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Carbon xerogels (CXs) were synthesized by polycondensation of resorcinol and formaldehyde, followed by thermal annealing, and subjected to hydrothermal oxidation. Solid-phase extraction (SPE) cartridges were filled with CXs and tested for extraction of metaflumizone and other seven environmental micropollutants (acetamiprid, atrazine, isoproturon, methiocarb, carbamazepine, diclofenac, and perfluorooctanesulfonic acid) before chromatographic analysis. The recoveries obtained with the pristine CX were low for most analytes, except for metaflumizone (69 ± 5%). Moreover, it was concluded that the adsorption/desorption process of the micropollutants performed better on CXs with a less acidic surface (i.e., pristine CX). Thus, cartridges were prepared with pristine CX and multi-walled carbon nanotubes (MWCNTs) in a multi-layer configuration. This reusable cartridge was able to simultaneously extract the eight micropollutants and was used to validate an analytical methodology based on SPE followed by ultra-high performance liquid chromatography-tandem mass spectrometry. A widespread occurrence of 6/8 target compounds was observed in surface water collected in rivers supplying three drinking water treatment plants and in the resulting drinking water at the endpoint of each distribution system. Therefore, the first study employing CXs and MWCNTs as sorbent in multi-layer SPE cartridges is herein reported as a proof of concept for determination of multi-class water micropollutants.

We have developed an efficient chalcogenylation of electron-rich naphthalene derivatives catalyzed by FeCl3 and KI. The methodology provides access to several nonsymmetrical diorganoyl chalcogenides (S, Se) by selective C1 chalcogenylation of 2-naphthols or 2-naphthylamines using simple and cheap catalysts. Several control experiments supported the hypothesis that a redox reaction between Fe(III) and KI produces I2, which catalyzed the chalcogenylation.

The excess of salts can affect several processes in the crops, and nitrogen (N) can attenuate the depressive effect of salinity. The objective was to evaluate the influence of nitrogen doses on the growth and gas exchange of corn crop irrigated with saline water. The experiment was conducted from June to September 2019 at the University of International Integration of Afro-Brazilian Lusophony, Redenção, CE, Brazil. The experimental design was completely randomized, in a 2 x 3 factorial scheme (supply water of 0.3 dS m-1 and saline solution of 3.0 dS m-1) and three nitrogen doses, 0, 80, and 160 kg ha-1, corresponding to 0, 50, and 100% of the recommended dose respectively, with six repetitions. At 30 and 45 days after sowing (DAS), plant height, leaf area, number of leaves, photosynthesis, transpiration, and stomatal conductance were evaluated. Saline stress affects plant height, leaf area, photosynthesis, transpiration, and conductance at 30 DAS. The doses of 80 and 160 kg ha-1 provide greater performance in plant height, leaf area, photosynthesis, transpiration, and conductance at 30 DAS. The use of low salinity water and doses of 80 and 160 kg ha-1 were more efficient in terms of plant height, leaf area, photosynthesis, transpiration, and conductance at 45 DAS. The dose of 160 kg ha-1 of N attenuates the harmful effects of salts in AG 1051 hybrid maize plants, providing higher values of photosynthesis, transpiration, and stomatal conductance at 45 DAS when irrigated with water of 3.0 dS m-1.

A polypyridyl ligand functionalized with a long alkyl chain (LC10) was prepared. The reaction of LC10 with selected iron salts of different stoichiometries formed two metal complexes: [Fe(LC10)(Cl)3] (1) and [Fe(LC10)2](ClO4)3·5H2O (2), which were fully characterized by a suite of physicochemical methods in which 1 had its crystal structure determined by XRD. The structural and spectroscopic data were tightly supported by DFT and TD-DFT calculations. The interaction between these two iron complexes and salmon sperm DNA was monitored spectrophotometrically in the UV region and binding constants (Kb) were estimated and docking studies were performed using the PatchDock® server. Both complexes had their biocide activity confirmed against selected microorganisms: Gram-positive (S. aureus) and Gram-negative (E. coli) bacteria, A. fumigatus and S. cerevisiae with good values of MBC and IC50. Finally, the cytotoxic activities of 1 and 2 were probed against the erythroleukemia K562 cell line after 24, 48 and 72 h of incubation. For all biological studies, the magnitude of the activity followed the order: 2 > 1 > LC10, which demonstrates the enhanced effect of iron when coordinated to the bioinspired ligand.

espanolEl frijol caupi es un cultivo importante para la seguridad alimentaria de la poblacion mundial; sin embargo, su produccion es afectada constantemente por la interferencia de las malezas. El objetivo de esta investigacion fue determinar el efecto de la interferencia de las malezas en diferentes densidades de competencia sobre las caracteristicas de crecimiento del cultivo. El estudio fue conducido mediante diseno de bloques al azar en arreglo factorial 2x4 para analisis del cultivo y 2x3 para las malezas. Fueron estudiadas dos especies de maleza (Cenchrus echinatus y Rottboellia exaltata) y cuatro intensidades de competencia (cero, dos, cuatro y seis individuos por maceta), con cuatro repeticiones. Las evaluaciones fueron realizadas en la etapa de floracion del cultivo y las variables medidas fueron area foliar, masa seca de las hojas, del tallo, de la raiz (MSR), de la parte aerea (MSPA), masa seca total y la relacion MSR/MSPA. Ademas, fueron cuantificadas en las malezas la masa seca de la parte aerea (MSPAM) y de la raiz (MSRM). El aumento de la densidad de competencia de las malezas resulto en disminucion de los valores de todas las variables analizadas en el cultivo. En las malezas, C. echinatus mostro mayor MSPAM que R. exaltata, aunque no hubo diferencias en MSRM. Ambas malezas afectan negativamente el crecimiento de las plantas de frijol, aunque con C. echinatus el efecto es aun mayor. El efecto de interferencia es mayor a medida que aumenta la densidad de las malezas EnglishCowpea is an important crop for the food security of the world population. However, their production is constantly affected by weed interferences. The objective of this research was to determine the effect of two different weeds at different densities of competition on the growth characteristics of the crop. The study was conducted using a randomized block design in a factorial arrangement of the treatments (2x4 for analysis in cowpea, and 2x3 for weeds). The weed species (Cenchrus echinatus and Rottboellia exaltata) and four competition densities (zero, two, four, and six individuals per pot), with four repetitions, were studied at the crop flowering stage. We measured leaf area, leaf and stem dry mass, root dry mass (RDM), dry mass of the aerial part (DMAP), total dry mass, and the ratio (RDM/DMAP); additionally, the dry mass of the aerial part and root (DMAW and DMRW) of the weeds was measured. The increase in the density of the weeds resulted in a decrease in the values of all the variables of the crop. In the case of weeds, C. echinatus showed higher DMAW than R. exaltata although there were no differences in DMRW. Both weeds negatively affect the growth of bean plants, though with C. echinatus the effect is even greater. The interference effect is higher as the density of the weeds increases

