Near-Atomic-Scale Mapping of Electronic Phases in Rare Earth Nickelate Superlattices.

Nanoscale mapping of the distinct electronic phases characterizing the metal-insulator transition displayed by most of the rare-earth nickelate compounds is fundamental for discovering the true nature of this transition and the possible couplings that are established at the interfaces of nickelate-based heterostructures. Here, we demonstrate that this can be accomplished by using scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. By tracking how the O K and Ni L edge fine structures evolve across two different NdNiO3/SmNiO3 superlattices, displaying either one or two metal-insulator transitions depending on the individual layer thickness, we are able to determine the electronic state of each of the individual constituent materials. We further map the spatial configuration associated with their metallic/insulating regions, reaching unit cell spatial resolution. With this, we estimate the width of the metallic/insulating boundaries at the NdNiO3/SmNiO3 interfaces, which is measured to be on the order of four unit cells.

Long-Term Calculation of Predicted Environmental Concentrations to Assess the Risk of Anticancer Drugs in Environmental Waters.

This study reports the consumption data for 132 anticancer drugs in Catalonia (NE Spain) during the period of 2013-2017 and calculates the predicted environmental concentrations (PECs) in wastewater effluents and rivers. This long-term analysis can determine the evolution of drugs present in the environment according to prescriptions and serve as an adequate tool to determine their presence and impact. Data showed that out of 132 compounds prescribed, 77 reached wastewater effluents, which accounted for the most consumed, those excreted in the highest doses, and the least biodegradable. Once diluted in receiving river waters, only mycophenolic acid and hydroxycarbamide had PEC values higher than 10 ng L-1, which is the value set by the European Medicines Agency (EMA) to carry out further risk assessment. It was also observed that compounds present in river water are those that can pose a high risk, given their persistence and capability to bioaccumulate. Therefore, this study shows that the estimation of PEC, together with physico-chemical properties of detected compounds, is a useful tool to determine the long-term presence and fate of this new class of emerging contaminants.

Length scales of interfacial coupling between metal and insulator phases in oxides.

Controlling phase transitions in transition metal oxides remains a central feature of both technological and fundamental scientific relevance. A well-known example is the metal-insulator transition, which has been shown to be highly controllable. However, the length scale over which these phases can be established is not yet well understood. To gain insight into this issue, we atomically engineered an artificially phase-separated system through fabricating epitaxial superlattices that consist of SmNiO3 and NdNiO3, two materials that undergo a metal-to-insulator transition at different temperatures. We demonstrate that the length scale of the interfacial coupling between metal and insulator phases is determined by balancing the energy cost of the boundary between a metal and an insulator and the bulk phase energies. Notably, we show that the length scale of this effect exceeds that of the physical coupling of structural motifs, which introduces a new framework for interface-engineering properties at temperatures against the bulk energetics.

CRP-cAMP mediates silencing of Salmonella virulence at the post-transcriptional level.

Invasion of epithelial cells by Salmonella enterica requires expression of genes located in the pathogenicity island I (SPI-1). The expression of SPI-1 genes is very tightly regulated and activated only under specific conditions. Most studies have focused on the regulatory pathways that induce SPI-1 expression. Here, we describe a new regulatory circuit involving CRP-cAMP, a widely established metabolic regulator, in silencing of SPI-1 genes under non-permissive conditions. In CRP-cAMP-deficient strains we detected a strong upregulation of SPI-1 genes in the mid-logarithmic growth phase. Genetic analyses revealed that CRP-cAMP modulates the level of HilD, the master regulator of Salmonella invasion. This regulation occurs at the post-transcriptional level and requires the presence of a newly identified regulatory motif within the hilD 3'UTR. We further demonstrate that in Salmonella the Hfq-dependent sRNA Spot 42 is under the transcriptional repression of CRP-cAMP and, when this transcriptional repression is relieved, Spot 42 exerts a positive effect on hilD expression. In vivo and in vitro assays indicate that Spot 42 targets, through its unstructured region III, the 3'UTR of the hilD transcript. Together, our results highlight the biological relevance of the hilD 3'UTR as a hub for post-transcriptional control of Salmonella invasion gene expression.

Nanoscale Correlations between Metal-Insulator Transition and Resistive Switching Effect in Metallic Perovskite Oxides.

