Unveiling the Cation Exchange Reaction between the NASICON Li1.5Al0.5Ge1.5(PO4)3 Solid Electrolyte and the pyr13TFSI Ionic Liquid.

Recently, the formation of the ceramic-ionic liquid composite has attracted huge interest in the scientific community. In this work, we investigated the chemical reactions occurring between NASICON LAGP ceramic electrolyte and ionic liquid pyr13TFSI. This study allowed us to identify the cation exchange reaction pyr13-Li occurring on the LAGP surface, forming a LiTFSI salt that was detected by the nuclear magnetic resonance analysis. In addition, using 6Li foils, we succeeded in demonstrating that both LAGP and LiTFSI:pyr13TFSI participate in the diffusion of Li ions by the formation of an ionic bridge between two species.

3d Metal Doping of Core@Shell Wüstite@ferrite Nanoparticles as a Promising Route toward Room Temperature Exchange Bias Magnets.

Nanometric core@shell wüstite@ferrite (Fe1-x O@Fe3 O4 ) has been extensively studied because of the emergence of exchange bias phenomena. Since their actual implementation in modern technologies is hampered by the low temperature at which bias is operating, the critical issue to be solved is to obtain exchange-coupled antiferromagnetic@ferrimagnetic nanoparticles (NPs) with ordering temperature close to 300 K by replacing the divalent iron with other transition-metal ions. Here, the effect of the combined substitution of Fe(II)  with Co(II)  and Ni(II)  on the crystal structure and magnetic properties is studied. To this aim, a series of 20 nm NPs with a wüstite-based core and a ferrite shell, with tailored composition, (Co0.3 Fe0.7 O@Co0.8 Fe2.2 O4  and Ni0.17 Co0.21 Fe0.62 O@Ni0.4 Co0.3 Fe2.3 O4 ) is synthetized through a thermal-decomposition method. An extensive morphological and crystallographic characterization of the obtained NPs shows how a higher stability against the oxidation process in ambient condition is attained when divalent cation doping of the iron oxide lattice with Co(II)  and Ni(II)  ions is performed. The dual-doping is revealed to be an efficient way for tuning the magnetic properties of the final system, obtaining Ni-Co doped iron oxide core@shell NPs with high coercivity (and therefore, high energy product), and increased antiferromagnetic ordering transition temperature, close to room temperature.

Optical and electronic properties of silver nanoparticles embedded in cerium oxide.

Wide bandgap oxides can be sensitized to visible light by coupling them with plasmonic nanoparticles (NPs). We investigate the optical and electronic properties of composite materials made of Ag NPs embedded within cerium oxide layers of different thickness. The electronic properties of the materials are investigated by x-ray and ultraviolet photoemission spectroscopy, which demonstrates the occurrence of static charge transfers between the metal and the oxide and its dependence on the NP size. Ultraviolet-visible spectrophotometry measurements show that the materials have a strong absorption in the visible range induced by the excitation of localized surface plasmon resonances. The plasmonic absorption band can be modified in shape and intensity by changing the NP aspect ratio and density and the thickness of the cerium oxide film.

Structural and functional characterization of TgpA, a critical protein for the viability of Pseudomonas aeruginosa.

Pseudomonas aeruginosa is an opportunistic pathogen associated with severe diseases, such as cystic fibrosis. During an extensive search for novel essential genes, we identified tgpA (locus PA2873) in P. aeruginosa PAO1, as a gene playing a critical role in bacterial viability. TgpA, the translated protein, is an internal membrane protein with a periplasmic soluble domain, predicted to be endowed with a transglutaminase-like fold, hosting the Cys404, His448, and Asp464 triad. We report here that Cys404 mutation hampers the essential role of TgpA in granting P. aeruginosa viability. Moreover, we present the crystal structure of the TgpA periplasmic domain at 1.6 Šresolution as a first step towards structure-activity analysis of a new potential target for the discovery of antibacterial compounds.

Magnetic Shape Memory Turns to Nano: Microstructure Controlled Actuation of Free-Standing Nanodisks.