Brazilian sweet cassava consumers are becoming more and more demanding in relation to sanitary conditions, organoleptic and nutritional characteristics of this vegetable products and their derivatives. Thus, more nutritious, early, productive, adapted to mechanized planting and good culinary quality sweet cassava cultivars were developed. This study aimed, therefore, to evaluate the performance of four sweet cassava cultivars in Uberaba, in Triângulo Mineiro region. The experiments were carried out in the experimental field of Faculdades Associadas de Uberaba (FAZU) during two harvest seasons. We adopted a randomized block design with three replicates, each plot consisting of four lines with ten plants. Trait averages were grouped by the Scott & Knott test. The results showed that cultivars BRS 399, BRS 397 and IAC 576-70 have potential to be grown in the region, since they showed root yield higher than 32 t ha-1 and up to 30-minute cooking time. BRS 399 stood out for its performance, showing root yield of 37 t ha-1 and 48 t ha-1 in 2015/2016 and 2016/2017 harvest seasons, respectively, with short-time cooking and presenting shoot productivities which allow its use even as animal feed. RESUMO Os consumidores brasileiros de mandioca de mesa estão se tornando mais exigentes quanto aos aspectos sanitários, organolépticos e nutricionais dos produtos e derivados de mandioca que adquirem. Em resposta, foram desenvolvidas cultivares de mandioca de mesa, mais nutritivas, precoces, produtivas, adaptadas ao plantio mecanizado e com boas qualidades culinárias. Nesse cenário, oportunizou-se a presente pesquisa, cujo objetivo foi avaliar o desempenho de quatro novas cultivares de mandioca de mesa em Uberaba na região do Triângulo Mineiro. Os experimentos foram conduzidos no campo experimental das Faculdades Associadas de Uberaba (FAZU) durante duas safras. Foi utilizado o delineamento de blocos casualizados com três repetições, cada parcela composta por quatro linhas com dez plantas. As médias dos caracteres foram agrupadas por meio do teste de Scott & Knott. Os resultados revelaram que as cultivares BRS 399, BRS 397 e IAC 576-70 têm potencial para cultivo na região, uma vez que apresentaram produtividade de raízes superior a 32 t ha-1 e tempo para o cozimento de até 30 minutos. A BRS 399 se destacou pelo desempenho apresentado, com produtividade de raízes de 37 t ha-1 e 48 t ha-1 nas safras 2015/2016 e 2016/2017, respectivamente, com baixos tempos para o cozimento e com produtividades de parte aérea que permitem utilizar a mesma até na alimentação animal.

Pristine and functionalized multi-walled carbon nanotubes (MWCNTs) were investigated as adsorbent materials inside solid-phase extraction (SPE) cartridges for extraction and preconcentration of 8 EU-relevant organic micropollutants (with different pKa and polarity) before chromatographic analysis of surface water. The recoveries obtained were > 60% for 5/8 target pollutants (acetamiprid, atrazine, carbamazepine, diclofenac, and isoproturon) using a low amount of this reusable adsorbent (50 mg) and an eco-friendly solvent (ethanol) for both conditioning and elution steps. The introduction of oxygenated surface groups in the carbon nanotubes by using a controlled HNO3 hydrothermal oxidation method, considerably improved the recoveries obtained for PFOS (perfluorooctanesulfonic acid) and methiocarb, which was ascribed to the hydrogen bond adsorption mechanism, but decreased those observed for the pesticide acetamiprid and for two pharmaceuticals (carbamazepine and diclofenac), suggesting π–π dispersive interactions. Moreover, a good correlation was found between the recovery obtained for methiocarb and the amount of oxygenated surface groups on functionalized MWCNTs, which was mainly attributed to the increase of phenols and carbonyl and quinone groups. Thus, the HNO3 hydrothermal oxidation method can be used to finely tune the surface chemistry (and texture) of MWCNTs according to the specific micropollutants to be extracted and quantified in real water samples.

In this work, the combination of advanced oxidation technologies (AOTs) and direct contact membrane distillation (DCMD) was investigated for the treatment of municipal wastewater collected from the secondary clarifier of a municipal wastewater treatment plant (MWWTP). Average removal efficiencies of the 12 micropollutants present in the wastewater samples were higher than 95 % with ozonation (O3) and photolytic ozonation (UV/O3), whereas only near 50 % of removal efficiency was achieved with UV-peroxidation (UV/H2O2). When the ozone-based processes were combined with DCMD, the concentration of these micropollutants were below the detection limits in the respective permeate, increasing the quality of the treated water. However, the permeate fluxes in DCMD were remarkably higher when the wastewater was pre-treated with UV/H2O2 instead of O3, most probably due to the better disinfection achieved by UV/H2O2. It was also confirmed that the dissolved organic carbon (DOC) of the wastewater strongly affects the permeate fluxes achieved by DCMD. In this regard, the combination of the oxidation and membrane separation processes is more appropriate for wastewaters with low DOC contents (

Owing to climate change, species’ geographical distribution may be extended, reduced or displaced in the future. Across species’ ranges, novel climate conditions may also expose species to thermal conditions for which they are not adapted. Migration toward more suitable climates will, however, only be possible if species are able to keep pace with climate change. Here, we analyze different metrics to predict the impacts of climate change on the distribution of Amazon primates. We found that this iconic group will be exposed to novel climate conditions in a large portion of their territories and most species might not be able to track their preferred environmental conditions, even when their range is forecasted to expand. Remaining future populations are expected to become fragmented and to occupy sub-optimal conditions at the periphery of their projected bioclimatic envelopes. Our results suggest that climate change may have unprecedented impacts on Amazon biodiversity, especially for species with low dispersal ability, such as primates. In addition to deforestation, hunting, and disease spread, climate change is likely to add up to conservation-defying feedbacks for Amazon primate populations’ fitness and resilience dynamics.

