Characterization of the Edge States in Colloidal Bi2Se3 Platelets.

The remarkable development of colloidal nanocrystals with controlled dimensions and surface chemistry has resulted in vast optoelectronic applications. But can they also form a platform for quantum materials, in which electronic coherence is key? Here, we use colloidal, two-dimensional Bi2Se3 crystals, with precise and uniform thickness and finite lateral dimensions in the 100 nm range, to study the evolution of a topological insulator from three to two dimensions. For a thickness of 4-6 quintuple layers, scanning tunneling spectroscopy shows an 8 nm wide, nonscattering state encircling the platelet. We discuss the nature of this edge state with a low-energy continuum model and ab initio GW-Tight Binding theory. Our results also provide an indication of the maximum density of such states on a device.

Reversible MnO to Mn3 O4 Oxidation in Manganese Oxide Nanoparticles.

Manganese is an attractive element for sustainable solutions. It is largely available in the earth's crust, making it ideal for cost-effective and large-scale applications. Especially MnO nanoparticles have recently received attention for applications in battery technology. However, manganese has many oxidation states that are energetically very similar, indicating that they may easily transform from one to the other. Herein, the reversible oxidation of MnO nanoparticles to Mn3 O4 studied with in situ transmission electron microscopy is shown. The oxygen sublattices of MnO and Mn3 O4 are found to be perfectly aligned, and an atomic mechanism where the transformation is facilitated by the migration of Mn cations on the shared O sublattice is proposed. Even when protected with an amorphous carbon layer, MnO particles are highly unstable and oxidize to Mn3 O4 in ethanol. The poor stability of MnO lacks discussion in many battery-related works, and strategies aimed at avoiding this should be developed.

Bandgap tuning of two-dimensional materials by sphere diameter engineering.

Developing a precise and reproducible bandgap tuning method that enables tailored design of materials is of crucial importance for optoelectronic devices. Towards this end, we report a sphere diameter engineering (SDE) technique to manipulate the bandgap of two-dimensional (2D) materials. A one-to-one correspondence with an ideal linear working curve is established between the bandgap of MoS2 and the sphere diameter in a continuous range as large as 360 meV. Fully uniform bandgap tuning of all the as-grown MoS2 crystals is realized due to the isotropic characteristic of the sphere. More intriguingly, both a decrease and an increase of the bandgap can be achieved by constructing a positive or negative curvature. By fusing individual spheres in the melted state, post-synthesis bandgap adjustment of the supported 2D materials can be realized. This SDE technique, showing good precision, uniformity and reproducibility with high efficiency, may further accelerate the potential applications of 2D materials.

Tailoring the stoichiometry of C3N4 nanosheets under electron beam irradiation.

Two-dimensional polymeric graphitic carbon nitride (g-C3N4) is a low-cost material with versatile properties that can be enhanced by the introduction of dopant atoms and by changing the degree of polymerization/stoichiometry, which offers significant benefits for numerous applications. Herein, we investigate the stability of g-C3N4 under electron beam irradiation inside a transmission electron microscope operating at different electron acceleration voltages. Our findings indicate that the degradation of g-C3N4 occurs with N species preferentially removed over C species. However, the precise nitrogen group from which N is removed from g-C3N4 (C-N-C, [double bond, length as m-dash]NH or -NH2) is unclear. Moreover, the rate of degradation increases with decreasing electron acceleration voltage, suggesting that inelastic scattering events (radiolysis) dominate over elastic events (knock-on damage). The rate of degradation by removing N atoms is also sensitive to the current density. Hence, we demonstrate that both the electron acceleration voltage and the current density are parameters with which one can use to control the stoichiometry. Moreover, as N species were preferentially removed, the d-spacing of the carbon nitride structure increased. These findings provide a deeper understanding of g-C3N4.

Monitoring Glyphosate- and Chlorimuron- resistant Conyza spp. Populations in Brazil.