Magnetic shape memory materials hold a great promise for next-generation actuation devices and systems for energy conversion, thanks to the intimate coupling between structure and magnetism in their martensitic phase. Here novel magnetic shape memory free-standing nanodisks are proposed, proving that the lack of the substrate constrains enables the exploitation of new microstructure-controlled actuation mechanisms by the combined application of different stimuli-i.e., temperature and magnetic field. The results show that a reversible areal strain (up to 5.5%) can be achieved and tuned in intensity and sign (i.e., areal contraction or expansion) by the application of a magnetic field. The mechanisms at the basis of the actuation are investigated by experiments performed at different length scales and directly visualized by several electron microscopy techniques, including electron holography, showing that thermo/magnetomechanical properties can be optimized by engineering the martensitic microstructure through epitaxial growth and lateral confinement. These findings represent a step forward toward the development of a new class of temperature-field controlled nanoactuators and smart nanomaterials.

Ab Initio Structure Determination of Cu2- xTe Plasmonic Nanocrystals by Precession-Assisted Electron Diffraction Tomography and HAADF-STEM Imaging.

We investigated pseudo-cubic Cu2- xTe nanosheets using electron diffraction tomography and high-resolution HAADF-STEM imaging. The structure of this metastable nanomaterial, which has a strong localized surface plasmon resonance in the near-infrared region, was determined ab initio by 3D electron diffraction data recorded in low-dose nanobeam precession mode, using a new generation background-free single-electron detector. The presence of two different, crystallographically defined modulations creates a 3D connected vacancy channel system, which may account for the strong plasmonic response of this material. Moreover, a pervasive rotational twinning is observed for nanosheets as thin as 40 nm, resulting in a tetragonal pseudo-symmetry.

Role of the Crystal Structure in Cation Exchange Reactions Involving Colloidal Cu2Se Nanocrystals.

Stoichiometric Cu2Se nanocrystals were synthesized in either cubic or hexagonal (metastable) crystal structures and used as the host material in cation exchange reactions with Pb2+ ions. Even if the final product of the exchange, in both cases, was rock-salt PbSe nanocrystals, we show here that the crystal structure of the starting nanocrystals has a strong influence on the exchange pathway. The exposure of cubic Cu2Se nanocrystals to Pb2+ cations led to the initial formation of PbSe unselectively on the overall surface of the host nanocrystals, generating Cu2Se@PbSe core@shell nanoheterostructures. The formation of such intermediates was attributed to the low diffusivity of Pb2+ ions inside the host lattice and to the absence of preferred entry points in cubic Cu2Se. On the other hand, in hexagonal Cu2Se nanocrystals, the entrance of Pb2+ ions generated PbSe stripes "sandwiched" in between hexagonal Cu2Se domains. These peculiar heterostructures formed as a consequence of the preferential diffusion of Pb2+ ions through specific (a, b) planes of the hexagonal Cu2Se structure, which are characterized by almost empty octahedral sites. Our findings suggest that the morphology of the nanoheterostructures, formed upon partial cation exchange reactions, is intimately connected not only to the NC host material, but also to its crystal structure.

Colloidal Monolayer ß-In2Se3 Nanosheets with High Photoresponsivity.

We report a low-temperature colloidal synthesis of single-layer, five-atom-thick, ß-In2Se3 nanosheets with lateral sizes tunable from ∼300 to ∼900 nm, using short aminonitriles (dicyandiamide or cyanamide) as shape controlling agents. The phase and the monolayer nature of the nanosheets were ascertained by analyzing the intensity ratio between two diffraction peaks from two-dimensional slabs of the various phases, determined by diffraction simulations. These findings were further backed-up by comparing and fitting the experimental X-ray diffraction pattern with Debye formula simulated patterns and with side-view high-resolution transmission electron microscopy imaging and simulation. The ß-In2Se3 nanosheets were found to be indirect band gap semiconductors (Eg = 1.55 eV), and single nanosheet photodetectors demonstrated high photoresponsivity and fast response times.

