Temperature Dependent near Infrared Spectroscopy of Electron Irradiated Ceria Single Crystals.

The FTIR absorption bands of virgin and electron-irradiated CeO2 single crystals were measured from 20 K to 500 K between 4000 cm-1 and 12,000 cm-1 (~830 nm to 2500 nm). Three broad bands centered at about 6100 cm-1 (~0.75 eV), 7000 cm-1 (~0.87 eV), and 10,500 cm-1 (~1.3 eV) were recorded above 100 K for the 2.5 MeV electron energy. Two smaller bands at about 4300 cm-1 (~0.53 eV) and 5500 cm-1 (~0.68 eV) were also recorded below 100 K. Similar broad bands centered at about 4100 cm-1 (~0.52 eV), 6400 cm-1 (~0.79 eV), 7600 cm-1 (~0.94 eV), and 10,500 cm-1 (~1.3 eV) are also found for the 1.4 MeV electron energy above 300 K. The evolution of these absorption bands was followed as a function of temperature. The plots of band intensity ratios show a thermally activated process corresponding to the ionization of the deep electronic levels of point defects in the band gap of ceria of ~26,000 cm-1 (~3.2 eV). These five bands are assigned to the different charge states (0, -1, -2, -3, -4) of the Ce vacancies produced by elastic collisions above 1.0 MeV.

Multi-wavelength Raman microscopy of nickel-based electron transport in cable bacteria.

Cable bacteria embed a network of conductive protein fibers in their cell envelope that efficiently guides electron transport over distances spanning up to several centimeters. This form of long-distance electron transport is unique in biology and is mediated by a metalloprotein with a sulfur-coordinated nickel (Ni) cofactor. However, the molecular structure of this cofactor remains presently unknown. Here, we applied multi-wavelength Raman microscopy to identify cell compounds linked to the unique cable bacterium physiology, combined with stable isotope labeling, and orientation-dependent and ultralow-frequency Raman microscopy to gain insight into the structure and organization of this novel Ni-cofactor. Raman spectra of native cable bacterium filaments reveal vibrational modes originating from cytochromes, polyphosphate granules, proteins, as well as the Ni-cofactor. After selective extraction of the conductive fiber network from the cell envelope, the Raman spectrum becomes simpler, and primarily retains vibrational modes associated with the Ni-cofactor. These Ni-cofactor modes exhibit intense Raman scattering as well as a strong orientation-dependent response. The signal intensity is particularly elevated when the polarization of incident laser light is parallel to the direction of the conductive fibers. This orientation dependence allows to selectively identify the modes that are associated with the Ni-cofactor. We identified 13 such modes, some of which display strong Raman signals across the entire range of applied wavelengths (405-1,064 nm). Assignment of vibrational modes, supported by stable isotope labeling, suggest that the structure of the Ni-cofactor shares a resemblance with that of nickel bis(1,2-dithiolene) complexes. Overall, our results indicate that cable bacteria have evolved a unique cofactor structure that does not resemble any of the known Ni-cofactors in biology.

Charge-driven arrested phase-separation of polyelectrolyte-gold nanoparticle assemblies leading to plasmonic oligomers.

Aggregates of charged metal particles obtained by electrostatic coupling with a compound of opposite charge in the vicinity of the net zero charge ratio are of interest in the field of plasmonics because the inter-particle distance is minimal, which favours plasmonic coupling. However, these structures present a low colloidal stability limiting the development of applications. In this article we show that globally neutral aggregates formed by electrostatic complexation of citrate-stabilized gold particles and a quaternized chitosan (i.e., polycation) around the net zero charge ratio could be stabilized at a nanometric size by the subsequent addition of polyelectrolyte chains. Furthermore, the sign of the charge carried by the stabilizing chains determines the sign of the global charge carried by the stabilized complexes. The stabilization is demonstrated in saline environment on a broad pH range as well as in a cell culture media over periods of several days. Contrarily to stabilization by charged particles, our stabilized complexes are found to retain their initial characteristics (i.e. shape, size, internal structure and optical properties) after stabilization. Hence, the plasmonic coupling allows to maximize the optical absorption around the 800 nm wavelength at which the lasers used for thermoplasmonic and surface enhanced Raman scattering analysis operate.

Lithium Borates from the Glass to the Melt: A Temperature-Induced Structural Transformation Viewed from the Boron and Oxygen Atoms.

