Oxidation State and Structure of Fe in Nontronite: From Oxidizing to Reducing Conditions.

The redox reaction between natural Fe-containing clay minerals and its sorbates is a fundamental process controlling the cycles of many elements such as carbon, nutrients, redox-sensitive metals, and metalloids (e.g., Co, Mn, As, Se), and inorganic as well as organic pollutants in Earth's critical zone. While the structure of natural clay minerals under oxic conditions is well-known, less is known about their behavior under anoxic and reducing conditions, thereby impeding a full understanding of the mechanisms of clay-driven reduction and oxidation (redox) reactions especially under reducing conditions. Here we investigate the structure of a ferruginous natural clay smectite, nontronite, under different redox conditions, and compare several methods for the determination of iron redox states. Iron in nontronite was gradually reduced chemically with the citrate-bicarbonate-dithionite (CBD) method. 57Fe Mössbauer spectrometry, X-ray photoelectron spectroscopy (XPS), X-ray absorption near edge structure (XANES) spectroscopy including its pre-edge, extended X-ray absorption fine structure (EXAFS) spectroscopy, and mediated electrochemical oxidation and reduction (MEO/MER) provided consistent Fe(II)/Fe(III) ratios. By combining X-ray diffraction (XRD) and transmission electron microscopy (TEM), we show that the long-range structure of nontronite at the highest obtained reduction degree of 44% Fe(II) is not different from that of fully oxidized nontronite except for a slight basal plane dissolution on the external surfaces. The short-range order probed by EXAFS spectroscopy suggests, however, an increasing structural disorder and Fe clustering with increasing reduction of structural Fe.

Low Temperature Nitriding of Metal Alloys for Surface Mechanical Performance.

Metallic alloys are, by essence, ductile and stiff and can support loads without sudden rupture. This ductility becomes a disadvantage when applications require wear resistance. In this case, the hardening of the surface is required while retaining a core performance. Here, nitriding at low temperatures has proven to be beneficial and has potential. In fact, any phase transitions or unwanted compound precipitations that occur at higher temperatures have to be avoided as they would have a deleterious effect on the chemical homogeneity and mechanical properties. The present contribution summarizes the achievements made with such treatments on metallic alloys. We considered the most popular treatments, namely plasma, implantation, and gas nitridings.

Effect of Nanographene Coating on the Seebeck Coefficient of Mesoporous Silicon.

Nanographene-mesoporous silicon (G-PSi) composites have recently emerged as a promising class of nanomaterials with tuneable physical properties. In this study, we investigated the impact of nanographene coating on the Seebeck coefficient of mesoporous silicon (PSi) obtained by varying two parameters: porosity and thickness. To achieve this, an electrochemical etching process on p + doped Si is presented for the control of the parameters (thicknesses varying from 20 to 160 µm, and a porosity close to 50%), and for nanographene incorporation through chemical vapor deposition. Raman and XPS spectroscopies confirmed the presence of nanographene on PSi. Using a homemade ZT meter, the Seebeck coefficient of the p + doped Si matrix was evaluated at close to 100 ± 15 µV/K and confirmed by UPS spectroscopy analysis. Our findings suggest that the Seebeck coefficient of the porous Si can be measured independently from that of the substrate by fitting measurements on samples with a different thickness of the porous layer. The value of the Seebeck coefficient for the porous Si is of the order of 750 ± 40 µV/K. Furthermore, the incorporation of nanographene induced a drastic decrease to approximately 120 ± 15 µV/K, a value similar to that of its silicon substrate.

Relation between Mechanical Hardening and Nitrogen Profile of PBII Nitrided Titanium Alloy.

Surface treatments of Ti-6Al-4V alloys are of utmost importance for biomedical applications since they allow for tribological gain. Here, Ti-6Al-4V disks have been PBII nitrided at either 500, 600, 700 and 800 °C. A set of techniques (XRD, SEM-EDS, EBSD and GDOES) was used to characterize the surface microstructural and chemical changes. Nanoindentation was used to assess the induced changes in terms of mechanical properties. Two types of nitrided domains are revealed. Starting from the surface, a nitride bilayer composed of δ-TiN/ϵ-Ti2N with enhanced surface resistance is supported by an α-Ti(N) solid solution formed at depth. Hardness values peak at 12-14 GPa at the surface, which is almost twice as large as the bulk value (about 7 GPa). For the moderate temperatures used here, a deep (10-15 µm) and strong hardness (14 GPa) enhancement together with a smooth gradient can be achieved.