The small RNA ReaL: a novel regulatory element embedded in the Pseudomonas aeruginosa quorum sensing networks.

The small RNA ReaL of the opportunistic pathogen Pseudomonas aeruginosa has been characterized. Our results indicate that ReaL contributes to P. aeruginosa virulence. In the Galleria mellonella infection model, reaL gene deletion resulted in decreased virulence, while ReaL overexpression resulted in a hyper-virulent phenotype. We also demonstrate that ReaL is embedded in the P. aeruginosa quorum sensing (QS) with the role of linking las to pqs systems. We show that ReaL is negatively regulated by the las regulator LasR and impacts positively the synthesis of the pqs quinolone signal PQS by a positive post-transcriptional effect on the pqsC gene. Perturbations of ReaL levels affect pyocyanin synthesis, biofilm formation and swarming motility, processes that are known to be influenced by PQS synthesis. In addition to being regulated by LasR, ReaL is also responding to infection relevant cues that P. aeruginosa can experience in mammalian hosts such as temperature and oxygen availability. Furthermore, ReaL shows a growth phase-dependent pattern of expression, being up-regulated in stationary phase, due to the activity of the alternative σ factor RpoS. Together, these regulations of ReaL expression are expected to contribute to the fine co-modulation of PQS synthesis and, ultimately, virulence.

Contraction, cation oxidation state and size effects in cerium oxide nanoparticles.

An accurate description of the structural and chemical modifications of cerium oxide nanoparticles (NPs) is mandatory for understanding their functionality in applications. In this work we investigate the relation between local atomic structure, oxidation state, defectivity and size in cerium oxide NPs with variable diameter below 10 nm, using x-ray absorption fine structure analysis in the near and extended energy range. The NPs are prepared by physical methods under controlled conditions and analyzed in morphology and crystalline quality by high resolution transmission electron microscopy. We resolve here an important question on the local structure of cerium oxide NPs: we demonstrate a progressive contraction in the Ce-O interatomic distance with decreasing NP diameter and we relate the observed effect to the reduced dimensionality. The contraction is not significantly modified by inducing a 4%-6% higher Ce3+ concentration through thermal annealing in high vacuum. The consequences of the observed average cation-anion distance contraction on the properties of the NPs are discussed.

Accelerated Removal of Fe-Antisite Defects while Nanosizing Hydrothermal LiFePO4 with Ca(2).

Based on neutron powder diffraction (NPD) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM), we show that calcium ions help eliminate the Fe-antisite defects by controlling the nucleation and evolution of the LiFePO4 particles during their hydrothermal synthesis. This Ca-regulated formation of LiFePO4 particles has an overwhelming impact on the removal of their iron antisite defects during the subsequent carbon-coating step since (i) almost all the Fe-antisite defects aggregate at the surface of the LiFePO4 crystal when the crystals are small enough and (ii) the concomitant increase of the surface area, which further exposes the Fe-antisite defects. Our results not only justify a low-cost, efficient and reliable hydrothermal synthesis method for LiFePO4 but also provide a promising alternative viewpoint on the mechanism controlling the nanosizing of LiFePO4, which leads to improved electrochemical performances.

Influence of the Ion Coordination Number on Cation Exchange Reactions with Copper Telluride Nanocrystals.