Strongly correlated perovskite oxides are a class of materials with fascinating intrinsic physical functionalities due to the interplay of charge, spin, orbital ordering, and lattice degrees of freedom. Among the exotic phenomena arising from such an interplay, metal-insulator transitions (MITs) are fundamentally still not fully understood and are of large interest for novel nanoelectronics applications, such as resistive switching-based memories and neuromorphic computing devices. In particular, rare-earth nickelates and lanthanum strontium manganites are archetypical examples of bandwidth-controlled and band-filling-controlled MIT, respectively, which are used in this work as a playground to correlate the switching characteristics of the oxides and their MIT properties by means of local probe techniques in a systematic manner. These findings suggest that an electric-field-induced MIT can be triggered in these strongly correlated systems upon generation of oxygen vacancies and establish that lower operational voltages and larger resistance ratios are obtained in those films where the MIT lies closer to room temperature. This work demonstrates the potential of using MITs in the next generation of nanoelectronics devices.

Thickness-Dependent Perovskite Octahedral Distortions at Heterointerfaces.

In this study, we analyze how the octahedral tilts and rotations of thin films of LaNiO3 and LaAlO3 grown on different substrates, determined using synchrotron X-ray diffraction-measured half-integer Bragg peaks, depend upon the total film thickness. We find a striking difference between films grown on SrTiO3 and LaAlO3 substrates which appears to stem not only from the difference in epitaxial strain state but also from the level of continuity at the heterointerface. In particular, the chemically and structurally discontinuous LaNiO3/SrTiO3 and LaAlO3/SrTiO3 interfaces cause a large variation in the octahedral network as a function of film thickness whereas the rather continuous LaNiO3/LaAlO3 interface seems to allow from just a few unit cells the formation of a stable octahedral pattern corresponding to that expected only given the applied biaxial strain.

Growth phase-dependent control of R27 conjugation is mediated by the interplay between the plasmid-encoded regulatory circuit TrhR/TrhY-HtdA and the cAMP regulon.

Plasmids of the incompatibility group HI1 (IncHI1) have been isolated from several Gram-negative pathogens and are associated with the spread of multidrug resistance. Their conjugation is tightly regulated and it is inhibited at temperatures higher than 30°C, indicating that conjugation occurs outside warm-blooded hosts. Using R27, the prototype of IncHI1 plasmids, we report that plasmid transfer efficiency in E. coli strongly depends on the physiological state of the donor cells. Conjugation frequency is high when cells are actively growing, dropping sharply when cells enter the stationary phase of growth. Accordingly, our transcriptomic assays show significant downregulation of numerous R27 genes during the stationary phase, including several tra (transfer) genes. Growth phase-dependent regulation of tra genes transcription is independent of H-NS, a silencer of horizontal gene transfer, and ppGpp and RpoS, regulators of the stationary phase, but highly dependent on the plasmid-encoded regulatory circuit TrhR/TrhY-HtdA. The metabolic sensor cAMP, whose synthesis is chromosomally encoded, is also involved in the growth phase regulation of R27 conjugation by modulating htdA expression. Our data suggest that the involvement of regulators encoded by both chromosome and plasmid are required for efficient physiological control of IncHI1 plasmid conjugation.

Signatures of polarized chiral spin disproportionation in rare earth nickelates.

In rare earth nickelates (RENiO3), electron-lattice coupling drives a concurrent metal-to-insulator and bond disproportionation phase transition whose microscopic origin has long been the subject of active debate. Of several proposed mechanisms, here we test the hypothesis that pairs of self-doped ligand holes spatially condense to provide local spin moments that are antiferromagnetically coupled to Ni spins. These singlet-like states provide a basis for long-range bond and spiral spin order. Using magnetic resonant X-ray scattering on NdNiO3 thin films, we observe the chiral nature of the spin-disproportionated state, with spin spirals propagating along the crystallographic (101)ortho direction. These spin spirals are found to preferentially couple to X-ray helicity, establishing the presence of a hitherto-unobserved macroscopic chirality. The presence of this chiral magnetic configuration suggests a potential multiferroic coupling between the noncollinear magnetic arrangement and improper ferroelectric behavior as observed in prior studies on NdNiO3 (101)ortho films and RENiO3 single crystals. Experimentally-constrained theoretical double-cluster calculations confirm the presence of an energetically stable spin-disproportionated state with Zhang-Rice singlet-like combinations of Ni and ligand moments.