A multiedge study of the local structure of lithium borate glasses and melts has been carried out using X-ray Raman scattering (XRS) as a function of temperature. Thanks to a wide range of compositions, from pure B2O3 up to the metaborate composition, we are able to finely interpret the modifications of the local environment of both the boron and oxygen atoms in terms of boron coordination number, formation of nonbridging oxygens (NBOs), and polymerization degree of the borate framework as a function of temperature and composition. A temperature-induced [4]B to [3]B conversion is observed above the glass transition temperature (Tg) from the glass to the melt from the triborate composition up to the metaborate composition. Two distinct melt structures are reported: a well-polymerized borate network-with few NBOs-below the triborate composition and a depolymerized borate network above the diborate composition with a rapid increase of the number of NBOs when Li2O is added. These two structurally distinct melts allow explaining the two dynamic regimes observed for lithium ion diffusion.

Unexpected intracellular biodegradation and recrystallization of gold nanoparticles.

Gold nanoparticles are used in an expanding spectrum of biomedical applications. However, little is known about their long-term fate in the organism as it is generally admitted that the inertness of gold nanoparticles prevents their biodegradation. In this work, the biotransformations of gold nanoparticles captured by primary fibroblasts were monitored during up to 6 mo. The combination of electron microscopy imaging and transcriptomics study reveals an unexpected 2-step process of biotransformation. First, there is the degradation of gold nanoparticles, with faster disappearance of the smallest size. This degradation is mediated by NADPH oxidase that produces highly oxidizing reactive oxygen species in the lysosome combined with a cell-protective expression of the nuclear factor, erythroid 2. Second, a gold recrystallization process generates biomineralized nanostructures consisting of 2.5-nm crystalline particles self-assembled into nanoleaves. Metallothioneins are strongly suspected to participate in buildings blocks biomineralization that self-assembles in a process that could be affected by a chelating agent. These degradation products are similar to aurosomes structures revealed 50 y ago in vivo after gold salt therapy. Overall, we bring to light steps in the lifecycle of gold nanoparticles in which cellular pathways are partially shared with ionic gold, revealing a common gold metabolism.

Speciation Change of Uranyl in Lithium Borate Glasses.

Determining the uranyl(VI) UO22+ reactivity in crystalline and amorphous oxides is necessary to control its mobility. The intrinsic versatility of borate structural units containing both triangular BO3 and tetrahedral BO4 makes them original and rich hosts for uranyl. As part of the effort to determine the uranium stability in borate oxides, we have determined the speciation of uranium(VI) in two lithium borate glasses containing, respectively, 10 mol % and 30 mol % Li2O using a combined structural and spectroscopic approach based on X-ray absorption spectroscopy (XAS). M4- and L3-edge high-resolution XAS demonstrates the speciation of U(VI) as uranyl in both glasses. Comparison of uranyl bond distances obtained by EXAFS with distances found in borate crystals reveals that in the low alkali borate glass, uranyl is present as hexagonal bipyramids with six equatorial oxygen ligands. This local environment was never observed in any other oxide glass. We show that the increase of the lithium content induces the decrease of the equatorial coordination number. The associated uranyl bond elongation suggests the influence of the alkali cations in relation with drastic changes in the structure of the borate network. The spectroscopic evidence of this speciation change is discussed in terms of change in the uranyl electronic structure and covalency.

Color-center production and recovery in electron-irradiated magnesium aluminate spinel and ceria.

Single crystals of magnesium aluminate spinel (MgAl2O4) with (1 0 0) or (1 1 0) orientations and cerium dioxide or ceria (CeO2) were irradiated by 1.0 MeV and 2.5 MeV electrons in a high-fluence range. Point-defect production was studied by off-line UV-visible optical spectroscopy after irradiation. For spinel, regardless of both crystal orientation and electron energy, two characteristic broad bands centered at photon energies of 5.4 eV and 4.9 eV were assigned to F and F(+) centers (neutral and singly ionized oxygen vacancies), respectively, on the basis of available literature data. No clear differences in color-center formation were observed for the two crystal orientations. Using calculations from displacement cross sections by elastic collisions, these results are consistent with a very large threshold displacement energy (200 eV) for oxygen atoms at room temperature. A third very broad band centered at 3.7 eV might be attributed either to an oxygen hole center (V-type center) or an F2 dimer center (oxygen di-vacancy). The onset of recovery of these color centers took place at 200 °C with almost full bleaching at 600 °C. Activation energies (~0.3-0.4 eV) for defect recovery were deduced from the isochronal annealing data by using a first-order kinetics analysis. For ceria, a sub-band-gap absorption feature, which peaked at ~3.1 eV, was recorded for 2.5 MeV electron irradiation only. Assuming a ballistic process, we suggest that the latter defect might result from cerium atom displacement on the basis of computed cross sections.