Conyza species are important weeds in global agriculture, especially due to their capacity to evolve resistance to multiple herbicide mechanisms of action. We aimed to evaluate the frequency and distribution of resistance to glyphosate and chlorimuron-ethyl in Conyza spp. populations from Brazil. Seed samples were collected from grain production areas across nine Brazilian states over five consecutive years (2014 to 2018). Prior to resistance monitoring trials, dose-response assays were conducted to determine a single dose of glyphosate or chlorimuron-ethyl to discriminate resistant and susceptible populations. Resistance monitoring based on plant responses to the application of discriminatory doses of glyphosate (960 g ha-1) or chlorimuron-ethyl (20 g ha-1). Populations were classified as resistant, moderately resistant, or susceptible to either herbicide. While glyphosate resistance was highly frequent (71.2%) in all the five years, chlorimuron-ethyl resistant populations occurred at 39.8% of the total. The frequency of multiple resistance to both herbicides (35.3%) was proportional to the occurrence of chlorimuron-ethyl resistance (39.6%). Resistance to glyphosate and to chlorimuron-ethyl were found across all states evaluated.

In Situ Formation of Free-Standing Single-Atom-Thick Antiferromagnetic Chromium Membranes.

Compared to van der Waals two-dimensional (2D) layers with lateral covalent bonds, metallic bonding systems favor close-packed structures, and thus, free-standing 2D metals have remained, for the most part, elusive. However, a number of theoretical studies suggest a number of metals can exist as 2D materials and a few early experiments support this notion. Here we demonstrate free-standing single-atom-thick crystalline chromium (Cr) suspended membranes using aberration-corrected transmission electron microscopy and image simulations. Density functional theory studies confirm the 2D Cr membranes have an antiferromagnetic ground state making them highly attractive for spintronic applications. Moreover, the work also helps consolidate the existence of a new family of 2D metal layers.

In Situ N-Doped Graphene and Mo Nanoribbon Formation from Mo2 Ti2 C3 MXene Monolayers.

Since the advent of monolayered 2D transition metal carbide and nitrides (MXenes) in 2011, the number of different monolayer systems and the study thereof have been on the rise. Mo2 Ti2 C3 is one of the least studied MXenes and new insights to this material are of value to the field. Here, the stability of Mo2 Ti2 C3 under electron irradiation is investigated. A transmission electron microscope (TEM) is used to study the structural and elemental changes in situ. It is found that Mo2 Ti2 C3 is reasonably stable for the first 2 min of irradiation. However, structural changes occur thereafter, which trigger increasingly rapid and significant rearrangement. This results in the formation of pores and two new nanomaterials, namely, N-doped graphene membranes and Mo nanoribbons. The study provides insight into the stability of Mo2 Ti2 C3 monolayers against electron irradiation, which will allow for reliable future study of the material using TEM. Furthermore, these findings will facilitate further research in the rapidly growing field of electron beam driven chemistry and engineering of nanomaterials.

Applications of 2D MXenes in energy conversion and storage systems.

Transition metal carbides and nitrides (MXenes), a family of two-dimensional (2D) inorganic compounds, are materials composed of a few atomic layers of transition metal carbides, nitrides, or carbonitrides. Ti3C2, the first 2D layered MXene, was isolated in 2011. This material, which is a layered bulk material analogous to graphite, was derived from its 3D phase, Ti3AlC2 MAX. Since then, material scientists have either determined or predicted the stable phases of >200 different MXenes based on combinations of various transition metals such as Ti, Mo, V, Cr, and their alloys with C and N. Extensive experimental and theoretical studies have shown their exciting potential for energy conversion and electrochemical storage. To this end, we comprehensively summarize the current advances in MXene research. We begin by reviewing the structure types and morphologies and their fabrication routes. The review then discusses the mechanical, electrical, optical, and electrochemical properties of MXenes. The focus then turns to their exciting potential in energy storage and conversion. Energy storage applications include electrodes in rechargeable lithium- and sodium-ion batteries, lithium-sulfur batteries, and supercapacitors. In terms of energy conversion, photocatalytic fuel production, such as hydrogen evolution from water splitting, and carbon dioxide reduction are presented. The potential of MXenes for the photocatalytic degradation of organic pollutants in water, such as dye waste, is also addressed, along with their promise as catalysts for ammonium synthesis from nitrogen. Finally, their application potential is summarized.

