Tuning Electronic and Structural Properties of Lead-Free Metal Halide Perovskites: A Comparative Study of 2D Ruddlesden-Popper and 3D Compositions.

In recent decades, two-dimensional (2D) perovskites have emerged as promising semiconductors for next-generation photovoltaics, showing notable advancements in solar energy conversion. Herein, we explore the impact of alternative inorganic lattice BX-based compositions (B=Ge or Sn, X=Br or I) on the energy gap and stability. Our investigation encompasses BA2Man-1BnX3n+1 2D Ruddlesden-Popper perovskites (for n=1-5 layers) and 3D bulk (MA)BX3 systems, employing first-principles calculations with spin-orbit coupling (SOC), DFT-1/2 quasiparticle, and D3 dispersion corrections. The study unveils how atoms with smaller ionic radii induce anisotropic internal and external distortions within the inorganic and organic lattices. Introducing the spacers in the low-layer regime reduces local distortions but widens band gaps. Our calculation protocol provides deeper insights into the physics and chemistry underlying 2D perovskite materials, paving the way for optimizing environmentally friendly alternatives that can efficiently replace with sustainable materials.

Ab initioscreening of two-dimensional CuQxand AgQxchalcogenides.

Two-dimensional (2D) chalcogenides have attracted great interest from the scientific community due to their intrinsic physical-chemical properties, which are suitable for several technological applications. However, most of the reported studies focused on particular compounds and composition, e.g., MoS2, MoSe2, WS2, and WSe2. Thus, there is an increased interest to extend our knowledge on 2D chalcogenides. Here, we report a density functional theory (DFT) screening of 2D coinage-metal chalcogenides (MQx), whereM= Cu, Ag,Q= S, Se, Te,x= 0.5, 1.0, 1.5, 2.0, with the aim to improve our atomistic understanding of the physical-chemical properties as a function of cation (M), anion (Q), and composition (x). Based on 258 DFT calculations, we selected a set of 22 stableMQxmonolayers based on phonons analyses, where we identified 9 semiconductors (7 AgQxand 2 CuQx), with band gaps from 0.07 eV up to 1.67 eV, while the remaining systems have a metallic character. Using all 258 systems, we found a logarithmic correlation between the average weighted bond lengths and effective coordination number of cations and anions. As expected, the monolayer cohesive energies increase with the radius of theQspecies (i.e., from S to Te). Furthermore, an increase in the anion size diminishes the work function for nearly allMQxmonolayers, which can be explained by the nature of the electronic states at the valence band maximum.

Clone worth? Genetic diversity in obligate apomictic Miconia albicans (Melastomataceae).

Apomixis is the asexual production of seeds by plants and, in theory, would render low genetic diversity and even clonal lineages. However, recent studies have shown otherwise, although is not always clear where the genetic diversity of obligate apomicts comes from. We evaluated the genetic diversity among sister seedlings of M. albicans, an obligate apomictic species in Cerrado, Neotropical Savannas in Central Brazil. A total of 50 seedlings from five individuals were analysed using ISSR primers. We obtained 107 fragments, all with good resolution, consistently observed and replicable. The percentage of polymorphic loci ranged from 28.04% to 33.64% and Shannon's information index (I) averaged 0.173. The expected heterozygosity (He) averaged 0.117, similar to the observed for populations of M. albicans and other selfed species. Only two seedlings showed the same genotype (possible clones), but most differed at least for five loci. Most of variance was among progenies (62%), but we found that 38% was within progenies. Genetic distances separated the progenies in two groups, and analogous analyses between individuals reconstructed the original progenies clustering. The results confirmed a relatively high genetic diversity among sister seedling of this obligatory apomictic plant and clones were rare. This diversity can be generated during development, probably by restitutional meiosis or other recombination processes. These differences may accumulate into lineages and populations well adapted to heterogenous Cerrado environment.

Robust room temperature emissions of trion in darkish WSe2 monolayers: effects of dark neutral and charged excitonic states.