Exchange bias in LaNiO3-LaMnO3 superlattices.

The wide spectrum of exotic properties exhibited by transition-metal oxides stems from the complex competition between several quantum interactions. The capacity to select the emergence of specific phases at will is nowadays extensively recognized as key for the design of diverse new devices with tailored functionalities. In this context, interface engineering in complex oxide heterostructures has developed into a flourishing field, enabling not only further tuning of the exceptional properties of these materials, but also giving access to hidden phases and emergent physical phenomena. Here we demonstrate how interfacial interactions can induce a complex magnetic structure in a non-magnetic material. We specifically show that exchange bias can unexpectedly emerge in heterostructures consisting of paramagnetic LaNiO3 (LNO) and ferromagnetic LaMnO3 (LMO). The observation of exchange bias in (111)-oriented LNO-LMO superlattices, manifested as a shift of the magnetization-field loop, not only implies the development of interface-induced magnetism in the paramagnetic LNO layers, but also provides us with a very subtle tool for probing the interfacial coupling between the LNO and LMO layers. First-principles calculations indicate that this interfacial interaction may give rise to an unusual spin order, resembling a spin-density wave, within the LNO layers.

New insights in the role of HtdA in the regulation of R27 conjugation.

R27 is the prototype of the IncHI group of conjugative plasmids, which are associated with multidrug resistance in several relevant pathogens. The transfer of this plasmid is thermodependent and all transfer-related genes are encoded in six operons (tra operons). Very little is known about the factors involved in the regulation of the R27 conjugation. This report describes transcriptional studies of the six tra operons. Our results indicate that HtdA, encoded in the R27 plasmid, is involved in the transcriptional repression of four tra operons (F, H, AC and Z). Although HtdA plays a pivotal role in the transcriptional regulation of those operons, it does not exert its effect as a classical repressor. The data indicate the existence of a crosstalk between HtdA and other unknown regulatory factors. The HtdA-mediated regulation of conjugation is independent of the R27 H-NS protein.

Metal-insulator transition in composition-tuned nickel oxide films.

Thin films of the solid solution Nd1-xLaxNiO3are grown in order to study the expected 0 K phase transitions at a specific composition. We experimentally map out the structural, electronic and magnetic properties as a function ofxand a discontinuous, possibly first order, insulator-metal transition is observed at low temperature whenx= 0.2. Raman spectroscopy and scanning transmission electron microscopy show that this is not associated with a correspondingly discontinuous global structural change. On the other hand, results from density functional theory (DFT) and combined DFT and dynamical mean field theory calculations produce a 0 K first order transition at around this composition. We further estimate the temperature-dependence of the transition from thermodynamic considerations and find that a discontinuous insulator-metal transition can be reproduced theoretically and implies a narrow insulator-metal phase coexistence withx. Finally, muon spin rotation (µSR) measurements suggest that there are non-static magnetic moments in the system that may be understood in the context of the first order nature of the 0 K transition and its associated phase coexistence regime.

In Situ Monitoring and Quantitative Determination of R27 Plasmid Conjugation.

Horizontal gene transfer (HGT) by plasmid conjugation is a major driving force in the spread of antibiotic resistance among Enterobacteriaceae. Most of the conjugation studies are based on calculation of conjugation ratios (number of transconjugants/number of donors) after viable counting of transconjugant and donor cells. The development of robust, fast and reliable techniques for in situ monitoring and quantification of conjugation ratios might accelerate progress in understanding the impact of this cellular process in the HGT. The IncHI1 plasmids, involved in multiresistance phenotypes of relevant pathogens such as Salmonella and E. coli, are distinguished by the thermosensitivity of their conjugative transfer. Conjugation mediated by IncHI1 plasmids is more efficient at temperatures lower than 30 °C, suggesting that the transfer process takes place during the environmental transit of the bacteria. In this report, we described a methodology to monitor in situ the conjugation process during agar surface matings of the IncHI1 plasmid R27 and its derepressed derivative drR27 at different temperatures. A three-color-labeling strategy was used to visualize the spatial distribution of transconjugants within the heterogeneous environment by epifluorescence and confocal microscopy. Moreover, the fluorescent labelling was also used to quantify conjugation frequencies in liquid media by flow cytometry.