Edge-to-Edge Oriented Self-Assembly of ReS2 Nanoflakes.

The self-assembly of two-dimensional (2D) nanomaterials, an emerging research area, still remains largely unexplored. The strong interlayer attraction between 2D nanosheets leads to face-to-face stacking rather than edge-to-edge coupling. We demonstrate, for the first time, how one can induce and control an edge-to-edge self-assembly process for 2D nanomaterials. The extremely weak van der Waals coupling and strong anisotropy of ReS2 allow us to realize an oriented self-assembly (OSA) process. The aspect ratio of the resulting ReS2 nanoscrolls can be well controlled. In addition, we perform simulations to further explain and confirm the OSA process, demonstrating its great potential to be expanded as a general edge-to-edge self-assembly process suitable for other 2D nanomaterials.

Ultrafast Self-Limited Growth of Strictly Monolayer WSe2 Crystals.

The controllable synthesis of uniform tungsten diselenide (WSe2 ) is crucial for its emerging applications due to the high sensitivity of its extraordinary physicochemical properties to its layer numbers. However, undesirable multilayer regions inevitably form during the fabrication of WSe2 via the traditional chemical vapor deposition process resulted from the lack of significantly energetically favorable competition between layer accumulation and size expansion. This work innovatively introduces Cu to occupy the hexagonal site positioned at the center of the six membered ring of the WSe2 surface, thus filtrates the undesired reaction path through precisely thermodynamical control and achieves self-limited growth WSe2 crystals. The as-obtained WSe2 crystals are characterized as strictly single-layer over the entire wafer. Furthermore, the strictly self-limited growth behavior can achieve the "win-win" cooperation with the synthesis efficiency. The fastest growth (≈15 times of the growth rate in the previous work) of strictly monolayer WSe2 crystals thus far is realized due to the high-efficiency simultaneous selenization process. The as-proposed ultrafast Cu-assisted self-limited growth method opens a new avenue to fabricate strictly monolayer transition metal dichalcogenides crystals and further promotes their practical applications in the future industrial applications.

Synthesis and toxicity characterization of carbon coated iron oxide nanoparticles with highly defined size distributions.

BACKGROUND: Iron oxide nanoparticles hold great promise for future biomedical applications. To this end numerous studies on iron oxide nanoparticles have been conducted. One aspect these studies reveal is that nanoparticle size and shape can trigger different cellular responses through endocytic pathways, cell viability and early apoptosis. However, systematic studies investigating the size dependence of iron oxide nanoparticles with highly defined diameters across multiple cells lines are not available yet. METHODS: Iron oxide nanoparticles with well-defined size distributions were prepared. All samples were thoroughly characterized and the cytotoxicity for four standard cell lines (HeLa Kyoto, human osteosarcoma (U2OS), mouse fibroblasts (NIH 3T3) and mouse macrophages (J7442)) where investigated. RESULTS: Our findings show that small differences in size distribution (ca. 10nm) of iron oxide nanoparticles do not influence cytotoxicity, while uptake is size dependent. Cytotoxicity is dose-dependent. Broad distributions of nanoparticles are more easily internalized as compared to the narrow distributions for two of the cell lines tested (HeLa Kyoto and mouse macrophages (J7442)). CONCLUSION: The data indicate that it is not feasible to probe changes in cytotoxicity within a small size range (10nm). However, TEM investigations of the nanoparticles indicate that cellular uptake is size dependent. GENERAL SIGNIFICANCE: The present work compares narrow and broad distributions for various samples of carbon-coated iron oxide nanoparticles. The data highlights that cells differentiate between nanoparticle sizes as indicated by differences in cellular uptake. This information provides valuable knowledge to better understand the interaction of nanoparticles and cells.

