Influence of thermal history on the structure and properties of silicate glasses

We studied a set of float glass samples prepared with different fictive temperature by previous annealing around the glass transition temperature. We compared the results to previous measurements on a series of amorphous silica samples, also prepared with different fictive temperature. We showed that the modifications on the structure at a local scale are very small, the changes of physical properties are moderate but the changes on density fluctuations at a nanometer scale are rather large: 12 and 20% in float glass and silica, for relative changes of fictive temperature equal to 13 and 25% respectively. Local order and mechanical properties of silica vary in the opposite way compared to float glass (anomalous behavior) but the density fluctuations in both glasses increase with temperature and fictive temperature

In situ measurements of density fluctuations and compressibility in silica glass as a function of temperature and thermal history

In this paper, small-angle X-ray scattering measurements are used to determine the different compressibility contributions, as well as the isothermal compressibility, in thermal equilibrium in silica glasses having different thermal histories. Using two different methods of analysis, in the supercooled liquid and in the glassy state, we obtain respectively the temperature and fictive temperature dependences of the isotheraml compressibility. The values obtained in the glass and supercooled liquid states are very close to each other. They agree with previous determinations of the literature. The compressibility in the glass state slightly decreases with increasing fictive temperature. The relaxational part of the compressibility is also calculated and compared to previous determinations. We discussed the small differences between the different determinations

Characterization of recombinant human lactoferrin N-glycans expressed in the milk of transgenic cows.

Lactoferrin (LF) is one of the most abundant bioactive glycoproteins in human milk. Glycans attached through N-glycosidic bonds may contribute to Lactoferrin functional activities. In contrast, LF is present in trace amounts in bovine milk. Efforts to increase LF concentration in bovine milk led to alternative approaches using transgenic cows to express human lactoferrin (hLF). This study investigated and compared N-glycans in recombinant human lactoferrin (rhLF), bovine lactoferrin (bLF) and human lactoferrin by Nano-LC-Chip-Q-TOF Mass Spectrometry. The results revealed a high diversity of N-glycan structures, including fucosylated and sialylated complex glycans that may contribute additional bioactivities. rhLF, bLF and hLF had 23, 27 and 18 N-glycans respectively with 8 N-glycan in common overall. rhLF shared 16 N-glycan with bLF and 9 N-glycan with hLF while bLF shared 10 N-glycan with hLF. Based on the relative abundances of N-glycan types, rhLF and hLF appeared to contain mostly neutral complex/hybrid N-glycans (81% and 52% of the total respectively) whereas bLF was characterized by high mannose glycans (65%). Interestingly, the majority of hLF N-glycans were fucosylated (88%), whereas bLF and rhLF had only 9% and 20% fucosylation, respectively. Overall, this study suggests that rhLF N-glycans share more similarities to bLF than hLF

Raman spectroscopy of GeSe and AgGeSe thin films

The structural properties of Agy(Ge0.25Se0.75)1-y thin films (y=0, 0.07, 0.10, 0.15, 0.20 and 0.25 at. fraction) were studied. The films were prepared by pulsed laser deposition using bulk glass targets of the studied ternary system and deposited onto microscope slides. Their amorphous structures were confirmed by XRD (X-ray Diffraction). The effect of silver content on films structures was analysed by Raman spectroscopy. Typical Raman vibration modes were observed in the Ge0.25Se0.75 binary film: Ge-Se corner-sharing tetrahedra mode (CS) at 199 cm-1, edge sharing tetrahedra mode (ES) at 217 cm-1, and SeSe rings and chains mode at 255-265 cm-1 (CM). In the Agy(Ge0.25Se0.75)1-y ternary thin films, the same modes were observed but with a red shift and an intensity reduction in the ES and CM bands.Fil: Conde Garrido, Juan Manuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería "Hilario Fernández Long". Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías y Ciencias de la Ingeniería ; Argentina. Universidad de Buenos Aires. Facultad de Ingenieria. Departamento de Fisica. Laboratorio de Sólidos Amorfos; ArgentinaFil: Piarristeguy, A.. Universidad de Buenos Aires. Facultad de Ingenieria. Departamento de Fisica. Laboratorio de Sólidos Amorfos; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Houssay. Instituto de Tecnologías y Ciencias de la Ingeniería "Hilario Fernández Long". Universidad de Buenos Aires. Facultad de Ingeniería. Instituto de Tecnologías y Ciencias de la Ingeniería ; ArgentinaFil: Le Parc, R.. Centre National de la Recherche Scientifique; Francia. Universite Montpellier II; FranciaFil: Ureña, Maria Andrea.Fil: Fontana, Marcelo.Fil: Arcondo, B..Fil: Pradel, A.. Universite Montpellier Ii; Franci

