematite/titania mixture, Fe/Ti was estimated as 4.4%, indicating the Rietveld method reliability for estimation of phase composition. Because the band gap energy, estimated as 3.2 eV for TiO(2), gradually ranged from 3.0 to 2.7 eV with increasing Fe content at Fe:TiO(2), it can be assumed that a Fe fraction was also inserted as dopant in the TiO(2) lattice. Extended X-ray absorption fine structure spectra obtained for the Ti K-edge and Fe K-edge indicated that absorbing Fe occupied a Ti site in the TiO(2) lattice, but hematite features were not observed. Hematite particles also could not be identified in the images obtained by transmission electron microscopy, in spite of iron identification by elemental mapping, suggesting that hematite can be segregated at the grain boundaries of Fe:TiO(2).

Preparation and characterization of ethanol-treated silk fibroin dense membranes for biomaterials application using waste silk fibers as raw material.

The possibility of producing valued devices from low cost natural resources is a subject of broad interest. The present study explores the preparation and characterization of silk fibroin dense membranes using waste silk fibers from textile processing. Morphology, crystallinity, thermal resistance and cytotoxicity of membranes as well as the changes on the secondary structure of silk fibroin were analyzed after undergoing treatment with ethanol. Membranes presented amorphous patterns as determined via X-ray diffraction. The secondary structure of silk fibroin on dense membranes was either random coil (silk I) or beta-sheet (silk II), before and after ethanol treatment, respectively. The sterilized membranes presented no cytotoxicity to endothelial cells during in vitro assays. This fact stresses the material potential to be used in the fabrication of biomaterials, as coatings of cardiovascular devices and as membranes for wound dressing or drug delivery systems.

Functional and small-angle X-ray scattering studies of a new stationary phase survival protein E (SurE) from Xylella fastidiosa--evidence of allosteric behaviour.

The genome data of bacterium Xylella fastidiosa strain 9a5c has identified several orfs related to its phytopathogenic adaptation and survival. Among these genes, the surE codifies a survival protein E (XfSurE) whose function is not so well understood, but functional assays in Escherichia coli revealed nucleotidase and exopolyphosphate activity. In the present study, we report the XfSurE protein overexpression in E. coli and its purification. The overall secondary structure was analyzed by CD. Small-angle X-ray scattering and gel filtration techniques demonstrated that the oligomeric state of the protein in solution is a tetramer. In addition, functional kinetics experiments were carried out with several monophosphate nucleoside substrates and revealed a highly positive cooperativity. An allosteric mechanism involving torsion movements in solution is proposed to explain the cooperative behaviour of XfSurE. This is the first characterization of a SurE enzyme from a phytopathogen organism and, to our knowledge, the first solution structure of a SurE protein to be described.

Diamond thermal expansion measurement using transmitted X-ray back-diffraction.

The linear thermal expansion coefficient of diamond has been measured using forward-diffracted profiles in X-ray backscattering. This experimental technique is presented as an alternative way of measuring thermal expansion coefficients of solids in the high-resolution Bragg backscattering geometry without the intrinsic difficulty of detecting the reflected beam. The temperature dependence of the lattice parameter is obtained from the high sensitivity of the transmitted profiles to the Bragg angle variation with temperature. The large angular width of the backscattering profiles allows the application of this technique to mosaic crystals with high resolution. As an application of this technique the thermal expansion coefficient of a synthetic type-Ib diamond (110) single crystal was measured from 10 to 300 K. Extremely low values (of the order of 1 x 10(-7) +/- 5 x 10(-7)) for the linear thermal expansion coefficient in the temperature range from 30 to 90 K are in good agreement with other reported measurements.