Cu2-xTe nanocubes were used as starting seeds to access metal telluride nanocrystals by cation exchanges at room temperature. The coordination number of the entering cations was found to play an important role in dictating the reaction pathways. The exchanges with tetrahedrally coordinated cations (i.e., with coordination number 4), such as Cd(2+) or Hg(2+), yielded monocrystalline CdTe or HgTe nanocrystals with Cu2-xTe/CdTe or Cu2-xTe/HgTe Janus-like heterostructures as intermediates. The formation of Janus-like architectures was attributed to the high diffusion rate of the relatively small tetrahedrally coordinated cations, which could rapidly diffuse in the Cu2-xTe NCs and nucleate the CdTe (or HgTe) phase in a preferred region of the host structure. Also, with both Cd(2+) and Hg(2+) ions the exchange led to wurtzite CdTe and HgTe phases rather than the more stable zinc-blende ones, indicating that the anion framework of the starting Cu2-xTe particles could be more easily deformed to match the anion framework of the metastable wurtzite structures. As hexagonal HgTe had never been reported to date, this represents another case of metastable new phases that can only be accessed by cation exchange. On the other hand, the exchanges involving octahedrally coordinated ions (i.e., with coordination number 6), such as Pb(2+) or Sn(2+), yielded rock-salt polycrystalline PbTe or SnTe nanocrystals with Cu2-xTe@PbTe or Cu2-xTe@SnTe core@shell architectures at the early stages of the exchange process. In this case, the octahedrally coordinated ions are probably too large to diffuse easily through the Cu2-xTe structure: their limited diffusion rate restricts their initial reaction to the surface of the nanocrystals, where cation exchange is initiated unselectively, leading to core@shell architectures. Interestingly, these heterostructures were found to be metastable as they evolved to stable Janus-like architectures if annealed at 200 °C under vacuum.

Solution Synthesis Approach to Colloidal Cesium Lead Halide Perovskite Nanoplatelets with Monolayer-Level Thickness Control.

We report a colloidal synthesis approach to CsPbBr3 nanoplatelets (NPLs). The nucleation and growth of the platelets, which takes place at room temperature, is triggered by the injection of acetone in a mixture of precursors that would remain unreactive otherwise. The low growth temperature enables the control of the plate thickness, which can be precisely tuned from 3 to 5 monolayers. The strong two-dimensional confinement of the carriers at such small vertical sizes is responsible for a narrow PL, strong excitonic absorption, and a blue shift of the optical band gap by more than 0.47 eV compared to that of bulk CsPbBr3. We also show that the composition of the NPLs can be varied all the way to CsPbBr3 or CsPbI3 by anion exchange, with preservation of the size and shape of the starting particles. The blue fluorescent CsPbCl3 NPLs represent a new member of the scarcely populated group of blue-emitting colloidal nanocrystals. The exciton dynamics were found to be independent of the extent of 2D confinement in these platelets, and this was supported by band structure calculations.

Crystal structure of YeaZ from Pseudomonas aeruginosa.

The Pseudomonas aeruginosa PA3685 locus encodes a conserved protein that shares 49% sequence identity with Escherichia coli YeaZ, which was recently reported as involved in the biosynthesis of threonylcarbamoyl adenosine (t(6)A), a universal modified tRNA nucleoside. Many YeaZ orthologues were reported as "essential for life" among various bacterial species, suggesting a critical role for both these proteins and for the t(6)A biosynthetic pathway. We provide here evidences that PA3685 protein (PaYeaZ) is essential. Additionally, we describe its purification, crystallization, and crystallographic structure. The crystal structure shows that PaYeaZ is composed of two domains one of which is the platform to form protein-protein interaction involved either in homodimeric assembly or in the formation of the multiprotein complex required for the synthesis of t(6)A. These features make the PaYeaZ protein a potential target candidate for the design of novel inhibitors able to hinder the complex formation and expected to abolish the crucial activity of t(6)A synthesis.

Tet-Trap, a genetic approach to the identification of bacterial RNA thermometers: application to Pseudomonas aeruginosa.

