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International audience; Hard and strong transparent glass-ceramics (TGCs) can be used as cooktop plates, telescope mirrors, armor materials, and screens for smartphones and tablets. In this work, transparent glass-ceramics from the MgO-Al2O3-SiO2 (MAS) system were obtained after a refined heat-treatment protocol. The evolution in fracture toughness, KIC (Single Edge Precracked Beam), and Vickers hardness (H-V) were characterized as a function of the crystallization progress. The K-IC of the parent glass was 0.6 MPa m(1/2), whereas the TGC samples present values around 1.1 MPa m(1/2). The average glass hardness was 8.5 and PLUSMN; 0.8 GPa for loads of 0.6-5 N, whereas the H-V of the TGC samples varied from 9 to 10 GPa, for indentation loads ranging from 4.9 to 9.8 N. These results are discussed in light of our previous findings on the evolution of elastic modulus in the same glass-ceramics.

Made available in DSpace on 2022-04-28T19:47:44Z (GMT). No. of bitstreams: 0 Previous issue date: 2022-02-01 Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Ministerio de Ciencia, Innovación y Universidades Universitat Jaume I This work elucidates the morphology-photoluminescence (PL) emission relationships, based on experimental and calculated results, on β-Ag2MoO4 samples synthesized by microwave-assisted hydrothermal method. It was shown that the solvent (water and ammonia) and temperature (120, 130, 140, and 150 °C) play a crucial role in the morphology and PL emissions. A crystal structure model, composed by the local coordination of both Ag and Mo atoms at bulk and exposed surfaces, was built, and the possible mechanism along the synthesis progress was proposed and analyzed. This study provides an idea for the preparation and development of β-Ag2MoO4 based materials with desirable properties. CDMF Federal University of São Carlos, P.O. Box 676 Institute of Chemistry State University of Campinas, Campinas Universidade Estadual Paulista Laboratório Interdisciplinary de Eletroquímica e Cerâmica Department of Physics Federal University of São Carlos, P.O. Box 676 Department of Analytical and Physical Chemistry University Jaume I Brazilian Nanotechnology National Laboratory (LNNano)/CNPEM, Campinas Universidade Estadual Paulista Laboratório Interdisciplinary de Eletroquímica e Cerâmica CAPES: 001 CNPq: 142035/2017-3 FAPESP: 2013/07296-2 FAPESP: 2016/23891-6 FAPESP: 2017/26105-4 FAPESP: 2019/01732-1 CNPq: 305792/2020-2 Ministerio de Ciencia, Innovación y Universidades: PGC2018-094417-B-I00 Universitat Jaume I: UJI-B2019-30

CdTe/CdS core/shell quantum dots (QDs) are formed in aqueous synthesis via the partial decomposition of hydrophilic thiols, used as surface ligands. In this work, we investigate the influence of the chemical nature (functional group and chain length) of the used surface ligands on the shell formation. Four different surface ligands are compared: 3-mercaptopropionic acid, MPA, thioglycolic acid, TGA, sodium 3-mercaptopropanesulfonate, MPS, and sodium 2-mercaptoethanesulfonate, MES. The QD growth rate increases when the ligand aliphatic chain length decreases due to steric reasons. At the same time, the QDs stabilized with carboxylate ligands grow faster and achieve higher photoluminescence quantum yields compared to those containing sulfonate ligands. The average PL lifetime of TGA and MPA capped QDs is similar (≈20 ns) while in the case of MPS shorter (≈15 ns) and for MES significantly longer (≈30 ns) values are measured. A detailed structural analysis combining powder X-ray diffraction, and X-ray photoelectron spectroscopy (XPS) indicates the existence of two novel regimes of band alignment: in the case of the mercaptocarboxylate ligands the classic type I band alignment between the core and shell materials is predominant, while the mercaptosulfonate ligands induce a quasi-type II alignment (MES) or an inverted type I alignment (MPS). Finally, the effect of the pH value on the optical properties was evaluated: using a ligand excess in solution allows achieving better stability of the QDs while maintaining high photoluminescence intensity at low pH.