Introduction:Audits play a critical role in maintaining the integrity of observational cohort data. While previous work has validated the audit process, sending trained auditors to sites (“travel-audits”) can be costly. We investigate the efficacy of training sites to conduct “self-audits.”Methods:In 2017, eight research groups in the Caribbean, Central, and South America network for HIV Epidemiology each audited a subset of their patient records randomly selected by the data coordinating center at Vanderbilt. Designated investigators at each site compared abstracted research data to the original clinical source documents and captured audit findings electronically. Additionally, two Vanderbilt investigators performed on-site travel-audits at three randomly selected sites (one adult and two pediatric) in late summer 2017.Results:Self- and travel-auditors, respectively, reported that 93% and 92% of 8919 data entries, captured across 28 unique clinical variables on 65 patients, were entered correctly. Across all entries, 8409 (94%) received the same assessment from self- and travel-auditors (7988 correct and 421 incorrect). Of 421 entries mutually assessed as “incorrect,” 304 (82%) were corrected by both self- and travel-auditors and 250 of these (72%) received the same corrections. Reason for changing antiretroviral therapy (ART) regimen, ART end date, viral load value, CD4%, and HIV diagnosis date had the most mismatched corrections.Conclusions:With similar overall error rates, findings suggest that data audits conducted by trained local investigators could provide an alternative to on-site audits by external auditors to ensure continued data quality. However, discrepancies observed between corrections illustrate challenges in determining correct values even with audits.

This work aimed to investigate the possible effect of 2 quenchers commonly used in H2O2-based advanced oxidation technologies (AOTs), i.e. catalase and sodium sulphite (Na2SO3), on the analytical signal of 3 detectors coupled to liquid chromatography (LC): tandem mass spectrometry (LC-MS/MS), fluorescence detection (LC-FD) and LC-diode array detection (LC-DAD). The observation of analytical interferences for a group of compounds when studying the removal by continuous mode UV/H2O2 of 26 micropollutants (MPs) from a spiked surface water (SW), for which the residual H2O2 in the samples was quenched by Na2SO3, triggered the need of understanding these effects and thus catalase was used as comparative quencher. From the 26 MPs having a wide range of polarity and pKa, those monitored after electrospray ionization (ESI) under positive ionization (PI) mode and presenting a pKa higher than 5.9 revealed a great signal suppression, but only when using Na2SO3 as H2O2 quencher. In this sense, we further explored this effect by selecting 2 MPs, metoprolol and diclofenac, which had respectively signal suppression and no interference in the LC-MS/MS response. These MPs were analysed before and after addition of H2O2 and catalase or Na2SO3 in reaction vials, using: (i) different detectors coupled to LC, namely LC-MS/MS with ESI under PI and negative ionization (NI) modes, LC-FD and LC-DAD; (ii) different environmental matrices (SW, drinking water, wastewater) and ultrapure water; and (iii) different magnitude levels (0.1–10 mg L−1). The results demonstrated a remarkable signal suppression in LC-MS/MS analyses under PI mode for those compounds with pKa higher than 5.9, confirming the interfering effect of H2O2/Na2SO3. To the best of our knowledge, the analytical interference in the LC-MS/MS analysis, after adding Na2SO3 to quench H2O2 in AOTs experiments was never reported before and the results presented herein support the recommendation to use catalase instead of Na2SO3 as quencher in AOTs studies.

Self-organized nanowires were formed on topographically and orderly modified surfaces by a focused ion beam. Silver catalyst nanoparticles were deposited on the regular shallow hole arrangements on the InP (001), which were prepared with three different gallium ion doses, and acted as preferential nucleation sites for InAs grown using Metal-Organic Vapor Phase Epitaxy. Ion doses ranging from 0.8 × 1014 to 4.2 × 1014 Ga+/cm2 were used, and InAs was grown with two sub-monolayer coverages. Two-dimensional ordered InAs nanowire arrays were grown in the templates, despite the randomly deposited silver nanoparticles and the cavities full of defects generated by ion beam irradiation. For the 1 s growth time sample using templates produced with a high ion dose, most of the InAs nanostructures were found to fill either entirely or a large fraction of the cavities. Nanowires were grown in the 2 s growth time sample, using low and medium ion dose. Although the nanowires' growth mechanism is described by the most widely employed vapor-liquid-solid model, the site-selective nanowires growth with randomly deposited catalyst nanoparticle occurs due to net adatom flow to the cavities assisted by modified surface potential. The competition between the coarsening and the vapor-liquid-solid mechanisms plays a critical role in determining the growth of nanowires or islands by providing a simple model able to properly describe the type of the nanostructure (islands or nanowires) dependence with the growth time and the ion dose.

Glycerol from biodiesel production was used as a substrate for valerate production in a 13.1-L anaerobic filter with an open microbiome. Ethanol at 15% of the influent chemical oxygen demand was supplemented as an additional electron donor source. The 114-day experimental period was divided in three phases which included initial adaptation phase, external sludge addition from a caproic acid producing reactor and valerate extraction using a pertraction system. Propionate (0.63–1.75 g COD L−1 day−1) and valerate (0.86–1.81 g COD L−1 day−1) were the main carboxylates formed throughout all operational phases. An increase in production rates of butyrate (0.26–0.31 g COD L−1 day−1), caproate (0.01–0.08 g COD L−1 day−1), and 1,3-propanediol (0.43–0.52 g COD L−1 day−1) was observed with addition of external caproic acid producing sludge rich in Clostridium members. In the operational phase with pertraction, a sudden decrease in 1,3-propanediol and concomitant increase in acid production were verified. Propionate and valerate reached higher production rates compared with the other two phases, suggesting that the pertraction system favored the oxidative pathway of glycerol fermentation. Valerate extraction reached a maximum of 30 g COD m−2 day−1. The filter microbiome was highly diverse with Simpson index values close to 0.1 for the four sludge samples collected, and a concomitant increase in Megasphaera elsdenii and an increase in valerate production rates were observed. Hence, high valerate production and extraction rates through the carboxylate platform are a feasible alternative for crude glycerol valorization with a great potential for improvement in future research.

Climate change will redistribute the global biodiversity in the Anthropocene. As climates change, species might move from one place to another, due to local extinctions and colonization of new environments. However, the existence of permeable migratory routes precedes faunal migrations in fragmented landscapes. Here, we investigate how dispersal will affect the outcome of climate change on the distribution of Amazon's primate species. We modeled the distribution of 80 Amazon primate species, using ecological niche models, and projected their potential distribution on scenarios of climate change. Then, we imposed landscape restrictions to primate dispersal, derived from a natural biogeographical barrier to primates (the main tributaries of the Amazon river) and an anthropogenic constraint to the migration of many canopy‐dependent animals (deforested areas). We also highlighted potential conflict zones, i.e. regions of high migration potential but predicted to be deforested. Species response to climate change varied across dispersal limitation scenarios. If species could occupy all newly suitable climate, almost 70% of species could expand ranges. Including dispersal barriers (natural and anthropogenic), however, led to range expansion in only less than 20% of the studied species. When species were not allowed to migrate, all of them lost an average of 90% of the suitable area, suggesting that climate may become unsuitable within their present distributions. All Amazon primate species may need to move as climate changes to avoid deleterious effects of exposure to non‐analog climates. The effect of climate change on the distribution of Amazon primates will ultimately depend on whether landscape permeability will allow climate‐driven faunal migrations. The network of protected areas in the Amazon could work as ‘stepping stones’ but most are outside important migratory routes. Therefore, protecting important dispersal corridors is foremost to allow effective migrations of the Amazon fauna in face of climate change and deforestation.