Owing to nonzero charge and spin degrees of freedom, trions offer unprecedented tunability and open new paths for applications in devices based on 2D semiconductors. However, in monolayer WSe2, the trion photoluminescence is commonly detected only at low temperatures and vanishes at room temperature, which undermines practical applications. To unveil how to overcome this obstacle, we have developed a comprehensive theory to probe the impact of different excitonic channels on the trion emission in WSe2 monolayers, which combines ab initio tight-binding formalism, Bethe-Salpeter equation and a set of coupled rate equations to describe valley dynamics of excitonic particles. Through a systematic study in which new scattering channels are progressively included, we found that, besides the low electron density, strong many-body correlations between bright and dark excitonic states quenches the trion emission in WSe2. Therefore, the reduction of scatterings from bright to dark states is required to achieve trion emission at room temperature for experimentally accessible carrier concentrations.

Shifting abundances of communities associated with nitrogen cycling in soils promoted by sugarcane harvest systems.

Sugarcane cultivation supports Brazil as one of the largest world sugar and ethanol producer. In order to understand the impact of changing sugarcane harvest from manual to mechanized harvest, we studied the effect of machinery traffic on soil and consequently soil compaction upon soil microbial communities involved in nitrogen cycling. The impact of sugarcane harvest was dependent on soil depth and texture. At deeper soil layers, mechanized harvesting increases the abundance of nitrogen fixers and denitrifying communities (specifically nosZ clade I and II) while manual harvesting increases the abundance of ammonia oxidizers (specifically AOA) and increases denitrifying communities (nosZ clade I and II) on top and at intermediate depth. The effect of change on the harvest system is more evident on sandy soil than on clay soil, where soil indicators of compaction (bulk density and penetration resistance) were negatively correlated with soil microorganisms associated with the nitrogen cycle. Our results point to connections between soil compaction and N transformations in sugarcane fields, besides naming biological variables to be used as proxies for alterations in soil structure.

Correction to: G3BP1 knockdown sensitizes U87 glioblastoma cell line to Bortezomib by inhibiting stress granules assembly and potentializing apoptosis.

In the initial online version of the article, author F.M. Soriani was missing. The original article has been corrected.

G3BP1 knockdown sensitizes U87 glioblastoma cell line to Bortezomib by inhibiting stress granules assembly and potentializing apoptosis.

INTRODUCTION: Glioblastoma multiforme (GBM) is the most lethal form of gliomas. New therapies are currently in development to tackle treatment limitations such as chemotherapy resistance. One mechanism of resistance may be the stress granules (SG) assembly, a stress-related cellular response that allows cells to recruit and protect mRNAs during stress. SG are composed of various proteins, being G3BP1 a core element that enucleates and results in SG assembly. Here, we aimed to evaluate the effects of inhibiting the G3PB1 expression in the chemotherapeutical-induced cell death of the U87 glioblastoma cell line. MATERIALS AND METHODS: G3BP1 mRNA and protein expression were modulated with short-interference RNA (siRNA). The viability of U87 cells after Bortezomib (BZM), a proteasome inhibitor, and Temozolomide (TMZ), an alkylating agent, was assessed by MTT assay. Apoptosis was evaluated by staining cells with Annexin-V/7-AAD and analyzing by flow cytometry. Caspase-3 activation was evaluated by immunoblotting. The chorioallantoic membrane in vivo assay was used to evaluate angiogenesis. RESULTS: When G3BP1 was knocked-down, the SG assembly was reduced and the BZM-treated cells, but not TMZ-treated cells, had a significant increase in the apoptotic response. Corroborating this data, we observed increased Caspase-3 activation in the BZM-treated and G3BP1-knocked-down cells when compared to vehicle-treated and scramble-transfected cells. Worth mentioning, the conditioned culture medium of G3BP1-knocked-down BZM-treated cells inhibited angiogenesis when compared to controls. CONCLUSION: Our data suggest G3BP1 knockdown diminishes SG formation and stimulates BZM-induced apoptosis of U87 cells in vitro, in addition to inhibiting glioblastoma-induced angiogenesis in vivo.

A systematic review of life cycle sustainability assessment: Current state, methodological challenges, and implementation issues.