A facile hydrothermal method to synthesize water-soluble copper indium sulfide (CIS) nanocrystals (NCs) at 150 &deg, C is presented. The obtained samples exhibited three distinct photoluminescence peaks in the red, green and blue spectral regions, corresponding to three size fractions, which could be separated by means of size-selective precipitation. While the red and green emitting fractions consist of 4.5 and 2.5 nm CIS NCs, the blue fraction was identified as in situ formed carbon nanodots showing excitation wavelength dependent emission. When used as light absorbers in quantum dot sensitized solar cells, the individual green and red fractions yielded power conversion efficiencies of 2.9% and 2.6%, respectively. With the unfractionated samples, the efficiency values approaching 5% were obtained. This improvement was mainly due to a significantly enhanced photocurrent arising from complementary panchromatic absorption.

Novel magnetic metals and metal oxides that use both the spin and charge of an electron offer exciting technological applications. Their discovery could boost research on functional nanoscale materials. Here, for the first time, we report the magnetization of α-Ag2WO4 under electron beam and femtosecond laser irradiation. The formation and growth of silver oxides (AgO, Ag2O, and Ag3O4) and Ag nanofilaments can be observed on the surface of α-Ag2WO4 crystals. These features were also present in the composition of an extruded material and could open new avenues for surface magnetism studies. In order to understand these results, we used first-principles density functional theory calculations. This allowed us to investigate several potential scenarios for controlling magnetic properties. The effect of electron addition on the crystalline structures of α-Ag2WO4, Ag3O4, Ag2O, and AgO has been analyzed in detail. The creation of Ag and O vacancies on these compounds was also analyzed. Based on structural and electronic changes at the local coordination site of Ag, a mechanism was proposed. The mechanism illustrates the processes responsible for the formation and growth of metallic Ag and the magnetic response to electron beam irradiation.

Dopant atoms can be incorporated into nanowires either via the vapor-liquid-solid mechanism through the catalyst droplet or by the vapor-solid growth on the sidewalls. Si is a typical n-type dopant for GaAs, but in nanowires it often suffers from a strongly amphoteric nature in the vapor-liquid-solid process. This issue can be avoided by using Te, which is a promising but less common alternative for n-type doping of GaAs nanowires. Here, we present a detailed investigation of Te-doped self-catalyzed GaAs nanowires. We use several complementary experimental techniques, such as atom probe tomography, off-axis electron holography, micro-Raman spectroscopy, and single-nanowire transport characterization, to assess the Te concentration, the free-electron concentration, and the built-in potential in Te-doped GaAs nanowires. By combing the experimental results with a theoretical model, we show that Te atoms are mainly incorporated by the vapor-liquid-solid process through the Ga droplet, which leads to both axial and radial dopant gradients due to Te diffusion inside the nanowires and competition between axial elongation and radial growth of nanowires. Furthermore, by comparing the free-electron concentration from Raman spectroscopy and the Te-atom concentrations from atom probe tomography, we show that the activation of Te donor atoms is 100% at a doping level of 4×1018cm-3, which is a significant result in terms of future device applications. acceptedVersion

In this work, we have synthesized CdTe quantum dots (QDs) dispersed in an aqueous medium at ambient temperature, and investigated their optical properties. Synthesis of CdTe QDs in the presence of simple amines removed the need for an additional energy source and inert atmosphere, in a simple and inexpensive experimental setup. The use of ammonia or hydrazine promoted nanoparticle growth by kinetic nanocrystal agglomeration in the initial growth stage. These weak electrolytes acted in the electrical double layer during the growth of the nanocrystals. A comparative study on the concentration of hydrazine in the reaction medium helped to investigate their role in nanocrystal growth. Substitution of hydrazine for ethylenediamine and other electrolytes like sodium chloride and ammonium chloride contributed to a better understanding of the mechanism that underlies the use of primary amines in the synthesis of CdTe. The synthesis conditions afforded the highest photoluminescence quantum yield for CdTe QDs prepared at room temperature (27.5%).