Assessment of Transition Element Speciation in Glasses Using a Portable Transmission Ultraviolet-Visible-Near-Infrared (UV-Vis-NIR) Spectrometer.

A new low-cost experimental setup based on two compact dispersive optical spectrometers has been developed to measure optical absorption transmission spectra over the 350-2500 nm energy range. We demonstrate how near-infrared (NIR) data are essential to identify the coloring species in addition to ultraviolet visible data. After calibration with reference glasses, the use of an original sample stage that maintains the window panel in the vertical position enables the comparison of ancient and modern glasses embedded in a panel from the Sainte-Chapelle of Paris, without any sampling. The spectral resolution enables to observe fine resonances arising in the absorption bands of Cr(3+), and the complementary information obtained in the NIR enables to determine the contribution of Fe(2+), a key indicator of glassmaking conditions.

Optical Absorption Microspectroscopy (µ-OAS) Based on Schwarzschild-Type Cassegrain Optics.

A new experimental setup, combining a custom-designed Schwarzschild-type Cassegrain-based microscope and an ultraviolet-visible-near infrared (UV-Vis-NIR) spectrophotometer, has been developed, focusing the light beam down to 20 µm diameter. Optical absorption spectra (in the 300-2500 nm range) have been measured on micrometer-sized natural glass inclusions providing information on iron speciation in magmatic melts. The absence of contribution from the host crystal matrix provides a test of the efficiency of micro-focusing. A microthermometric stage has been adapted on the microscope for measuring optical absorption spectra up to 900 K with application to the thermochromism of minute natural spinel crystals (MgAl2O4:Fe(2+),Cr(3+)). This experimental setup provides an easy and fast way to follow the evolution of spectral properties and color of glasses or crystals with temperature as well as the possibility of measuring spatially resolved optical absorption spectra.

Detecting non-bridging oxygens: non-resonant inelastic X-ray scattering in crystalline lithium borates.

Probing the local environment of low-Z elements, such as oxygen, is of great interest for understanding the atomic-scale behavior in materials, but it requires experimental techniques allowing it to work with versatile sample environments. In this paper, the local environment of lithium borate crystals is investigated using non-resonant inelastic X-ray scattering (NRIXS) at energy losses corresponding to the oxygen K-edge. Large variations of the spectral features are observed close to the edge onset in the 535-540 eV energy range when varying the Li2O content. Calculations allow identification of contributions associated with bridging oxygen (BO) and non-bridging oxygen (NBO) atoms. The main result resides in the observed core-level shift of about 1.7 eV in the spectral signatures of the BO and NBO. The clear signature at 535 eV in the O K-edge NRXIS spectrum is thus an original way to probe the presence of NBOs in borates, with the great advantage of making possible the use of complex environments such as a high-pressure cell or high-temperature device for in situ measurements.

Crystal structures of Li6B4O9 and Li3B11O18 and application of the dimensional reduction formalism to lithium borates.

The crystal structures of two members of the Li2O-B2O3 phase diagram, Li6B4O9 and Li3B11O18, have been solved from single-crystal X-ray diffraction, and their structure has been further confirmed by Rietveld refinement on powder samples. Li6B4O9 crystallizes in the P2(1)/n space group with a = 3.31913(15) Å, b = 23.361(2) Å, c = 9.1582(4) Å, and ß = 92.650(4)°. It is the only lithium borate being built upon clusters made of four BO3 triangular units linked by vertices. Li3B11O18 adopts also a monoclinic symmetry with a = 17.7607(8) Å, b = 7.7737(4) Å, c = 9.6731(4) Å, and ß = 100.906(4)° (space group P2(1)/c); it contains 73% BO3 triangular units and 27% BO4 tetrahedra, linked by vertices such that it forms a 3D network containing B3O7 and B5O10 rings. These two new structures and their specificities are discussed in the framework of the dimensional reduction formalism together with other reported lithium borates and may serve as a crystalline reference to study borate glasses.

Molecular dynamics and neutron scattering study of glucose solutions confined in MCM-41.

Glucose aqueous solutions confined in MCM-41 cylindrical pores of diameter 3.2 nm have been studied by molecular dynamics (MD) simulations and quasielastic neutron scattering (QENS). MD simulations reveal a strong preferential interaction of glucose molecules with the silica walls, which induces significant concentration gradients within the pore. The influence of glucose on the structural and dynamical properties of water strongly depends on the region of the pore considered. The distortion of the hydrogen bond network (HBN) and of the tetrahedral organization of interfacial water molecules induced by silica is much stronger than that induced by glucose molecules. The interfacial glucose molecules diffuse about 1 order of magnitude slower than those in the core region. Differences in affinities for silica of the different species in confined hydrogen-bonded mixtures induce significant structural and dynamical heterogeneities not present in bulk solutions.