The life cycle sustainability assessment (LCSA) is a tool to assess sustainability from a life cycle perspective, which has been receiving increased attention over the years. This work presents a systematic review of the current application of LCSA, presenting the foundations, main methods, current operationalization state, and major challenges to its broad implementation. The review protocol considered the search of keywords in Scopus and Web of Science databases. The search has considered the literature published or in the press until December 2018, resulting in the selection of 144 articles written in English. Of those, 71 articles operationalize LCSA in real case studies, while the remaining consist of review, viewpoint, and methodological development articles. This review demonstrates that the use of LCSA has been increasing in recent years. Today, the most applied approach is to consider LCSA as the sum of life cycle assessment, life cycle costing, and social life cycle assessment because it is built on the methodologies that already exist and are under continuous development. However, the lack of harmonization of the methodology is a central challenge to its operationalization. Therefore, LCSA still requires further improvement in, among others, definition of coherent system boundaries, the development of robust databases to allow the assessment of economic and social perspectives, definition of impact categories that allow comparability between studies, development of impact assessment methods, development of methods to carry out uncertainty analysis, and communication strategies. Besides, further case studies should be developed to support the improvement of the methodology and a better understanding of the interaction of the environmental, economic, and social aspects.

Regionalizing eco-toxicity characterization factors for copper soil emissions considering edaphic information for Northern Spain and Portuguese vineyards.

The management of vineyards depends on the use of plant protection agents. Regardless of the numerous environmental impacts that these pesticides generate during their production, their dosage as pest control agents in vineyards causes an important toxic effect that must be monitored. Copper-based inorganic pesticides are the most widely used agents to control fungal diseases in humid wine-growing regions. It is, however, significant that the environmental analysis of their use through the Life Cycle Assessment (LCA) methodology does not provide detailed information on the potential toxicity of this type of pesticides. Hence, most studies report average values for copper characterization factors (CFs), excluding local soil characteristics. The objective of the study was the spatial characterization of the ecotoxicity factors of copper soil emissions as a function of the chemical characteristics of vineyard soils located in Portugal and Galicia (NW Spain). A multiple linear regression model was applied to calculate the comparative toxic potential. Subsequently, CFs for copper were calculated based on spatial differentiation considering the variable properties of the soil within each wine appellation. The CFs obtained for the area evaluated ranged from 141 to 5937 PAF·m3·day/kgCu emitted, for fibric histosols (HSf) and dystic cambisols (CMd), respectively. Moreover, the average values obtained for Galician and Portuguese soils were 1145 and 2274 PAF·m3·day/kgCu emitted, respectively. The results obtained illustrate the high variability of CF values as a function of the chemical characteristics of each type of soil. For example, Cu soil mobility was linked to organic carbon content and pH. Finally, to validate the representativeness of the calculated CFs, these were applied to the results of 12 literature life cycle inventories of grape production in the area evaluated, revealing that impact scores associated with Cu emissions can considerably vary when spatially-differentiated CFs are implemented.

Potential Effects of Future Climate Changes on Brazilian Cool-Adapted Stoneflies (Insecta: Plecoptera).

The continuous pursuit of welfare and economic development through the exploitation of natural resources by human societies consequently resulted in the ongoing process of climate change. Changes in the distribution of species towards the planet's poles and mountain tops are some of the expected to biological consequences of this process. Here, we assessed the potential effects of future climate change on four cool-adapted Gripopterygidae (Insecta: Plecoptera) species [Gripopteryx garbei Navás 1936, G. cancellata (Pictet 1841), Tupiperla gracilis (Burmeister 1839), and T. tessellata (Brauer 1866)] from Southeastern Brazilian Atlantic forest. As species adapted to cold conditions, in the future scenarios of climate change, we expected these organisms to shrink/change their distributions ranges towards areas with suitable climatic conditions in Southern Brazilian regions, when compared with their predicted distributions in present climatic conditions. We used seven principal components derived from 19 environmental variables from Worldclim database for the present scenario and also seven principal components obtained from 17 different Atmosphere-Ocean Global Circulation Models (AOGCMs), considering the most severe emission scenario for green-house gases to predict the species' distributions. Depending on the climatic scenario considered, there were polewards distribution range changes of the species. Additionally, we also observed an important decrease in the amount of protected modeled range for the species in the future scenarios. Considering that this Brazilian region may become hotter in the future and have its precipitation regime changed, as observed in the severe 2013-2014 drought, we believe these species adapted to high altitudes will be severely threatened in the future.