Stress-Assisted Thermal Diffusion Barrier Breakdown in Ion Beam Deposited Cu/W Nano-Multilayers on Si Substrate Observed by in Situ GISAXS and Transmission EDX.

The thermal stability of Cu/W nano-multilayers deposited on a Si substrate using ion beam deposition was analyzed in situ by GISAXS and transmission EDX-a combination of methods permitting the observation of diffusion processes within buried layers. Further supporting techniques such as XRR, TEM, WAXS, and AFM were employed to develop an extensive microstructural understanding of the multilayer before and during heating. It was found that the pronounced in-plane compressive residual stress and defect population induced by ion beam deposition result in low thermal stability driven by thermally activated self-interstitial and vacancy diffusion, ultimately leading to complete degradation of the layered structure at moderate temperatures. The formation of Cu protrusions was observed, and a model was formulated for stress-assisted Cu diffusion driven by Coble creep along W grain boundaries, along with the interaction with Si substrate, which showed excellent agreement with the observed experimental data. The model provided the explanation for the experimentally observed strong correlation between thin film deposition conditions, microstructural properties, and low thermal stability that can be applied to other multilayer systems.

Wavelength tunable ultrafast fiber laser via reflective mirror with taper structure.

Laser sources with a controllable flexible wavelength have found widespread applications in optical fiber communication, optical sensing, and microscopy. Here, we report a tunable mode-locked fiber laser using a graphene-based saturable absorber and a tapered mirror as an end mirror in the cavity. The phase layer in the mirror is precisely etched by focused ion beam (FIB) milling technology, and the resonant wavelength of the mirror shifts correspond to the different etch depths. By scanning the tapered mirror mechanically, the center wavelength of a mode-locked fiber laser can be continuously tuned from 1562 to 1532 nm, with a pulse width in the sub-ps level and repetition rate of 27 MHz.

Carbon nanotube-poly(methyl methacrylate) hybrid films: preparation using diazonium salt chemistry and mechanical properties.

HYPOTHESIS: The poor miscibility of carbon nanotubes (CNTs) in common organic solvents and organic monomers requires their modification by suitable functional (reactive or not) groups prior to their incorporation in thermoplastic polymers. EXPERIMENTS: Dispersion behavior of carbon nanotubes and mechanical properties of various CNT-poly(methylmethacrylate) (PMMA) nanocomposites were investigated. We studied the influence of the surface chemistry through the use of diazonium salts as an elegant and environmentally friendly platform to provide a suitable sidewall functionalization by methyl methacrylate functions. We used either a molecular size functional group through the grafting of methacryloxypropyltrimethoxysilane or a macromolecular size one, consisting in PMMA brushes grown by SI-ATRP in order to study the influence of the length of methacrylate function on the dispersion of CNT in PMMA. FINDINGS: The hardness and the elastic indentation modulus of all hybrid films were obtained through nanoindentation measurements and found to increase, using ATRP-modified CNTs, suggesting a better dispersion of CNTs in PMMA due to optimal inorganic-organic interactions promoted by the short chains of PMMA.

Structure-mechanical function relations at nano-scale in heat-affected human dental tissue.

The knowledge of the mechanical properties of dental materials related to their hierarchical structure is essential for understanding and predicting the effect of microstructural alterations on the performance of dental tissues in the context of forensic and archaeological investigation as well as laser irradiation treatment of caries. So far, few studies have focused on the nano-scale structure-mechanical function relations of human teeth altered by chemical or thermal treatment. The response of dental tissues to thermal treatment is thought to be strongly affected by the mineral crystallite size, their spatial arrangement and preferred orientation. In this study, synchrotron-based small and wide angle X-ray scattering (SAXS/WAXS) techniques were used to investigate the micro-structural alterations (mean crystalline thickness, crystal perfection and degree of alignment) of heat-affected dentine and enamel in human dental teeth. Additionally, nanoindentation mapping was applied to detect the spatial and temperature-dependent nano-mechanical properties variation. The SAXS/WAXS results revealed that the mean crystalline thickness distribution in dentine was more uniform compared with that in enamel. Although in general the mean crystalline thickness increased both in dentine and enamel as the temperature increased, the local structural variations gradually reduced. Meanwhile, the hardness and reduced modulus in enamel decreased as the temperature increased, while for dentine, the tendency reversed at high temperature. The analysis of the correlation between the ultrastructure and mechanical properties coupled with the effect of temperature demonstrates the effect of mean thickness and orientation on the local variation of mechanical property. This structural-mechanical property alteration is likely to be due to changes of HAp crystallites, thus dentine and enamel exhibit different responses at different temperatures. Our results enable an improved understanding of the mechanical properties correlation in hierarchical biological materials, and human dental tissue in particular.