Water Confined in Cylindrical Pores: A Molecular Dynamics Study.

Molecular dynamics simulations of water confined in two hydrophilic cylindrical pores-PH and PL-that differ in their silanol surface concentration (7.6 and 3.0 nm(-2), respectively) have been performed at 300 K. A strong interaction of interfacial water molecules with the pore was systematically found and gives rise to a layering effect, a significant distortion of both the hydrogen bond network (HBN) and the tetrahedral structure of these water molecules, and a corresponding subdiffusive mean square displacement along the main axis of the pores. By contrast, water molecules in the inner part of both pores were found to behave similarly to bulk water. The HBN and the tetrahedral configuration of water were more gradually distorted in the PL pore given the larger heterogeneity and rugosity of the surface, and the number of water-pore hydrogen bonds did not scale linearly with the silanol surface concentration of the pores, in part because of the close proximity between silanols in the PH pore. With the PL pore, the dynamic slowing down of water was found consistent with the experiment, suggesting that it provides a better model for the cylindrical MCM-41 mesopores. The structural and dynamical properties of water vary little with the silica force field.

Uptake of functionalized mesoporous silica nanoparticles by human cancer cells.

Mesoporous silica nanoparticles (MSN) were functionalised by aminofluorescein (AMF) with diethylenetriaminepentaacetic acid spacer molecules which provide free carboxylic groups for binding cell-specific ligands such as folate. AMF allowed the exploration of cellular uptake by HeLa cells using confocal microscopy and flow cytometry. The functionalized nanoparticles (MSN-AMF) penetrated efficiently into HeLa cell cytoplasm through a clathrin dependent endocytosis mechanism. The number of endocytosed MSN-AMF was enhanced when using folate as a targeting molecule. Uptake kinetics revealed that most of MSN-AMF were internalized within 4 h of incubation. Moreover, we found that MSN-AMF were capable of escaping the acidic endolysosomal vesicles of HeLa cells. Cytotoxicity studies suggested that these nanoparticles are non-toxic to HeLa cells up to a dose level of 50 microg/ml.

Translational and rotational dynamics of monosaccharide solutions.

Molecular dynamics computer simulations have been carried out on aqueous solutions of glucose at concentrations bracketing those previously measured with quasi-elastic neutron scattering (QENS), in order to investigate the motions and interactions of the sugar and water molecules. In addition, QENS measurements have been carried out on fructose solutions to determine whether the effects previously observed for glucose apply to monosaccharide solutions. The simulations indicate a dynamical analogy between higher solute concentration and lower temperature that could provide a key explanation of the bioprotective phenomena observed in many living organisms. The experimental results on fructose solutions show qualitatively similar behavior to the glucose solutions. The dynamics of the water molecules are essentially the same, while the translational diffusion of the sugar molecules is slightly faster in the fructose solutions.

Dynamics of trehalose molecules in confined solutions.

The dynamics of trehalose molecules in aqueous solutions confined in silica gel have been studied by quasielastic neutron scattering (QENS). Small-angle neutron scattering measurements confirmed the absence of both sugar clustering and matrix deformation of the gels, indicating that the results obtained are representative of homogeneous trehalose solutions confined in a uniform matrix. The pore size in the gel is estimated to be 18 nm, comparable to the distances in cell membranes. For the QENS measurements, the gel was prepared from D2O in order to accentuate the scattering from the trehalose. Values for the translational diffusion constant and effective jump distance were derived from model fits to the scattering function. Comparison with QENS and NMR results in the literature for bulk trehalose shows that confinement on a length scale of 18 nm has no significant effect on the translational diffusion of trehalose molecules.

Molecular dynamics of confined glucose solutions.

Silica gels containing solutions of glucose in heavy water at different concentrations have been prepared by a sol-gel method. Dynamical studies with quasielastic neutron scattering, compared with previous results on bulk solutions, show that the dynamics of the glucose molecules are not appreciably affected by the confinement, even though the gels behave macroscopically as solid materials. Small-angle neutron-scattering spectra on the same systems, fitted with a fractal model, yield a correlation length that decreases from 20 to 2.5 nm with increasing glucose concentration, suggesting a clustering of glucose molecules in concentrated solutions that is consistent with the dynamical measurements. These two sets of results imply that 20 nm is an upper limit for the scale at which the dynamics of glucose molecules in solution are affected by confinement.