Optically dark excitonic states mediated exciton and biexciton valley dynamics in monolayer WSe2.

We present a theory to address the photoluminescence (PL) intensity and valley polarization (VP) dynamics in monolayer WSe2, under the impact of excitonic dark states of both excitons and biexcitons. We find that the PL intensity of all excitonic channels including intravalley exciton (Xb), intravalley biexciton (XXk,k) and intervalley biexciton (XX[Formula: see text]) in particular for the XXk,k PL is enhanced by laser excitation fluence. In addition, our results indicate the anomalous temperature dependence of PL, i.e. increasing with temperature, as a result of favored phonon assisted dark-to-bright scatterings at high temperatures. Moreover, we observe that the PL is almost immune to intervalley scatterings, which trigger the exchange of excitonic states between the two valleys. As far as the valley polarization is concerned, we find that the VP of Xb shrinks as temperature increases, exhibiting opposite temperature response to PL, while the intravalley XXk,k VP is found almost independent of temperature. In contrast to both Xb and XXk,k, the intervalley XX[Formula: see text] VP identically vanishes, because of equal populations of excitons in the K and [Formula: see text] valleys bounded to form intervalley biexcitons. Notably, it is found that the Xb VP much more strongly depends on bright-dark scattering than that of XXk,k, making dark state act as a robust reservoir for valley polarization against intervalley scatterings for Xb at strong bright-dark scatterings, but not for XXk,k. Dark excitonic states enabled enhancement of VP benefits quantum technology for information processing based on the valley degree of freedom in valleytronic devices. Furthermore, the VP has strong dependence on intervalley scattering but maintains essentially constant with excitation fluence. Finally, the dependence of time evolution of PL and VP on temperature and excitation fluence is discussed.

Unexpectedly high genetic diversity and divergence among populations of the apomictic Neotropical tree Miconia albicans.

Since tropical trees often have long generation times and relatively small reproductive populations, breeding systems and genetic variation are important for population viability and have consequences for conservation. Miconia albicans is an obligate, diplosporous, apomictic species widespread in the Brazilian Cerrado, the savanna areas in central Brazil and elsewhere in the Neotropics. The genetic variability would be, theoretically, low within these male-sterile and possibly clonal populations, although some variation would be expected due to recombination during restitutional meiosis. We used ISSR markers to assess genetic diversity of M. albicans and to compare with other tropical trees, including invasive species of Melastomataceae. A total of 120 individuals from six populations were analysed using ten ISSR primers, which produced 153 fully reproducible fragments. The populations of M. albicans presented mean Shannon's information index (I) of 0.244 and expected heterozygosity (He ) of 0.168. Only two pairs of apparently clonal trees were identified, and genetic diversity was relatively high. A hierarchical amova for all ISSR datasets showed that 74% of the variance was found among populations, while only 26% of the variance was found within populations of this species. Multivariate and Bayesian analyses indicated marked separation between the studied populations. The genetic diversity generated by restitutional meiosis, polyploidy and possibly other genome changes may explain the morpho-physiological plasticity and the ability of these plants to differentiate and occupy such a wide territory and different environmental conditions. Producing enormous amounts of bird-dispersed fruits, M. albicans possess weedy potential that may rival other Melastomataceae alien invaders.

Availability of polycyclic aromatic hydrocarbons to earthworms in urban soils and its implications for risk assessment.

Polycyclic aromatic hydrocarbons (PAHs) are a global problem, and in urban soils they can be found at potentially hazard levels. Nevertheless, the real risks that these contaminants pose to the environment are not well known, since the bioavailability of PAHs in urban soils has been poorly studied. Therefore, the bioavailability of PAHs in some selected urban soils from Lisbon (Portugal) was evaluated. Moreover, the applicability of a first screening phase based on total contents of PAHs was assessed. Results show that bioavailability of PAHs is reduced (low levels in earthworms, low accumulation percentages, and low biota-to-soil accumulation factors values), especially in more contaminated soils. The aging of these compounds explains this low availability, and confirms the generally accepted assumption that accumulation of PAHs in urban areas is mostly related with a long-term deposition of contaminated particles. The comparison of measured PAHs concentrations in earthworm tissues with the ones predicted based on theoretical models, reinforce that risks based on total levels are overestimated, but it can be a good initial approach for urban soils. This study also highlights the need of more reliable ecotoxicological data.