Modulation of mRNA translatability either by trans-acting factors (proteins or sRNAs) or by in cis-acting riboregulators is widespread in bacteria and controls relevant phenotypic traits. Unfortunately, global identification of post-transcriptionally regulated genes is complicated by poor structural and functional conservation of regulatory elements and by the limitations of proteomic approaches in protein quantification. We devised a genetic system for the identification of post-transcriptionally regulated genes and we applied this system to search for Pseudomonas aeruginosa RNA thermometers, a class of regulatory RNA that modulates gene translation in response to temperature changes. As P. aeruginosa is able to thrive in a broad range of environmental conditions, genes differentially expressed at 37 °C versus lower temperatures may be involved in infection and survival in the human host. We prepared a plasmid vector library with translational fusions of P. aeruginosa DNA fragments (PaDNA) inserted upstream of TIP2, a short peptide able to inactivate the Tet repressor (TetR) upon expression. The library was assayed in a streptomycin-resistant merodiploid rpsL(+)/rpsL31 Escherichia coli strain in which the dominant rpsL(+) allele, which confers streptomycin sensitivity, was repressed by TetR. PaDNA fragments conferring thermosensitive streptomycin resistance (i.e., expressing PaDNA-TIP2 fusions at 37°C, but not at 28°C) were sequenced. We identified four new putative thermosensors. Two of them were validated with conventional reporter systems in E. coli and P. aeruginosa. Interestingly, one regulates the expression of ptxS, a gene implicated in P. aeruginosa pathogenesis.

Influence of defect distribution on the reducibility of CeO2-x nanoparticles.

Ceria nanoparticles (NPs) are fundamental in heterogeneous catalysis because of their ability to store or release oxygen depending on the ambient conditions. Their oxygen storage capacity is strictly related to the exposed planes, crystallinity, density and distribution of defects. In this work a study of ceria NPs produced with a ligand-free, physical synthesis method is presented. The NP films were grown by a magnetron sputtering based gas aggregation source and studied by high resolution- and scanning-transmission electron microscopy and x-ray photoelectron spectroscopy. In particular, the influence of the oxidation procedure on the NP reducibility has been investigated. The different reducibility has been correlated to the exposed planes, crystallinity and density and distribution of structural defects. The results obtained in this work represent a basis to obtain cerium oxide NP with desired oxygen transport properties.

Post-transcriptional regulation of the virulence-associated enzyme AlgC by the σ(22) -dependent small RNA ErsA of Pseudomonas aeruginosa.

The small RNA ErsA of Pseudomonas aeruginosa, transcribed from the same genomic context of the well-known Escherichia coli Spot 42, has been characterized. We show that, different from Spot 42, ErsA is under the transcriptional control of the envelope stress response, which is known to impact the pathogenesis of P. aeruginosa through the activity of the alternative sigma factor σ(22) . The transcriptional responsiveness of ErsA RNA also spans infection-relevant cues that P. aeruginosa can experience in mammalian hosts, such as limited iron availability, temperature shifts from environmental to body temperature and reduced oxygen conditions. Another difference between Spot 42 and ErsA is that ErsA does not seem to be involved in the regulation of carbon source catabolism. Instead, our results suggest that ErsA is linked to anabolic functions for the synthesis of exoproducts from sugar precursors. We show that ErsA directly operates in the negative post-transcriptional regulation of the algC gene that encodes the virulence-associated enzyme AlgC, which provides sugar precursors for the synthesis of several P. aeruginosa polysaccharides. Like ErsA, the activation of algC expression is also dependent on σ(22) . Altogether, our results suggest that ErsA and σ(22) combine in an incoherent feed-forward loop to fine-tune AlgC enzyme expression.

Redox centers evolution in phospho-olivine type (LiFe0.5Mn0.5 PO4) nanoplatelets with uniform cation distribution.