Disclosing the native blueberry rhizosphere community in Portugal-an integrated metagenomic and isolation approach.

Backgorund: The production of red fruits, such as blueberry, has been threatened by several stressors from severe periods of drought, nutrient scarcity, phytopathogens, and costs with fertilization programs with adverse consequences. Thus, there is an urgent need to increase this crop's resilience whilst promoting sustainable agriculture. Plant growth-promoting microorganisms (PGPMs) constitute not only a solution to tackle water and nutrient deficits in soils, but also as a control against phytopathogens and as green compounds for agricultural practices. Methods: In this study, a metagenomic approach of the local fungal and bacterial community of the rhizosphere of Vaccinium corymbosum plants was performed. At the same time, both epiphytic and endophytic microorganisms were isolated in order to disclose putative beneficial native organisms. Results: Results showed a high relative abundance of Archaeorhizomyces and Serendipita genera in the ITS sequencing, and Bradyrhizobium genus in the 16S sequencing. Diversity analysis disclosed that the fungal community presented a higher inter-sample variability than the bacterial community, and beta-diversity analysis further corroborated this result. Trichoderma spp., Bacillus spp., and Mucor moelleri were isolated from the V. corymbosum plants. Discussion: This work revealed a native microbial community capable of establishing mycorrhizal relationships, and with beneficial physiological traits for blueberry production. It was also possible to isolate several naturally-occurring microorganisms that are known to have plant growth-promoting activity and confer tolerance to hydric stress, a serious climate change threat. Future studies should be performed with these isolates to disclose their efficiency in conferring the needed resilience for this and several crops.

Peptaibiotics: Harnessing the potential of microbial secondary metabolites for mitigation of plant pathogens.

Agricultural systems are in need of low-cost, safe antibiotics to protect crops from pests and diseases. Peptaibiotics, a family of linear, membrane-active, amphipathic polypeptides, have been shown to exhibit antibacterial, antifungal, and antiviral activity, and to be inducers of plant resistance against a wide range of phytopathogens. Peptaibiotics belong to the new generation of alternatives to agrochemicals, aligned with the United Nations Sustainable Development Goals and the One Health approach toward ensuring global food security and safety. Despite that, these fungi-derived, non-ribosomal peptides remain surprisingly understudied, especially in agriculture, where only a small number has been tested against a reduced number of phytopathogens. This lack of adoption stems from peptaibiotics' poor water solubility and the difficulty to synthesize and purify them in vitro, which compromises their delivery and inclusion in formulations. In this review, we offer a comprehensive analysis of peptaibiotics' classification, biosynthesis, relevance to plant protection, and mode of action against phytopathogens, along with the techniques enabling researchers to extract, purify, and elucidate their structure, and the databases holding such valuable data. It is also discussed how chemical synthesis and ionic liquids could increase their solubility, how genetic engineering and epigenetics could boost in vitro production, and how omics can reduce screenings' workload through in silico selection of the best candidates. These strategies could turn peptaibiotics into effective, ultra-specific, biodegradable tools for phytopathogen control.

Towards a Sustainable Management of the Spotted-Wing Drosophila: Disclosing the Effects of Two Spider Venom Peptides on Drosophila suzukii.