Wnt antagonists bind through a short peptide to the first ß-propeller domain of LRP5/6.

The Wnt pathway inhibitors DKK1 and sclerostin (SOST) are important therapeutic targets in diseases involving bone loss or damage. It has been appreciated that Wnt coreceptors LRP5/6 are also important, as human missense mutations that result in bone overgrowth (bone mineral density, or BMD, mutations) cluster to the E1 propeller domain of LRP5. Here, we report a crystal structure of LRP6 E1 bound to an antibody, revealing that the E1 domain is a peptide recognition module. Remarkably, the consensus E1 binding sequence is a close match to a conserved tripeptide motif present in all Wnt inhibitors that bind LRP5/6. We show that this motif is important for DKK1 and SOST binding to LRP6 and for inhibitory function, providing a detailed structural explanation for the effect of the BMD mutations.

Dynamics of completely unfolded and native proteins through solid-state nanopores as a function of electric driving force.

We report experimentally the dynamic properties of the entry and transport of unfolded and native proteins through a solid-state nanopore as a function of applied voltage, and we discuss the experimental data obtained as compared to theory. We show an exponential increase in the event frequency of current blockades and an exponential decrease in transport times as a function of the electric driving force. The normalized current blockage ratio remains constant or decreases for folded or unfolded proteins, respectively, as a function of the transmembrane potential. The unfolded protein is stretched under the electric driving force. The dwell time of native compact proteins in the pore is almost 1 order of magnitude longer than that of unfolded proteins, and the event frequency for both protein conformations is low. We discuss the possible phenomena hindering the transport of proteins through the pores, which could explain these anomalous dynamics, in particular, electro-osmotic counterflow and protein adsorption on the nanopore wall.

Wnt isoform-specific interactions with coreceptor specify inhibition or potentiation of signaling by LRP6 antibodies.

ß-Catenin-dependent Wnt signaling is initiated as Wnt binds to both the receptor FZD and coreceptor LRP5/6, which then assembles a multimeric complex at the cytoplasmic membrane face to recruit and inactivate the kinase GSK3. The large number and sequence diversity of Wnt isoforms suggest the possibility of domain-specific ligand-coreceptor interactions, and distinct binding sites on LRP6 for Wnt3a and Wnt9b have recently been identified in vitro. Whether mechanistically different interactions between Wnts and coreceptors might mediate signaling remains to be determined. It is also not clear whether coreceptor homodimerization induced extracellularly can activate Wnt signaling, as is the case for receptor tyrosine kinases. We generated monoclonal antibodies against LRP6 with the unexpected ability to inhibit signaling by some Wnt isoforms and potentiate signaling by other isoforms. In cell culture, two antibodies characterized further show reciprocal activities on most Wnts, with one antibody antagonizing and the other potentiating. We demonstrate that these antibodies bind to different regions of LRP6 protein, and inhibition of signaling results from blocking Wnt binding. Antibody-mediated dimerization of LRP6 can potentiate signaling only when a Wnt isoform is also able to bind the complex, presumably recruiting FZD. Endogenous autocrine Wnt signaling in different tumor cell lines can be either antagonized or enhanced by the LRP6 antibodies, indicating expression of different Wnt isoforms. As anticipated from the roles of Wnt signaling in cancer and bone development, antibody activities can also be observed in mice for inhibition of tumor growth and in organ culture for enhancement of bone mineral density. Collectively, our results indicate that separate binding sites for different subsets of Wnt isoforms determine the inhibition or potentiation of signaling conferred by LRP6 antibodies. This complexity of coreceptor-ligand interactions may allow for differential regulation of signaling by Wnt isoforms during development, and can be exploited with antibodies to differentially manipulate Wnt signaling in specific tissues or disease states.

Reconstitution of a frizzled8.Wnt3a.LRP6 signaling complex reveals multiple Wnt and Dkk1 binding sites on LRP6.