On the basis of tissue-specific enzyme activity and inhibition by catalytic products, Hans Krebs first demonstrated the existence of multiple glutaminases in mammals. Currently, two human genes are known to encode at least four glutaminase isoforms. However, the phylogeny of these medically relevant enzymes remains unclear, prompting us to investigate their origin and evolution. Using prokaryotic and eukaryotic glutaminase sequences, we built a phylogenetic tree whose topology suggested that the multidomain architecture was inherited from bacterial ancestors, probably simultaneously with the hosting of the proto-mitochondrion endosymbiont. We propose an evolutionary model wherein the appearance of the most active enzyme isoform, glutaminase C (GAC), which is expressed in many cancers, was a late retrotransposition event that occurred in fishes from the Chondrichthyes class. The ankyrin (ANK) repeats in the glutaminases were acquired early in their evolution. To obtain information on ANK folding, we solved two high-resolution structures of the ANK repeat-containing C-termini of both kidney-type glutaminase (KGA) and GLS2 isoforms (glutaminase B and liver-type glutaminase). We found that the glutaminase ANK repeats form unique intramolecular contacts through two highly conserved motifs; curiously, this arrangement occludes a region usually involved in ANK-mediated protein-protein interactions. We also solved the crystal structure of full-length KGA and present a small-angle X-ray scattering model for full-length GLS2. These structures explain these proteins' compromised ability to assemble into catalytically active supra-tetrameric filaments, as previously shown for GAC. Collectively, these results provide information about glutaminases that may aid in the design of isoform-specific glutaminase inhibitors.

Human hair has three main regions, the medulla, the cortex and the cuticle. An existing model for the cortex suggests that the α-keratin- based intermediate filaments (IFs) align with the hair’s axis, but are orientationally disordered in-plane. We found that there is a new region in the cortex near the cuticle’s boundary in which the IFs are aligned with the hair’s axis, but additionally, they are orientationally ordered in-plane due to the presence of the cuticle/hair boundary. Further into the cortex, the IF arrangement becomes disordered, eventually losing all in-plane orientation. We also find that in the cuticle, a key diffraction feature is absent, indicating the presence of the β-keratin rather than that of the α-keratin phase. This is direct structural evidence that the cuticle contains β-keratin sheets. This work highlights the importance of using a sub-micron x-ray beam to unravel the structures of poorly ordered, multi-phase systems.

Rapid variations of the environmental energy caused by ultrashort laser pulses have induced phase transitions in carbon allotropes, therefore bringing the promise of revealing new carbon phases. Here, by exposing polycrystalline graphite to 25 fs laser pulses at 4 J/cm2 fluence under standard air atmosphere, we demonstrated the synthesis of translucent micrometer-sized structures carrying diamond-like and onion-like carbon phases. Texturized domains of the diamond phase were also identified. Concerning different synthesized carbon forms, pulse superposition and singularities of the thermodynamical process, we pinpoint the synthesis mechanism by the laser-induced subsequent products energetically evolving to attain the diamond-like phase.

We prepared very high-coercivity cobalt ferrite nanoparticles synthesized by a combustion method and using short-time high-energy mechanical milling to increase strain and the structural defects density. The coercivity (HC) of the milled sample reached 3.75 kOe—a value almost five times higher than that obtained for the non-milled material (0.76 kOe). To investigate the effect of the temperature on the magnetic behavior of the milled sample, we performed a thermal treatment on the milled sample at 300, 400, and 600 °C for 30 and 180 min. We analyzed the changes in the magnetic behavior of the nanoparticles due to the thermal treatment using the hysteresis curves, Williamson-Hall analysis, and transmission electron microscopy. The thermal treatment at 600 °C causes decreases in the microstructural strain and density of structural defects resulting in a significant decrease in HC. Furthermore, this thermal treatment increases the size of the nanoparticles and, as a consequence, there is a substantial increase in the saturation magnetization (MS). The HC of the samples treated at 600 °C for 30 and 180 min were 2.24 and 1.93 kOe, respectively, and the MS of these same samples increased from 57 emu/g to 66 and 70 emu/g, respectively. The HC and the MS are less affected by the thermal treatment at 300 and 400 °C.