The spotted-wing drosophila (Drosophila suzukii) is a polyphagous pest that causes severe damage and economic losses to soft-skinned fruit production. Current control methods are dominated by inefficient cultural practices and broad-spectrum insecticides that, in addition to having toxic effects on non-target organisms, are becoming less effective due to acquired resistance. The increasing awareness of the real impact of insecticides on health and the environment has promoted the exploration of new insecticidal compounds, addressing novel molecular targets. This study explores the efficacy of two orally delivered spider venom peptides (SVPs), J-atracotoxin-Hv1c (Hv1c) and µ-theraphotoxin-Hhn2b (TRTX), to manage D. suzukii, through survival assays and the evaluation of gene expression associated with detoxification pathways. Treatment with TRTX at 111.5 µM for 48 h enhanced fly longevity compared with the control group. Gene expression analysis suggests that detoxification and stress-related mechanisms, such as expression of P450 proteins and apoptotic stimuli signaling, are triggered in D. suzukii flies in response to these treatments. Our results highlight the potential interest of SVPs to control this pest, shedding light on how to ultimately develop improved target-specific formulations.

Development of iron ore tailings based wood-cement composite panels.

This article evaluated the effect of using mining waste on the mechanical, physical, thermal, and microstructural properties of cement-wood panels. The percentages of 10, 20, 30, and 40% were evaluated as replacing cement with mining waste. The wood particles of Pinus oocarpa were evaluated for their chemical, anatomical, and physical characteristics, and the mining waste was evaluated for its granulometry, chemical composition, and inhibition index. The composites were evaluated for their physical-mechanical properties, X-ray diffraction and infrared spectroscopy analysis, microstructural, thermal, and durability. All evaluated treatments met the requirements of the Bison standard for MOR and MOE for static bending and internal bonding, even after accelerated aging. It was possible to conclude that it is feasible to replace 40% of cement with mining waste for the production of cement-wood panels in industrial scale.

Drosophila suzukii energetic pathways are differently modulated by nutritional geometry in males and females.

As a polyphagous pest, Drosophila suzukii has a variety of host fruits available for feeding and oviposition, but how the nutritional geometry of different hosts influences its metabolism is still poorly understood. This work aimed to evaluate how D. suzukii metabolic and transcriptional pathways are influenced by feeding on different host fruits, and how sex influences these responses. Adult flies were allowed to feed on five different fruit-based media. Lipids, glucose, glycogen, and energy pathways-associated gene expression, were quantified. Females showed an energetic metabolism easily adaptable to the food's nutritional characteristics; in contrast, males' energetic metabolism was particularly influenced by food, predominantly those fed on raspberry media who showed changes in glucose levels and in the expression of genes associated with metabolic pathways, suggesting activation of gluconeogenesis and trehaloneogenesis as a result of nutritional deficiency. Here we present novel insight into how D. suzukii's energetic pathways are modulated depending on fruits' nutritional geometry and sex. While the females showed high adaptability in their energetic metabolism to the diet, males were more feeding-sensitive. These findings might be used not only to control this pest population but to better advise producers to invest in less suitable fruits based on the hosts' nutritional geometry.

Variability within a clonal population of Erwinia amylovora disclosed by phenotypic analysis.

Background: Fire blight is a destructive disease of pome trees, caused by Erwinia amylovora, leading to high losses of chain-of-values fruits. Major outbreaks were registered between 2010 and 2017 in Portugal, and the first molecular epidemiological characterization of those isolates disclosed a clonal population with different levels of virulence and susceptibility to antimicrobial peptides. Methods: This work aimed to further disclose the genetic characterization and unveil the phenotypic diversity of this E. amylovora population, resorting to MLSA, growth kinetics, biochemical characterization, and antibiotic susceptibility. Results: While MLSA further confirmed the genetic clonality of those isolates, several phenotypic differences were recorded regarding their growth, carbon sources preferences, and chemical susceptibility to several antibiotics, disclosing a heterogeneous population. Principal component analysis regarding the phenotypic traits allows to separate the strains Ea 630 and Ea 680 from the remaining. Discussion: Regardless the genetic clonality of these E. amylovora strains isolated from fire blight outbreaks, the phenotypic characterization evidenced a population diversity beyond the genotype clonality inferred by MLSA and CRISPR, suggesting that distinct sources or environmental adaptations of this pathogen may have occurred. Conclusion: Attending the characteristic clonality of E. amylovora species, the data gathered here emphasizes the importance of phenotypic assessment of E. amylovora isolates to better understand their epidemiological behavior, namely by improving source tracking, make risk assessment analysis, and determine strain-specific environmental adaptations, that might ultimately lead to prevent new outbreaks.