Tunable spin and valley dependent magneto-optical absorption in molybdenum disulfide quantum dots.

Photonic quantum computer, quantum communication, quantum metrology and quantum optical technologies rely on the single-photon source (SPS). However, the SPS with valley-polarization remains elusive and the tunability of magneto-optical transition frequency and emission/absorption intensity is restricted, in spite of being highly in demand for valleytronic applications. Here we report a new class of SPSs based on carriers spatially localized in two-dimensional monolayer transition metal dichalcogenide quantum dots (QDs). We demonstrate that the photons are absorbed (or emitted) in the QDs with distinct energy but definite valley-polarization. The spin-coupled valley-polarization is invariant under either spatial or magnetic quantum quantization. However, the magneto-optical absorption peaks undergo a blue shift as the quantization is enhanced. Moreover, the absorption spectrum pattern changes considerably with a variation of Fermi energy. This together with the controllability of absorption spectrum by spatial and magnetic quantizations, offers the possibility of tuning the magneto-optical properties at will, subject to the robust spin-coupled valley polarization.

Electrochemical cell design for the impedance studies of chlorine evolution at DSA(®) anodes.

A new electrochemical cell design suitable for the electrochemical impedance spectroscopy (EIS) studies of chlorine evolution on Dimensionally Stable Anodes (DSA(®)) has been developed. Despite being considered a powerful tool, EIS has rarely been used to study the kinetics of chlorine evolution at DSA anodes. Cell designs in the open literature are unsuitable for the EIS analysis at high DSA anode current densities for chlorine evolution because they allow gas accumulation at the electrode surface. Using the new cell, the impedance spectra of the DSA anode during chlorine evolution at high sodium chloride concentration (5 mol dm(-3) NaCl) and high current densities (up to 140 mA cm(-2)) were recorded. Additionally, polarization curves and voltammograms were obtained showing little or no noise. EIS and polarization curves evidence the role of the adsorption step in the chlorine evolution reaction, compatible with the Volmer-Heyrovsky and Volmer-Tafel mechanisms.

Robust effective Zeeman energy in monolayer MoS2 quantum dots.

We report a theoretical investigation on the energy spectrum and the effective Zeeman energy (EZE) in monolayer MoS2 circular quantum dots, subjected to an out-of-plane magnetic field. Interestingly, we observe the emergence of energy-locked modes, depending on the competition between the dot confinement and the applied magnetic field, for either the highest K-valley valence band or the lowest [Formula: see text]-valley conduction band. Moreover, an unusual dot-size-independent EZE behavior of the highest valence and the lowest conduction bands is found. Although the EZEs are insensitive to the variation of quantum confinement, both of them grow linearly with the magnetic field, similar to that in the monolayer MoS2 material. The EZEs along with their 'robustness' against dot confinements open opportunities of a universal magnetic control over the valley degree of freedom, for quantum dots of all sizes.

Castor bean (Ricinus communis L.) as a potential environmental bioindicator.

Biomonitoring of air quality using living organisms is a very interesting approach to environmental impact assessment. Organisms with a vast distribution, such as plants, are widely used for these purposes. The castor bean (Ricinus communis L.) is an oleaginous plant that can potentially be used as a bioindicator plant owing to its rapid growth and large leaves, which have a wide surface area of contact with the air and the pollutants therein. This study investigated the the bioindicator potential of the castor bean by performing several tests. We observed statistically significant differences in the concentrations of chlorophyll a and b in the leaves of plants in polluted areas compared to that in the control group plants, which were located in a pollution-free area. Leaves of plants in the former group had higher peroxidase activity and showed a greater buffering ability than those of plants in the control group. The pKa values obtained via buffering capacity tests, revealed the presence of aminoazobenzene (an industrial dye) in leaves of R. communis. Genotoxicity was evaluated through the comet assay technique and revealed that other than some differences in DNA fragmentation, there is no statistically significant difference in this parameter between places analyzed. Our data indicate that R. communis can be a highly useful biological indicator. Further, we hypothesized that the castor bean can be a potential candidate for phytoremediation owing its physiological buffering capacity when exposed to substantial pollution.