The phosphate-dependent transition between enzymatically inert dimers into catalytically capable tetramers has long been the accepted mechanism for the glutaminase activation. Here, we demonstrate that activated glutaminase C (GAC) self-assembles into a helical, fiber-like double-stranded oligomer and propose a molecular model consisting of seven tetramer copies per turn per strand interacting via the N-terminal domains. The loop 321LRFNKL326 is projected as the major regulating element for self-assembly and enzyme activation. Furthermore, the previously identified in vivo lysine acetylation (Lys311 in humans, Lys316 in mouse) is here proposed as an important down-regulator of superoligomer assembly and protein activation. Bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl)ethyl sulfide, a known glutaminase inhibitor, completely disrupted the higher order oligomer, explaining its allosteric mechanism of inhibition via tetramer stabilization. A direct correlation between the tendency to self-assemble and the activity levels of the three mammalian glutaminase isozymes was established, with GAC being the most active enzyme while forming the longest structures. Lastly, the ectopic expression of a fiber-prone superactive GAC mutant in MDA-MB 231 cancer cells provided considerable proliferative advantages to transformed cells. These findings yield unique implications for the development of GAC-oriented therapeutics targeting tumor metabolism. Background: GAC supplies for increased metabolic needs of tumors because of exclusive localization and kinetic properties. Results: Higher than tetramer oligomers are the active form in in vitro and in cellular assays. Bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl)ethyl sulfide disrupts oligomers. Conclusion: A novel molecular mechanism for GAC activation is proposed. Significance: The data affect the development of therapies targeting GAC in tumors, with emphasis on allosteric inhibitors.

Cell division in bacteria is regulated by proteins that interact with FtsZ and modulate its ability to polymerize into the Z ring structure. The best studied of these regulators is MinC, an inhibitor of FtsZ polymerization that plays a crucial role in the spatial control of Z ring formation. Recent work established that E. coli MinC interacts with two regions of FtsZ, the bottom face of the H10 helix and the extreme C-terminal peptide (CTP). Here we determined the binding site for MinC on Bacillus subtilis FtsZ. Selection of a library of FtsZ mutants for survival in the presence of Min overexpression resulted in the isolation of 13 Min-resistant mutants. Most of the substitutions that gave rise to Min resistance clustered around the H9 and H10 helices in the C-terminal domain of FtsZ. In addition, a mutation in the CTP of B. subtilis FtsZ also produced MinC resistance. Biochemical characterization of some of the mutant proteins showed that they exhibited normal polymerization properties but reduced interaction with MinC, as expected for binding site mutations. Thus, our study shows that the overall architecture of the MinC-FtsZ interaction is conserved in E. coli and B. subtilis. Nevertheless, there was a clear difference in the mutations that conferred Min resistance, with those in B. subtilis FtsZ pointing to the side of the molecule rather than to its polymerization interface. This observation suggests that the mechanism of Z ring inhibition by MinC differs in both species.