Heterogeneous photocatalysis under visible light was employed for the degradation of organic micropollutants (MPs) found in the biologically treated effluents of an urban wastewater treatment plant (UWWTP). The irradiation source consisted in 4 light emitting diodes (LEDs) with a nominal power of 400–500 W m–2 at 417 nm. Metal-free exfoliated graphitic carbon nitride (gCNT), which was synthetized through a simple thermal treatment using dicyandiamide as precursor, was employed as photocatalyst. The gCNT material was characterized using different techniques: N2 adsorption isotherms at 77 K, electron microscopy (scanning and transmission) and diffuse reflectance UV–Vis. The photocatalytic performance of the material was compared to the commercial TiO2-P25, confirming that gCNT led to a remarkable higher removal efficiency of the target MPs. Most of these MPs were removed in less than 10 min to levels below the limit of quantification (carbamazepine > isoproturon > clopidogrel > diclofenac > atenolol > bezafibrate > tramadol > venlafaxine > fluoxetine). Indirect photolysis, resulting from the secondary reactive oxidants generated during the irradiation of the aqueous matrix components, was found to partially contribute for the elimination of the occurring MPs. In addition, the gCNT photocatalyst was immobilized on glass rings for use under continuous mode operation, a minimum residence time of 25 min being required to attain significant removal efficiencies. Phytotoxicity experiments showed that heterogeneous photocatalysis did not enhance the toxicity of the wastewaters.

We report the synthesis of a new phenalenyl ligand, functionalized with a methyl ester electron withdrawing group, named 9-hydroxy-1-oxo-1H-phenalen-5-methyl carboxylate (L), and the generated complexes [Ru(bpy)2L]PF6 and [(η6-C6H6)Ru(L)Cl]. Compounds were characterized by spectroscopic and X-ray diffraction methods, and their electrochemical behavior was investigated via cyclic voltammetry and UV-vis spectroelectrochemistry. The one-electron oxidized compounds have an unpaired electron located in the phenalenyl ring, as supported by theoretical calculations (DFT) and EPR results. Langmuir-Blodgett (LB) films deposited by [Ru(bpy)2L]2+/3+ species mixed with stearic acid are electroactive, showing a quasi-reversible wave with E1/2Film1 = 0.74 V and E1/2Film2 = 0.81, which are promising systems that allow access to immobilized open-shell species in the film.

This work presents the development of an enantioselective method to quantify chiral drugs (CDs) in surface water and its application in the Douro River estuary monitoring. Different classes of CDs were targeted, including 23 compounds, namely beta-blockers, antidepressants, one beta2-adrenergic agonist, non-steroidal anti-inflammatory drugs, stimulants, and some illicit drugs as cocaine (COC) and its metabolites, and amphetamines. The analytical method was based on an innovative application of solid phase extraction (SPE), followed by liquid chromatography-tandem mass spectrometry (LC–MS/MS) using a triple quadrupole analyzer. The ground-breaking approach of SPE consists in the use of Oasis® MCX cartridges to pre-concentrate 500 mL of water samples, allowing the simultaneous extraction of acidic, basic and neutral analytes, rather than the conventional recovery of basic compounds only. Two chiral columns were used for enantiomeric separation in reverse elution mode, a Chirobiotic™V and a Pirkle type Whelk-O®1, for basic and acidic compounds, respectively. The method validation demonstrated good linearity (r2 > 0.99), selectivity and sensitivity, with method detection limits between 0.01 and 2.66 ng L−1 and method quantification limits between 0.02 and 5.71 ng L−1. The developed method was successfully applied to monitor daily variations along one week in surface waters collected in 5 locations of the Douro River estuary. Tramadol (TRM) and its metabolite N-desmethyltramadol (NDT), presented high concentrations near the affluent of a tributary river, while the second eluted enantiomer of O-desmethyltramadol (ODT) was found at high concentrations at the mouth of the Douro River. The metabolite NDT was quantified at higher concentrations than TRM. Venlafaxine (VNF) was found at high concentrations near the affluent of the same tributary river, but its metabolite, O-desmethylvenlafaxine (ODV), was found at concentrations 3 times higher. COC was found every day at all sampling points along the estuary, with slight variations.

This work presents numerical results for the thermal performance of a Solar Volumetric Receiver (SVR). The Thermal Non-Equilibrium Model and Rosseland approximation were used. Radiation boundary condition was implemented at the absorber inlet. The numerical technique employed for discretizing the governing equations was the control volume method with a boundary-fitted non-orthogonal coordinate system. The SIMPLE algorithm was used to handle the pressure-velocity coupling. Effects of inlet velocity (uin), porosity (ϕ), medium permeability (K), and thermal conductivity ratio (ks/kf) on the solid and fluid temperatures were investigated. Reduction of temperatures as porosity increases or thermal conductivity decreases was observed, in addition to an increase in entry length for lower porosities or higher thermal conductivity ratios. Increase in inlet solid temperature as permeability increases was accompanied by a longer entry length and reduced final equilibrium temperature.

Micropollutants (MPs) in the aquatic compartments are originated from many sources and particularly from the effluents of urban wastewater treatment plants (UWWTPs). Advanced oxidation technologies (AOTs) usually applied after biological processes, have recently emerged as effective tertiary treatments for the removal of MPs, but the oxidation rates of the single compounds may be largely affected by the constituent species of the water matrix. These species include dissolved organic matter and inorganic species (e.g., carbonate, bicarbonate, nitrite, sulphate, chloride). This review analyses the impact of such substances on common AOTs including photolysis, UV/H2O2, Fenton, photocatalysis, and ozone-based processes. The degradation efficiency of single MPs by AOTs results from the combined impact of the water matrix constituents, which can have neutral, inhibiting or promoting effect, depending on the process and the mechanism by which these water components react. Organic species can be either inhibitors (by light attenuation; scavenging effects; or adsorption to catalyst) or promoters (by originating reactive oxygen species (ROS) which enhance indirect photolysis; or by regenerating the catalyst). Inorganic species can also be either inhibitors (by scavenging effects; formation of radicals less active than hydroxyl radicals; iron complexation; adsorption to catalyst or decrease of its effective surface area) or promoters (e.g., nitrate ions by formation of ROS; iron ions as additional source of catalyst). The available data reviewed here is limited and the role and mechanisms of individual water components are still not completely understood. Further studies are needed to elucidate the wide spectrum of reactions occurring in complex wastewaters and to increase the adoption of AOTs in UWWTPs.