A Target-Site Mutation Confers Cross-Resistance to ALS-Inhibiting Herbicides in Erigeron sumatrensis from Brazil.

Cases of weed resistant to herbicides have changed the dynamics of agricultural areas in Brazil, and in recent years, Erigeron species have caused major problems to farmers in the country, mainly in relation to the ineffectiveness of herbicide treatments used. The objective of this study was to confirm the cross-resistance to ALS inhibitors in populations of Erigeron sumatrensis as well as to investigate the existence of mutations in the site of action of ALS-inhibiting herbicides. To do this, 30 populations collected in the 2016/2017 crop season were grown in a greenhouse. Dose-response (chlorimuron-ethyl and cloransulam-methyl), inhibition of cytochrome P-450 with malathion, and ALS gene sequencing experiments were carried out in the F1 generations of two fleabane populations. The results proved the cross-resistance to chlorimuron-ethyl and cloransulam-methyl herbicides applied in the post-emergence of the resistant population of E. sumatrensis. The higher activity of P450 enzymes is unlikely responsible for the resistance of the population studied. The resistance mechanism found in R was the target site mutation Pro197Ser at the ALS gene. This is the first study in Brazil to identify a target-site change as a survival mechanism in E. sumatrensis for the resistance to ALS-inhibiting herbicides.

Physical, mechanical, and thermal properties of concrete roof tiles produced with vermiculite.

This study aimed to evaluate the effect of using expanded vermiculite and its impact on the production of concrete roof tiles. The control treatment and replacement of 12.5, 25, 37.5, and 50% sand by vermiculite were evaluated. The concrete roof tiles were moulded by the simultaneous pressing and extrusion mechanical process. The control trace was comprised by 21.95% CPV-ARI cement, 65.85% sand, and 12.20% limestone. After production, the concrete roof tiles were cured for 28 days. The physical (roof tiles classification, samples dry weight, water absorption, and porosity), mechanical (splitting tensile strength), and microstructural properties were evaluated. All treatments were assessed before and after accelerated ageing. The thermal properties of the modification in the concrete roof tiles' composition were also analysed. The evaluated amounts of vermiculite significantly affected the physical, mechanical, and thermal properties of concrete roof tiles. The use of vermiculite in concrete roof tiles reduced their dry weight and thermal conductivity, not impairing their durability. The use of 31.0% vermiculite in concrete roof tiles was suggested for better thermal insulation optimization (20.29% reduction) and weight reduction (7.92% and 7.94% at 28 days of curing and after accelerated ageing, respectively), along with adequate physical, mechanical, and durability properties.

Pectin-based color indicator films incorporated with spray-dried Hibiscus extract microparticles.

Colorimetric films incorporated with anthocyanins as an indicator for freshness monitoring have aroused growing interest recently. The pH-sensing colorimetric film were developed based on pectin (HM), containing aqueous hibiscus extract microparticles (HAE). HAE microparticles were obtained by spray drying with different wall materials (Inulin -IN, maltodextrin- MD and their combination). The films were obtained on large scale by continuous casting. These films were characterized for physicochemical analysis, morphological structure, thermal and barrier properties, antioxidant activity, and color change at different pH. The addition of HAE microparticles caused relevant changes to HM-based films, such as in mechanical behavior and improved barrier property (11-22% WVTR reduction) depending on the type of wall material used and the concentration added. It was verified with the thermal stability of films, with a slight increase being observed. The color variation of smart films was entirely pH-dependent. Overall, the proposed color indicator films showed unique features and functionalities and could be used as an alternative natural pH indicator in smart packaging systems.