Top-Layer Engineering Reshapes Charge Transfer at Polar Oxide Interfaces.

Charge-transfer phenomena at heterointerfaces are a promising pathway to engineer functionalities absent in bulk materials but can also lead to degraded properties in ultrathin films. Mitigating such undesired effects with an interlayer reshapes the interface architecture, restricting its operability. Therefore, developing less-invasive methods to control charge transfer will be beneficial. Here, an appropriate top-interface design allows for remote manipulation of the charge configuration of the buried interface and concurrent restoration of the ferromagnetic trait of the whole film. Double-perovskite insulating ferromagnetic La2 NiMnO6 (LNMO) thin films grown on perovskite oxide substrates are investigated as a model system. An oxygen-vacancy-assisted electronic reconstruction takes place initially at the LNMO polar interfaces. As a result, the magnetic properties of 2-5 unit cell LNMO films are affected beyond dimensionality effects. The introduction of a top electron-acceptor layer redistributes the electron excess and restores the ferromagnetic properties of the ultrathin LNMO films. Such a strategy can be extended to other interfaces and provides an advanced approach to fine-tune the electronic features of complex multilayered heterostructures.

Large Tuning of Electroresistance in an Electromagnetic Device Structure Based on the Ferromagnetic-Piezoelectric Interface.

The electrical control of the conducting state through phase transition and/or resistivity switching in heterostructures of strongly correlated oxides is at the core of the large on-going research activity of fundamental and applied interest. In an electromechanical device made of a ferromagnetic-piezoelectric heterostructure, we observe an anomalous negative electroresistance of ∼-282% and a significant tuning of the metal-to-insulator transition temperature when an electric field is applied across the piezoelectric. Supported by finite-element simulations, we identify the electric field applied along the conducting bridge of the device as the plausible origin: stretching the underlying piezoelectric substrate gives rise to a lattice distortion of the ferromagnetic manganite overlayer through epitaxial strain. Large modulations of the resistance are also observed by applying static dc voltages across the thickness of the piezoelectric substrate. These results indicate that the emergent electronic phase separation in the manganites can be selectively manipulated when interfacing with a piezoelectric material, which offers great opportunities in designing oxide-based electromechanical devices.

Self-organized Ce(1-x)Gd(x)O(2-y) nanowire networks with very fast coarsening driven by attractive elastic interactions.

Assembling arrays of ordered nanowires is a key objective for many of their potential applications. However, a lack of understanding and control of the nanowires' growth mechanisms limits their thorough development. In this work, an appealing new path towards self-organized epitaxial nanowire networks produced by high-throughput solution methods is reported. Two requisites are identified to generate the nanowires: a thermodynamic driving force for an unrestricted elongated equilibrium island shape, and a very fast effective coarsening rate. These requirements are met in anisotropically strained Ce(1-x)Gd(x)O(2-y) nanowires with the (011) orientation grown on the (001) surface of LaAlO(3) substrates. Nanowires with aspect ratios above ≈100 oriented along two mutually orthogonal axes are obtained leading to labyrinthine networks. A very fast effective nanowire growth rate (≈60 nm min(-1)) for ex-situ thermally annealed nanostructures derives from simultaneous kinetic processes occurring in a branched network. Ostwald ripening and anisotropic dynamic coalescence, both promoted by strain-driven attractive nanowire interaction, and rapid recrystallization, enabled by fast atomic diffusion associated with a high concentration of oxygen vacancies, contribute to such an effective growth rate. This bottom-up approach to self-organized nanowire growth has a wide potential for many materials and functionalities.

Orientational ordering of solution derived epitaxial Gd-doped ceria nanowires induced by nanoscratching.

When one-dimensional nanostructures are epitaxially grown on a substrate a key goal is to control the nanowire's position and orientation. Nanoscratching of single crystalline (001)- LaAlO(3) substrates is demonstrated to be extraordinarily effective in directing the self-assembly of Ce(0.9)Gd(0.1)O(2-y) epitaxial nanowires grown by chemical solution deposition. The local anisotropic elastic strain field imposed by the indentation lines is responsible for the breaking of the pre-existing orientation energy degeneracy and selects the nanowires' orientation parallel to the lines to an extent that can reach 100%.