Lignocellulosic fibers extracted from plants are considered an interesting raw material for environmentally friendly products with multiple applications. This work investigated the feasibility of using hemp- and flax-based materials in the form of felts as biosorbents for the removal of metals present in aqueous solutions. Biosorption of Al, Cd, Co, Cu, Mn, Ni and Zn from a single solution by the two lignocellulosic-based felts was examined using a batch mode. The parameters studied were initial metal concentration, adsorbent dosage, contact time, and pH. In controlled conditions, the results showed that: (i) the flax-based felt had higher biosorption capacities with respect to the metals studied than the hemp-based felt, (ii) the highest removal efficiency was always obtained for Cu ions, and the following order of Cu &gt, Cd &gt, Zn &gt, Ni &gt, Co &gt, Al &gt, Mn was found for both examined biosorbents, (iii) the process was rapid and 10 min were sufficient to attain the equilibrium, (iv) the efficiency improved with the increase of the adsorbent dosage, and (v) the biosorption capacities were independent of pH between 4 and 6. Based on the obtained results, it can be considered that plant-based felts are new, efficient materials for metal removal.

The coherence time of the 17-electron, mixed sandwich complex [CpTi(cot)], (η8 -cyclooctatetraene)(η5 -cyclopentadienyl)titanium, reaches 34 μs at 4.5 K in a frozen deuterated toluene solution. This is a remarkable coherence time for a highly protonated molecule. The intramolecular distances between the Ti and H atoms provide a good compromise between instantaneous and spin diffusion sources of decoherence. Ab initio calculations at the molecular and crystal packing levels reveal that the characteristic low-energy ring rotations of the sandwich framework do not yield a too detrimental spin-lattice relaxation because of their small spin-phonon coupling. The volatility of [CpTi(cot)] and the accessibility of the semi-occupied, non-bonding d z 2 orbital make this neutral compound an ideal candidate for single-qubit addressing on surface and quantum sensing in combination with scanning probe microscopy.

This work analyzes the role of natural groundwater, as well as the effect of HCO3−, Ca2+, Mg2+, K+, SO42- and Cl− concentrations, upon the photocatalytic nitrate reduction using ilmenite as catalyst and oxalic acid as hole scavenger. The nitrate removal and the selectivity towards N2 are significantly limited compared to previous experiments using ultrapure water matrix. Calcium (Ca2+), bicarbonate (HCO3−) as well as pH are claimed as the major controlling factors related to the process yield. Thus, Ca2+ promotes the formation of insoluble oxalate microcrystals, reducing the amount of hole scavenger available. The presence of HCO3− leads to a steeply increase in the pH value, favoring the adsorption onto the ilmenite surface of ions OH−instead of NO3−, NO2− and C2O42. The aforementioned issues are overcome by working with C2O42−/NO3− ratio well above the stoichiometric one, that also maintains the pH value in an acid range. A completed depletion of the starting NO3−, the no detection of either NO2− or NH4+ in the aqueous phase, and a selectivity towards N2 above 95% were achieved using two times the stoichiometric dose, This work has been supported by AEI (10.13039/501100011033) through the project PID2019-106884GB-I00 and Comunidad de Madrid through the project P2018/EMT-4341. A.R.R thanks the Post-Doctoral scholarship awarded by the public agency São Paulo State Research Foundation (FAPESP), grant #2018/09697-8. J. Carbajo wants to thank the Ministerio de Ciencia, Innovación y Universidades (MICIU) for a grant under the Juan de la Cierva_Incorporación programme (IJCI-2017-32682)

We have characterized the NF-YB gene family in R. communis using bioinformatics, ecotopic expression, and transcriptomics. A total of 14 RcNF-YB genes were identified in R. communis genome using the conserved NF-YB region. This number is similar to what is found in A. thaliana (13 genes) and O. sativa (11 genes), whereas it is considerably lower to what is found in P. trichocarpa (21 genes) and S. lycopersycum (29 genes). Several regulatory cis-elements were identified in the promoter region, including low temperature, defense and stress, MIC, MYB, and abscisic acid. RcNF-YB is strongly modulated by temperature and it is dependent on the stage of germination. In general, RcNF-YB genes showed higher expression levels in dry seeds and early imbibition (EI) samples as compared to later stages of seedling development. Ectopic expression of RcNF-YB8 reduced flowering time in Arabidopsis reducing the time required for the formation of the first visible bud, the time required to open the first flower, and the time required for the formation of the first visible silique. At the end of the life cycle, ectopic expression of RcNF-YB8 affected plant height (PH), silique length (SL), the total number of silique per plant, 1000-seed weight, and seed size. Our data demonstrated the role of RcNF-YB8 in flowering time, plant height and seed production, and it shows that it may constitute a key target gene for breeding superior R. communis genotypes.

Without any doubt, the 21st century has kick-started a great evolution in all aspects of our everyday life [...]

Despite its importance as a medicinal plant, there is a lack of studies that assessed the chemical composition of A. cochliacarpos extracts. Herein, we used a metabolite profiling approach and chemometrics as a powerful strategy to correlate the chemical composition with the antioxidant activity of A. cochliacarpos extracts. Extracts obtained with ethyl acetate showed greater antioxidant activity and higher total phenolic content than extracts obtained with hexane. The chemical composition was assessed by HPLC/HR-MS and it encompassed fatty alcohols, terpenoids, phenolic derivatives, lipids, carotenoid-like compounds, alkaloids, flavonoids, polyketides, and glycerophospholipids. Chemometrics successfully differentiated not only the chemical composition of extracts in response to the nature of the extraction solvent and the botanical part used during extraction but also it allowed us to associate the chemical composition with the antioxidant activity of the extracts, which might be particularly helpful for drug discovery and development programs.