In phospho-olivine type structures with mixed cations (LiM1M2PO4), the octahedral M1 and M2 sites that dictate the degree of intersites order/disorder play a key role in determining their electrochemical redox potentials. In the case of LiFexMn1-xPO4, for example, in micrometer-sized particles synthesized via hydrothermal route, two separate redox centers corresponding to Fe(2+)/Fe(3+) (3.5 V vs Li/Li(+)) and Mn(2+)/Mn(3+) (4.1 V vs Li/Li(+)), due to the collective Mn-O-Fe interactions in the olivine lattice, are commonly observed in the electrochemical measurements. These two redox processes are directly reflected as two distinct peak potentials in cyclic voltammetry (CV) and equivalently as two voltage plateaus in their standard charge/discharge characteristics (in Li ion batteries). On the contrary, we observed a single broad peak in CV from LiFe0.5Mn0.5PO4 platelet-shaped (∼10 nm thick) nanocrystals that we are reporting in this work. Structural and compositional analysis showed that in these nanoplatelets the cations (Fe, Mn) are rather homogeneously distributed in the lattice, which is apparently the reason for a synergetic effect on the redox potentials, in contrast to LiFe0.5Mn0.5PO4 samples obtained via hydrothermal routes. After a typical carbon-coating process in a reducing atmosphere (Ar/H2), these LiFe0.5Mn0.5PO4 nanoplatelets undergo a rearrangement of their cations into Mn-rich and Fe-rich domains. Only after such cation rearrangement (via segregation) in the nanocrystals, the redox processes evolved at two distinct potentials, corresponding to the standard Fe(2+)/Fe(3+) and Mn(2+)/Mn(3+) redox centers. Our experimental findings provide new insight into mixed-cation olivine structures in which the degree of cations mixing in the olivine lattice directly influences the redox potentials, which in turn determine their charge/discharge characteristics.

Etched colloidal LiFePO4 nanoplatelets toward high-rate capable Li-ion battery electrodes.

LiFePO4 has been intensively investigated as a cathode material in Li-ion batteries, as it can in principle enable the development of high power electrodes. LiFePO4, on the other hand, is inherently "plagued" by poor electronic and ionic conductivity. While the problems with low electron conductivity are partially solved by carbon coating and further by doping or by downsizing the active particles to nanoscale dimensions, poor ionic conductivity is still an issue. To develop colloidally synthesized LiFePO4 nanocrystals (NCs) optimized for high rate applications, we propose here a surface treatment of the NCs. The particles as delivered from the synthesis have a surface passivated with long chain organic surfactants, and therefore can be dispersed only in aprotic solvents such as chloroform or toluene. Glucose that is commonly used as carbon source for carbon-coating procedure is not soluble in these solvents, but it can be dissolved in water. In order to make the NCs hydrophilic, we treated them with lithium hexafluorophosphate (LiPF6), which removes the surfactant ligand shell while preserving the structural and morphological properties of the NCs. Only a roughening of the edges of NCs was observed due to a partial etching of their surface. Electrodes prepared from these platelet NCs (after carbon coating) delivered a capacity of ∼ 155 mAh/g, ∼ 135 mAh/g, and ∼ 125 mAh/g, at 1 C, 5 C, and 10 C, respectively, with significant capacity retention and remarkable rate capability. For example, at 61 C (10.3 A/g), a capacity of ∼ 70 mAh/g was obtained, and at 122 C (20.7 A/g), the capacity was ∼ 30 mAh/g. The rate capability and the ease of scalability in the preparation of these surface-treated nanoplatelets make them highly suitable as electrodes in Li-ion batteries.

Hollow and concave nanoparticles via preferential oxidation of the core in colloidal core/shell nanocrystals.

Hollow and concave nanocrystals find applications in many fields, and their fabrication can follow different possible mechanisms. We report a new route to these nanostructures that exploits the oxidation of Cu(2-x)Se/Cu(2-x)S core/shell nanocrystals with various etchants. Even though the Cu(2-x)Se core is encased in a thick Cu(2-x)S shell, the initial effect of oxidation is the creation of a void in the core. This is rationalized in terms of diffusion of Cu(+) ions and electrons from the core to the shell (and from there to the solution). Differently from the classical Kirkendall effect, which entails an imbalance between in-diffusion and out-diffusion of two different species across an interface, the present mechanism can be considered as a limiting case of such effect and is triggered by the stronger tendency of Cu(2-x)Se over Cu(2-x)S toward oxidation and by fast Cu(+) diffusion in copper chalcogenides. As the oxidation progresses, expansion of the inner void erodes the entire Cu(2-x)Se core, accompanied by etching and partial collapse of the shell, yielding Cu(2-x)S(y)Se(1-y) concave particles.