Temperature Dependent Control of the R27 Conjugative Plasmid Genes.

Conjugation of R27 plasmid is thermoregulated, being promoted at 25°C and repressed at 37°C. Previous studies identified plasmid-encoded regulators, HtdA, TrhR and TrhY, that control expression of conjugation-related genes (tra). Moreover, the nucleoid-associated protein H-NS represses conjugation at non-permissive temperature. A transcriptomic approach has been used to characterize the effect of temperature on the expression of the 205 R27 genes. Many of the 35 tra genes, directly involved in plasmid-conjugation, were upregulated at 25°C. However, the majority of the non-tra R27 genes-many of them with unknown function-were more actively expressed at 37°C. The role of HtdA, a regulator that causes repression of the R27 conjugation by counteracting TrhR/TrhY mediated activation of tra genes, has been investigated. Most of the R27 genes are severely derepressed at 25°C in an htdA mutant, suggesting that HtdA is involved also in the repression of R27 genes other than the tra genes. Interestingly, the effect of htdA mutation was abolished at non-permissive temperature, indicating that the HtdA-TrhR/TrhY regulatory circuit mediates the environmental regulation of R27 gene expression. The role of H-NS in the proposed model is discussed.

Crosstalk between bacterial conjugation and motility is mediated by plasmid-borne regulators.

Plasmid conjugation is a major horizontal gene transfer mechanism. The acquisition of a plasmid may cause a perturbation of the cell functions in addition to provide advantageous properties for the recipient cell, such as the gaining of antibiotic resistances. The interplay between plasmid and chromosomal functions has been studied using the IncHI1 plasmid R27. Plasmids of the incompatibility group HI1, isolated from several Gram-negative pathogens, are associated with the spread of multidrug resistance. Their conjugation is tightly regulated by temperature, being repressed at temperatures within the host (37°C). In this report, we described that at permissive temperature, when conjugation of plasmid R27 is prompted, a reduction in the motility of the cells is observed. This reduction is mediated by the plasmid-encoded regulators TrhR/TrhY, which together with HtdA form a plasmid-borne regulatory circuit controlling R27 conjugation. TrhR/TrhY, required to induce R27 conjugation, is responsible for the downregulation of the flagella synthesis and the consequent decrease in motility. TrhR/TrhY repress, direct or indirectly, the expression of the specific flagellar sigma subunit FliA and, consequently, the expression of all genes located bellow in the flagellar expression cascade.

Scale-invariant magnetic textures in the strongly correlated oxide NdNiO3.

Strongly correlated quantum solids are characterized by an inherently granular electronic fabric, with spatial patterns that can span multiple length scales in proximity to a critical point. Here, we use a resonant magnetic X-ray scattering nanoprobe with sub-100 nm spatial resolution to directly visualize the texture of antiferromagnetic domains in NdNiO3. Surprisingly, our measurements reveal a highly textured magnetic fabric, which we show to be robust and nonvolatile even after thermal erasure across its ordering temperature. The scale-free distribution of antiferromagnetic domains and its non-integral dimensionality point to a hitherto-unobserved magnetic fractal geometry in this system. These scale-invariant textures directly reflect the continuous nature of the magnetic transition and the proximity of this system to a critical point. The present study not only exposes the near-critical behavior in rare earth nickelates but also underscores the potential for X-ray scattering nanoprobes to image the multiscale signatures of criticality near a critical point.

Conductivity and Local Structure of LaNiO3 Thin Films.

A marked conductivity enhancement is reported in 6-11 unit cell LaNiO3 thin films. A maximal conductivity is also observed in ab initio calculations for films of the same thickness. In agreement with results from state of the art scanning transmission electron microscopy, the calculations also reveal a differentiated film structure comprising characteristic surface, interior, and heterointerface structures. Based on this observation, a three-element parallel conductor model is considered and leads to the conclusion that the conductivity enhancement for films of 6-11 unit cells, stems from the onset of intercompetition between the three local structures in the film depth.