Antimutagenic action of the triterpene betulinic acid isolated from Scoparia dulcis (Scrophulariaceae).

The mutagenic and antimutagenic activities of triterpene betulinic acid {3b-3-hydroxy-lup-20(29)-en-28-oic} isolated from the roots of Scoparia dulcis (Scrophulariaceae) were analyzed using the somatic mutation and recombination test (SMART) in the wings of Drosophila melanogaster. The mutagenic potential of betulinic acid was evaluated at 3 different concentrations (1.64, 3.28, and 6.57 mM). Antimutagenic activity evaluation was performed by co-treatment trials in which the flies received betulinic acid at 3 different concentrations in addition to 10 mM pro-mutagenic urethane. The results demonstrated that betulinic acid was not capable of causing DNA damage. However, the frequency of small single spots, large spots, and twin spots was significantly reduced. In the high bioactivation cross, betulinic acid was significantly active and exerted enhanced antimutagenic activity, possibly as a desmutagen.

Assessment of the influence of traffic-related particles in urban dust using sequential selective extraction and oral bioaccessibility tests.

Urban dust is a heterogeneous mix, where traffic-related particles can combine with soil mineral compounds, forming a unique and site-specific material. These traffic-related particles are usually enriched in potentially harmful elements, enhancing the health risk for population by inhalation or ingestion. Urban dust samples from Estarreja city and traffic-related particles (brake dust and white traffic paint) were studied to understand the relative contribution of the traffic particles in the geochemical behaviour of urban dust and to evaluate the long-term impacts of the metals on an urban environment, as well as the risk to the populations. It was possible to distinguish two groups of urban dust samples according to Cu behaviour: (1) one group with low amounts of fine particles (<38 µm), low contents of organic material, high percentage of Cu in soluble phases, and low Cu bioaccessible fraction (Bf) values. This group showed similar chemical behaviour with the brake dust samples of low- to mid-range car brands (with more than 10 years old), composed by coarser wear particles; and (2) another group with greater amounts of fine particles (<38 µm), with low percentage of Cu associated with soluble phases, and with greater Cu Bf values. This group behaved similar to those found for brake dust of mid- to high-range car brands (with less than 10 years old). The results obtained showed that there is no direct correlation between the geoavailability of metals estimated by sequential selective chemical extraction (SSCE) and the in vitro oral bioaccessibility (UBM) test. Thus, oral bioaccessibility of urban dust is site specific. Geoavailability was greatly dependent on particle size, where the bioaccessibility tended to increase with a reduction in particle diameter. As anthropogenic particles showed high metal concentration and a smaller size than mineral particles, urban dusts are of major concern to the populations' health, since fine particles are easily re-suspended, easily ingested, and show high metal bioaccessibility. In addition, Estarreja is a coastal city often influenced by winds, which favours the re-suspension of small-sized contaminated particles. Even if the risk to the population does not represent an acute case, it should not be overlooked, and this study can serve as baseline study for cities under high traffic influence.

The mobility and human oral bioaccessibility of Zn and Pb in urban dusts of Estarreja (N Portugal).

Twenty-one samples of urban dust were collected from Estarreja city (Portugal). The main objective of this work was to assess the potential availability of Pb and Zn present dust samples from Estarreja city via the oral ingestion exposure route using a combination of geochemical tests: (a) using sequential extraction to identify the fractionation of the Pb and Zn within the geochemical components that make up the dust and (b) in vitro bioaccessibility (BA) measurements to identify which components are the source(s) of the bioaccessible fraction (Bf). These samples were analysed for their quasi-total contents of Pb and Zn by inductively coupled plasma mass spectrometry, for their element solid-phase distribution using selective sequential extraction method and for the Bfs of these elements using a physiologically based extraction test. The study showed that the concentrations of Zn were higher than Pb, but both are site-specific. The sequential extraction test shows that the exchangeable and acid-soluble phases are important bearing phases for Pb and Zn. The BA test showed that a high proportion of the total concentration is available for absorption into the human body (ranges from 22.5 to 84.1% for Pb and 28.7 to 86.3% for Zn).