Wnt/beta-catenin signaling is initiated at the cell surface by association of secreted Wnt with its receptors Frizzled (Fz) and low density lipoprotein receptor-related protein 5/6 (LRP5/6). The study of these molecular interactions has been a significant technical challenge because the proteins have been inaccessible in sufficient purity and quantity. In this report we describe insect cell expression and purification of soluble mouse Fz8 cysteine-rich domain and human LRP6 extracellular domain and show that they inhibit Wnt/beta-catenin signaling in cellular assays. We determine the binding affinities of Wnts and Dickkopf 1 (Dkk1) to the relevant co-receptors and reconstitute in vitro the Fz8 CRD.Wnt3a.LRP6 signaling complex. Using purified fragments of LRP6, we further show that Wnt3a binds to a region including only the third and fourth beta-propeller domains of LRP6 (E3E4). Surprisingly, we find that Wnt9b binds to a different part of the LRP6 extracellular domain, E1E2, and we demonstrate that Wnt3a and Wnt9b can bind to LRP6 simultaneously. Dkk1 binds to both E1E2 and E3E4 fragments and competes with both Wnt3a and Wnt9b for binding to LRP6. The existence of multiple, independent Wnt binding sites on the LRP6 co-receptor suggests new possibilities for the architecture of Wnt signaling complexes and a model for broad-spectrum inhibition of Wnt/beta-catenin signaling by Dkk1.

Phosphorylation of a borealin dimerization domain is required for proper chromosome segregation.

The chromosomal passenger complex (CPC) has been identified as a master regulator of mitosis. In particular, proper chromosome segregation and cytokinesis depend on the correct localization and function of the CPC. Within the complex, the kinase Aurora B associates with Incenp, Survivin, and Borealin. The stoichiometry of the complex as well as a complete understanding of how these four components interact with each other remains to be elucidated. Here, we identify a new domain of Borealin. We determined its structure using NMR spectroscopy and discovered a novel dimerization motif. Interestingly, we found that substitutions at Borealin T230, recently identified as an Mps1 phosphorylation site, can modulate the dimerization state of Borealin. Mutation of this single residue to alanine or valine impairs Aurora B activity during mitosis and causes chromosome segregation defects. This study reveals that Mps1 regulates the CPC through a novel Borealin domain.

The mitotic regulator Survivin binds as a monomer to its functional interactor Borealin.

Survivin is a member of the IAP (inhibitor of apoptosis) protein family, defined in part by the presence of a zinc-binding baculoviral inhibitory repeat (BIR) domain. Most BIR domains bind short sequences beginning with alanine, and in this manner, they recognize and block the action of key targets in apoptotic pathways. However, Survivin binds only very weakly to typical IAP ligands. Unique features of Survivin are the long C-terminal helix following the BIR domain and a short segment (linking the helix and BIR domains) that mediates Survivin homodimerization. Despite this detailed knowledge of the structure of Survivin itself, there is a current lack of understanding about how Survivin recognizes cellular binding partners, and consequently, many questions about Survivin function remain unanswered. We determined two co-crystal structures of Survivin and a minimal binding fragment from the chromosomal passenger protein Borealin, a well validated functional interactor. The interaction between Survivin and Borealin involves extensive packing between the long C-terminal helix of Survivin and a long Borealin helix. Surprisingly, an additional important interaction occurs between the Survivin homodimerization interface and a short segment of Borealin. This segment both structurally mimics and displaces one Survivin monomer. The relevance of this unexpected interaction was tested by mutagenesis of two key Borealin residues. Mutant Borealin introduced into HeLa cells failed to localize properly during mitosis and also caused mislocalization of other chromosomal passenger proteins. This suggests that the mutant is dominant-negative and confirms the functional importance of the interaction surface identified in the crystal structures.

ORMOSIL thin films: tuning mechanical properties via a nanochemistry approach.

The mechanical properties (hardness and elastic modulus) of organically modified silicate thin films can be finely tuned by varying the degree of alkylation and thus the fraction of six- and four-membered siloxane rings in the organosilica matrix. This opens the way to large tunability of parameters that are of crucial practical importance for films that are finding increasing application in numerous fields ranging from microelectronics to chemical sensing.

Fabrication and characterization of fluorescent rare-earth-doped glass-particle-based tips for near-field optical imaging applications.

Fluorescent rare-earth-doped glass particles glued to the end of an atomic force microscope tip have been used to perform scanning near-field optical measurements on nanostructured samples. The fixation procedure of the fluorescent fragment at the end of the tip is described in detail. The procedure consists of depositing a thin adhesive layer on the tip. Then a tip approach is performed on a fragment that remains stuck near the tip extremity. To displace the particle and position it at the very end of the tip, a nanomanipulation is achieved by use of a second tip mounted on piezoelectric scanners. Afterward, the particle size is reduced by focused ion beam milling. These particles exhibit a strong green luminescence where excited in the near infrared by an upconversion mechanism. Images obtained near a metallic edge show a lateral resolution in the 180-200-nm range. Images we obtained by measuring the light scattered by 250-nm holes show a resolution well below 100 nm. This phenomenon can be explained by a local excitation of the particle and by the nonlinear nature of the excitation.