Submitted by Guilherme Lemeszenski (guilherme@nead.unesp.br) on 2013-08-22T19:01:22Z No. of bitstreams: 1 S0103-97332004000400022.pdf: 163059 bytes, checksum: cd009132f334dd2586e6a14554357af3 (MD5) Made available in DSpace on 2013-08-22T19:01:22Z (GMT). No. of bitstreams: 1 S0103-97332004000400022.pdf: 163059 bytes, checksum: cd009132f334dd2586e6a14554357af3 (MD5) Previous issue date: 2004-06-01 Made available in DSpace on 2013-09-30T20:01:20Z (GMT). No. of bitstreams: 2 S0103-97332004000400022.pdf: 163059 bytes, checksum: cd009132f334dd2586e6a14554357af3 (MD5) S0103-97332004000400022.pdf.txt: 13097 bytes, checksum: 41e6751a54fdae567496162132c6b3bb (MD5) Previous issue date: 2004-06-01 Submitted by Vitor Silverio Rodrigues (vitorsrodrigues@reitoria.unesp.br) on 2014-05-20T15:15:41Z No. of bitstreams: 2 S0103-97332004000400022.pdf: 163059 bytes, checksum: cd009132f334dd2586e6a14554357af3 (MD5) S0103-97332004000400022.pdf.txt: 13097 bytes, checksum: 41e6751a54fdae567496162132c6b3bb (MD5) Made available in DSpace on 2014-05-20T15:15:41Z (GMT). No. of bitstreams: 2 S0103-97332004000400022.pdf: 163059 bytes, checksum: cd009132f334dd2586e6a14554357af3 (MD5) S0103-97332004000400022.pdf.txt: 13097 bytes, checksum: 41e6751a54fdae567496162132c6b3bb (MD5) Previous issue date: 2004-06-01 Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Fundação para o Desenvolvimento da UNESP (FUNDUNESP) In this work we investigated the optical and structural properties of GaAs/GaInP quantum wells (QW) grown by Chemical Beam Epitaxy (CBE). The samples were characterized by photoluminescence (PL), photoluminescence excitation (PLE) and transmission electron microscopy (TEM). Simulations of the quantum well potential profiles, using the Van de Walle-Martin model, supplemented by our experimental results, allowed us to associate the interface properties with the growth procedures. We concluded that a thin GaP layer grown at the interface improves its quality and also that the observed broad emission band in the PL spectrum is related to quaternary Ga1-xIn xAs1-yPy. Universidade Estadual Paulista - UNESP Departamento de Física UNICAMP Instituto de Física Gleb Wathagin Laboratório Nacional de Luz Sincroton - LNLS Universidade Estadual Paulista - UNESP Departamento de Física

The exploitation of the spin in charge-based systems is opening revolutionary opportunities for device architecture. Surprisingly, room temperature electrical transport through magnetic nanowires is still an unresolved issue. Here, we show that ferromagnetic (Co) suspended atom chains spontaneously display an electron transport of half a conductance quantum, as expected for a fully polarized conduction channel. Similar behavior has been observed for Pd (a quasi-magnetic 4d metal) and Pt (a non-magnetic 5d metal). These results suggest that the nanowire low dimensionality reinforces or induces magnetic behavior, lifting off spin degeneracy even at room temperature and zero external magnetic field., 4 pages, 3 eps figs

Formation of electrical isolation in n- and p-type In0.49Ga0.51P epitaxial layers grown on semi-insulating GaAs substrates was investigated using proton or helium ion irradiation. Sheet resistance increases with the irradiation dose, reaching a saturation level of ≈109 Ω/□. The results show that the threshold dose necessary for complete isolation linearly depends on the original carrier concentration either in p- or n-type doped InGaP layers. Thermal stability of the isolation during postirradiation annealing was found to increase with accumulation of the ion dose. The maximum temperature at which the isolation persists is ≅500 °C.

In bacteria selenocysteyl-tRNA(sec) (SelC) is synthesized by selenocysteine synthase (SelA). Here we show by fluorescence anisotropy binding assays and electron microscopical symmetry analysis that the SelA-tRNA(sec) binding stoichiometry is of one tRNA(sec) molecule per SelA monomer (1:1) rather than the 1:2 value proposed previously. Negative stain transmission electron microscopy revealed a D5 pointgroup symmetry for the SelA-tRNA(sec) assembly both with and without tRNA(sec) bound. Furthermore, SelA can associate forming a supramolecular complex of stacked decamer rings, which does not occur in the presence of tRNA(sec). We discuss the structure-function relationships of these assemblies and their regulatory role in bacterial selenocysteyl-tRNA(sec) synthesis.