Lepidium meyenii is an edible plant that has been used as a nutritional supplement worldwide due to its medicinal properties. However, most of the studies have focused on the pharmacological activities of the extracts rather than their chemical composition. Herein, we used a combination of a multiplatform metabolite profiling approach and chemometrics to identify bioactive metabolites in L. meyenii. Extracts obtained with ethyl acetate and ethanol showed the promising antioxidant, anti-glioma and antibacterial activities. Sixty metabolites were identified by HPLC-MS, whereas fifteen were identified by GC-MS. Partial least squares discriminant analysis (PLS-DA), hierarchical cluster analysis (HCA), and Variable Importance in Projection (VIP) successfully discriminated extracts obtained in different organic solvents from in natura dry roots and commercial product samples of L. meyenii. Additionally, correlation analysis allowed us to pinpoint potential candidates responsible for each biological activity tested for the extracts, which could be extrapolate for other food-related species.

Corn silk has been widely used as a nutritional and medicinal supplement due to its pharmacological properties, but there is a lack of studies that correlate the extracts’ chemical composition with their biological activities. Herein, we performed the large-scale chemical characterization of corn silk extracts and used chemometrics to correlate the chemical composition with the biological activities of the extracts. Twenty-two metabolites were identified by High-Performance Liquid Chromatography coupled to Mass Spectrometry (HPLC-MS), whereas twelve were identified by Gas Chromatography coupled to Mass Spectrometry (GC–MS). Chemometrics allowed us to discriminate extracts obtained in different organic solvents from in natura and commercial product samples and to pinpoint potential candidate metabolites for the antioxidant and anti-glioma activities. Two flavone glycosides (7 and 8), along with a O-methylated anthocyanidin (26) seems to be the main contributors for the biological activities of the corn silk extracts.

Limited studies, particularly in the low-latitudes, exist that monitor cave ventilation, an important process dictating cave geochemical properties. To investigate cave ventilation, we present multi-year monitoring results, including observations of cave-air CO2, cave-air temperature, and cave-air relative humidity, from three Brazilian caves: Paraiso (4.07°S, 55.45°W), Tamboril (16.19°S, 46.59°W), and Jaragua (21.08°S, 56.58°W). Cave ventilation regimes on numerous temporal scales are established. Highest concentrations of cave-air CO2 are recorded during austral summers from a multi-year monitoring effort at Jaragua Cave. Conversely, lowest cave-air CO2 concentration are recorded during austral winters. The variability in cave-air CO2 is attributed to seasonally varying temperature contrasts between surface- and cave-air, which results in buoyancy-driven cave-air CO2 exchange with surface-air CO2. Speleothem growth as calcite precipitation is expected to be biased towards the austral winter season when cave-air CO2 is lowest. This understanding of cave ventilation affects the geochemical interpretation of speleothems as recorders of past climate change from caves in the low-latitudes. Next, continuous CO2 measurements near the entrance of Tamboril Cave suggest diurnal ventilation attributed to diurnal cave- and surface-air temperature differences. CO2 monitored from the deeper part of Paraiso and Jaragua Cave do not exhibit this diurnal cycle. Further, virtual temperature calculations suggest that buoyancy contrasts between cave- and surface-air drive daily to weekly cave ventilation in all three caves. The established cave ventilation regimes provide an additional framework to interpret speleothem based terrestrial environmental change spanning the low- and mid-latitudes. By investigating spatially disparate caves across Brazil, we find buoyancy driven cave ventilation to be a unifying mechanism. Our results suggest that exchange between cave- and surface-air occurs seasonally in caves across the low- and mid-latitudes. These results suggest buoyancy driven ventilation is important not only at mid-latitudes but also in the tropics where speleothems are typically suited to investigate paleomonsoon variability. Therefore, prior knowledge of cave ventilation in caves that contain speleothems suitable for paleoclimate reconstructions is critical to robustly infer subsequent geochemical trends across different timescales (seasonal - centennial).

One of the main problems that remain in the implant industry is poor osseointegration due to bioinertness of implants. In order to promote bioactivity, calcium (Ca), phosphorus (P) and strontium (Sr) were incorporated into a TiO2 porous layer produced by micro-arc oxidation. Ca and P as bioactive elements are already well reported in the literature, however, the knowledge of the effect of Sr is still limited. In the present work, the effect of various amounts of Sr was evaluated and the morphology, chemical composition and crystal structure of the oxide layer were investigated. Furthermore, in vitro studies were carried out using human osteoblast-like cells. The oxide layer formed showed a triplex structure, where higher incorporation of Sr increased Ca/P ratio, amount of rutile and promoted the formation of SrTiO3 compound. Biological tests revealed that lower concentrations of Sr did not compromise initial cell adhesion neither viability and interestingly improved mineralization. However, higher concentration of Sr (and consequent higher amount of rutile) showed to induce collagen secretion but with compromised mineralization, possibly due to a delayed mineralization process or induced precipitation of deficient hydroxyapatite. Ca-P-TiO2 porous layer with less concentration of Sr seems to be an ideal candidate for bone implants., This work was supported by FCT with the reference projects UID/EEA/04436/2019, M-ERA-NET/0001/2015 and FCT/CAPES Procs.. 4.4.1.00. Also the support of FAPESP is acknowledged (Proc. 2017/24300-4). A.I. Costa is very grateful for the PhD grant through NORTE-08-5369-FSE-000051 project. The authors would like to thank the LABNANO/CBPF and Centro Nacional de Biologia Estrutural e Bioimagem (Cenabio) in Rio de Janeiro for technical support during electron microscopy work.

Ozonation followed by ultrafiltration (O3 + UF) was employed at pilot scale for the treatment of secondary urban wastewater, envisaging its safe reuse for crop irrigation. Chemical contaminants of emerging concern (CECs) and priority substances (PSs), microbial load, estrogenic activity, cell viability and cellular metabolic activity were measured before and immediately after O3 + UF treatment. The microbial load was also evaluated after one-week storage of the treated water to assess potential bacteria regrowth. Among the organic micropollutants detected, only citalopram and isoproturon were not removed below the limit of quantification. The treatment was also effective in the reduction in the bacterial loads considering current legislation in water quality for irrigation (i.e., in terms of enterobacteria and nematode eggs). However, after seven days of storage, total heterotrophs regrew to levels close to the initial, with the concomitant increase in the genes 16S rRNA and intI1. The assessment of biological effects revealed similar water quality before and after treatment, meaning that O3 + UF did not produce detectable toxic by-products. Thus, the findings of this study indicate that the wastewater treated with this technology comply with the water quality standards for irrigation, even when stored up to one week, although improvements must be made to minimise microbial overgrowth.