High-pressure behavior of polyiodides confined into single-walled carbon nanotubes: A Raman study

International audienceThe high-pressure behavior of polyiodides confined into the hollow core of single-walled carbon nanotubes organized into bundles has been studied by means of Raman spectroscopy. Several regimes of the structural properties are observed for the nanotubes and the polyiodides under pressure. Raman responses of both compounds exhibit correlations over the whole pressure range (0–17 GPa). Modifications, in particular, take place, respectively, between 1 and 2.3 GPa for polyiodides and between 7 and 9 GPa for nanotubes, depending on the experiment. Differences between one experiment to another are discussed in terms of nanotube filling homogeneity. These transitions can be presumably assigned to the tube ovalization pressure and to the tube collapse pressure. A nonreversibility of several polyiodide mode modifications is evidenced and interpreted in terms of a progressive linearization of the iodine polyanions and a reduction in the charged species on pressure release. Furthermore, the significant change in the mode intensities could be associated to an enhancement of lattice modes, suggesting the formation of a new structure inside the nanotube. Changes in the nanotube mode positions after pressure release point out a decrease in the charge transfer in the hybrid system consistent with the observed evolution of the charged species

High-pressure behavior of polyiodides confined into single-walled carbon nanotubes: A Raman study

International audienceThe high-pressure behavior of polyiodides confined into the hollow core of single-walled carbon nanotubes organized into bundles has been studied by means of Raman spectroscopy. Several regimes of the structural properties are observed for the nanotubes and the polyiodides under pressure. Raman responses of both compounds exhibit correlations over the whole pressure range (0–17 GPa). Modifications, in particular, take place, respectively, between 1 and 2.3 GPa for polyiodides and between 7 and 9 GPa for nanotubes, depending on the experiment. Differences between one experiment to another are discussed in terms of nanotube filling homogeneity. These transitions can be presumably assigned to the tube ovalization pressure and to the tube collapse pressure. A nonreversibility of several polyiodide mode modifications is evidenced and interpreted in terms of a progressive linearization of the iodine polyanions and a reduction in the charged species on pressure release. Furthermore, the significant change in the mode intensities could be associated to an enhancement of lattice modes, suggesting the formation of a new structure inside the nanotube. Changes in the nanotube mode positions after pressure release point out a decrease in the charge transfer in the hybrid system consistent with the observed evolution of the charged species

Chromophore Ordering by Confinement into Carbon Nanotubes

International audienceWe report an experimental study on the confinement of oligothiophene derivatives into single-walled carbon nanotubes over a large range of diameter (from 0.68 to 1.93 nm). We evidence by means of Raman spectroscopy and transmission electron microscopy that the supramolecular organizations of the confined oligothiophenes depend on the nanocontainer size. The Raman Radial Breathing Mode frequency is shown to be monitored by both the number of confined molecules into a nanotube section and the competition between oligothiophene/oligothiophene and oligothiophene/tube wall interactions. We finally propose simple Raman criteria to characterize oligothiophene supramolecular organization at the nanoscale

Fermi level shift in carbon nanotubes by dye confinement

International audienceDye confinement into carbon nanotube significantly affects the electronic charge density distribution of the final hybrid system. Using the electron-phonon coupling sensitivity of the Raman G-band, we quantify experimentally how charge transfer from thiophene oligomers to single walled carbon nanotube is modulated by the diameter of the nano-container and its metallic or semiconducting character. This charge transfer is shown to restore the electron-phonon coupling into defected metallic nanotubes. For sub-nanometer diameter tube, an electron transfer optically activated is observed when the excitation energy matches the HOMO-LUMO transition of the confined oligothiophene. This electron doping accounts for an important enhancement of the photoluminescence intensity up to a factor of nearly six for optimal confinement configuration. This electron transfer shifts the Fermi level, acting on the photoluminescence efficiency. Therefore, thiophene oligomer encapsulation allows modulating the electronic structure and then the optical properties of the hybrid system