The exploitation of natural origin macromolecules, as complex physical mixtures or drugs, increases in biomedical or tissue engineering (TE) solutions. Aloe Vera is a highly explored medicinal plant, from which the main polysaccharide is acemannan (ACE). The ACE combination with chitosan and alginate results in interactions that lead to mixed junction zones formation, predicting membrane functionality improvement. This work proposes the development and characterization of ACE-based blended films as a promising strategy to design a nature-derived bioactive platform. The results confirmed that stable complex polyelectrolyte structures were formed through different intermolecular interactions. The films present good dimensional stability, flexibility, an adequate swelling ability with mostly radial water uptake, and a sustainable ACE release to the medium. Positive biological performance of the ACE-based blended films with L929 cells also suggested that they can be applied in TE solutions, with the potential to act as bioactive topical platforms., L.C. Rodrigues especially acknowledges financial support from Portuguese FCT (SFRH/BPD/93697/2013). This work is also financially supported by the FCT R&D&I projects with references PTDC/CTM-BIO/ 4706/2014-(POCI-01-0145-FEDER-016716), PTDC/CTM-CTM/29813/ 2017-(POCI-01-0145-FEDER-029813), PTDC/BII-BIO/31570/2017, and R&D&I Structured Projects with reference NORTE-01-0145- FEDER-000021.

Transmission–Reflection Analysis (TRA) is an inexpensive technique used in distributed monitoring systems for single perturbation tracking. However, TRA is limited to long distance applications ( ~ km), since it has poor spatial resolution ( ~ m) when combined to standard silica fibers. This paper proposes the use of a magnesium and erbium co-doped optical fiber in conjunction with the TRA technique. The goal is to improve spatial resolution and accuracy for detection of loss-inducing disturbances along the sensing fiber. Bending losses are induced at several points of the fiber spaced at 50 cm over a 5.4 m fiber length, where each curve is clearly identified with a maximum hysteresis of 1.65%. The localization of a strong disturbance with an estimated accuracy of ± 0.8 mm near the source end and ± 7.2 mm near the fiber end is analytically demonstrated. Regarding weak disturbances, the proposed approach is vulnerable to noisy measurements. However, the response accuracy has been estimated up to ± 36.7 mm.

The importance of the investigation of magnetic superstorms is not limited to academic interest, because these superstorms can cause catastrophic impact on the modern civilisation due to our increasing dependency on technological infrastructure. In this context, the Carrington storm in September 1859 is considered as a benchmark of observational history owing to its magnetic disturbance and equatorial extent of the auroral oval. So far, several recent auroral reports at that time have been published but those reports are mainly derived from the Northern Hemisphere. In this study, we analyse datable auroral reports from South America and its vicinity, assess the auroral extent using philological and astrometric approaches, identify the auroral visibility at - 17.3{\deg} magnetic latitude and further poleward and reconstruct the equatorial boundary of the auroral oval to be 25.1{\deg} +/- 0.5{\deg} in invariant latitude. Interestingly, brighter and more colourful auroral displays were reported in the South American sector than in the Northern Hemisphere. This north-south asymmetry is presumably associated with variations of their magnetic longitude and the weaker magnetic field over South America compared to the magnetic conjugate point and the increased amount of magnetospheric electron precipitation into the upper atmosphere. These results attest that the magnitude of the Carrington storm indicates that its extent falls within the range of other superstorms, such as those that occurred in May 1921 and February 1872, in terms of the equatorial boundary of the auroral oval., Comment: 11 pages, 3 figures, and 1 table

Three new caged polyprenylated benzophenone derivatives named burlemarxiones D-F (1–3) were isolated from the hexane extract of Clusia burle-marxii trunks. Burlemarxione D (1) contains the tetracyclo[8.3.1.03,11.05,10]tetradecane core skeleton also observed for burlemarxione A, its probable immediate precursor. However, two additional rings are formed to produce an unprecedented complex-caged core skeleton. These additional rings could be formed by a radical cyclization reaction of one prenyl group at C-5 with C-1 and C-33, followed by oxidative dehydrogenation (rearomatization) or by an intramolecular [4 + 2] radical cycloaddition (Diels-Alder reaction), followed by an enolization reaction (rearomatization). Burlemarxiones E and F were isolated after methylation with diazomethane that was necessary to avoid the interconversion of the pair of β-diketones in tautomeric equilibrium. The proposed biosynthetic pathway for burlemarxiones D-F involves the condensation of either lavandulyl pyrophosphate or 2-(1-methylvinyl)-hexa-5-enyl pyrophosphate with the acylphloroglucinol derivative 6-benzoyl-5-hydroxy-5-cyclohexen-1,3-dione, followed by consecutive prenylation reactions. Therefore, Clusia burle-marxii reinforces the claim that the genus Clusia is an important source of sophisticated caged polyprenylated benzophenone derivatives.

Even though a gap exists in understanding the behavior of radical scavengers and interfering species, they have been extensively employed to elucidate degradation mechanisms or to improve the degradation efficiency in heterogeneous photocatalysis. Focusing on the influence of different species, such as scavengers (t-butanol, formic acid, methanol, p-benzoquinone, oxalate, superoxide dismutase, and azide), interfering species (sulfite, dichromate, bromate, carbonate, chloride, and iodide) and inorganic ions (nitrate, sulfate, and phosphate), this work investigated the production of hydroxyl radicals and singlet oxygen during TiO2/UVA reactions. Electron paramagnetic resonance spectroscopy (EPR) was applied to investigate radicals formed in the presence of each interfering/scavenger species. Some scavengers and interfering species were studied during phenol degradation, chosen as a model substrate. All species, except bromate, hindered the degradation. para-Benzoquinone showed an increased hydroxyl radical production, attributed to the photo-reduction of quinones. Radicals other than hydroxyl radicals, such as carbon dioxide, hydroxymethyl, azide, and semiquinone, were identified in the presence of oxalate, methanol, azide, and para-benzoquinone, respectively. Some of these radicals can possibly interact with organic substrates due to their reduction potential; as a result, a critical interpretation must be done when these species are added to a heterogeneous photocatalysis process.

The motivation for this paper comes from offshore engineering, in which pre-stressed heavy chains, vertical cables, and rods attached to floating buoys are subjected to imposed heave motions induced by waves. Hence, the energy source in these systems is provided by parametric excitation. A piezoelectric element conveniently coupled to a slender-rod model is studied herewith. It is seen that if the system is tuned into modal asynchronicity, it has a superior performance, as far as energy harvesting is concerned. The very concept of modal asynchronicity, which is not widely spread, is addressed, establishing its phenomenological connection with localisation. Also, the so-called inverse effect associated with piezoelectricity is discussed to explain both the system’s quasi-static and dynamical behaviours.

Alzheimer's disease (AD) is one of the most common age-related neurodegenerative disorders. Aggregation of amyloid-β peptide into extracellular plaques with incorporation of metal ions, such as Cu2+, and reduction of the neurotransmitter acetylcholine levels are among the factors associated to the AD brain. Hence, a series of 7-chloro-4-aminoquinoline Schiff bases (HLa–e) were synthesized and their cytotoxicity and anti-cholinesterase activity, assessed for Alzheimer's disease. The intrinsic relationship between Cu2+ and the amyloidogenic plaques encouraged us to investigate the chelating ability of HLa–e. Dimeric tetracationic compounds, [Cu2(NHLa–e)4]Cl4, containing quinoline protonated ligands were isolated from the reactions with CuCl2·2H2O and fully characterized in the solid state, including an X ray diffraction study, whereas EPR data showed that the complexes exist as monomers in DMSO solution. The inhibitory activity of all compounds was evaluated by Ellman's spectrophotometric method in acetylcholinesterase (AChE) from Electrophorus electricus and butyrylcholinesterase (BChE) from equine serum. HLa–e and [Cu(NHLd)2]Cl2 were selective for AChE (IC50 = 4.61–9.31 μM) and were not neurotoxic in primary brain cultures. Docking and molecular dynamics studies of HLa–e inside AChE were performed and the results suggested that these compounds are able to bind inside AChE similarly to other AChE inhibitors, such as donepezil. Studies of the affinity of HLd for Cu2+ in DMSO/HEPES at pH 6.6 and pH 7.4 in μM concentrations showed formation of analogous 1:2 Cu2+/ligand complexes, which may suggest that in the AD-affected brain HLd may scavenge Cu2+ and the complex, also inhibit AChE.

Phytochemical investigation of the non-polar extract of Clusia burle-marxii led to the identification of a new steroid (1), along with friedelinol (2), β-sitosterol (3), friedelin (4), stigmast-5-en-3β,7β-diol (5), stigmast-5-en-3β,7α-diol (6), stigmasterol (7), sitostenone (8), betulinic acid (9), butyrospermol (10), euphol (11), betulin aldehyde (12), 2,2-dimethyl-5-hydroxy-7-phenyl-chromane (13), 6-deoxyisojacareubin (14), padiaxanthone (15) and betulonic acid (16). This is the first report of the identification of compounds 5, 6 and 10 in the family, the first report of compounds 14 and 15 in the genus, and the first report of compounds 2, 3, 7, 8, 12, 16 in the species. Chemotaxonomic significance of these compounds is described herein.

The occurrence of micropollutants in the environment is a matter of high concern. Some regulations have been published in the last years and a Watch List of contaminants of emerging concern (CECs) for European Union monitoring of surface water was launched in the Decision 2015/495, including three estrogens (estrone, E1; 17-β-estradiol, E2; and 17-α-ethinylestradiol, EE2), four pharmaceuticals (diclofenac and the macrolide antibiotics azithromycin, clarithromycin and erythromycin), an anti-oxidant (2,6-ditert-butyl-4-methylphenol, BHT), an UV filter (2-ethylhexyl 4-methoxycinnamate, EHMC), some pesticides (methiocarb and the neonicotinoids imidacloprid, thiacloprid, thiamethoxam, clothianidin and acetamiprid) and two herbicides (oxadiazon and triallate). This study provides the first spatial and seasonal monitoring campaign in the Ave and the Sousa Rivers for the all set of the 17 Watch List CECs (not reported yet for any country), in order to assess their occurrence, distribution, frequency and risk assessment. It also highlights the need of extend the study to other regions and environmental matrices to investigate the occurrence and possible sources of contamination of CECs, aiming to give insights for decision makers to define mitigation strategies for a more sustainable water policy.

Two decavanadates (trisH)4[H2V10O28]·10H2O ( 1 ) and (trisH)6[V10O28] ( 2 ) have been synthesised from NaVO3 or V2O5 in an aqueous solution of tris(hydroxymethyl)aminomethane (tris). Bimetallic derivatives [Cu(OH2)5(trisH)]2[V10O28]·6H2O ( 3 ) and [Cu(OH2)3(2–amp)]2(trisH)2 [V10O28]·2H2O ( 4 ) were obtained by the addition of CuCl2 or CuCl2 / 2–amp (2–(aminomethyl)pyridine) to the route that gave 2 . The products were characterised by single-crystal X-ray diffractometry, thermogravimetric analysis, FTIR, Raman and EPR spectroscopies. Moreover, 4 was effective in bleaching a methylene blue (MB) solution under natural light in acidic media by either degradation of the dye or precipitation of a MB-decavanadate salt depending on the experimental conditions.

The European Union (EU) has recommended the monitoring of specific priority substances (PSs, Directive 2013/39) and some contaminants of emerging concern (CECs, Decision 2015/495) in surface waterbodies. The present study provides spatial distributions and temporal variations of a wide range of multi-class PSs and CECs in four stressed rivers in Portugal (Ave, Leca, Antua, and Certima). Thirteen micropollutants were found in all four rivers, including the priority pesticide isoproturon (up to 92 ng L−1), various pharmaceuticals (up to 396 ng L−1), and the UV-filter 2-ethyl-hexyl-4-methoxycinnamate (EHMC, up to 562 ng L−1) identified in Decision 2015/495. The industrial priority compound perfluorooctanesulfonic acid (PFOS) was found in three rivers (Antua, Certima, and Leca) below the method quantification limit, together with four pharmaceuticals not included in these EU guidelines. The already banned priority pesticide atrazine was detected in Ave, Antua, and Leca (up to 41 ng L−1) and simazine in Certima and Leca (up to 26 ng L−1). Acetamiprid and imidacloprid (included in Decision 2015/495) were only detected during the dry season in the Ave. Leca river was selected as a waterbody case study for assessment of fluorescence excitation-emission matrices (EEMs). These results matched the spatial distribution trend of micropollutants along the river, with stronger fluorescence response and higher concentrations being found downstream of industrial areas and urban wastewater treatment plants (WWTPs). Moreover, the fluorescence signature of surface water collected downstream of an urban WWTP aligned very well with that obtained for the respective WWTP effluent. Thus, actions are needed to preserve a good environmental status of these stressed European waterbodies.

Periodic modulations in chiral nematic liquid crystals (CLCs) are used in several optical and photonic devices. A remarkable way of fabricating and controlling such patterns is in a thin wetting layer that grows as temperature is decreased. Here, we study this stripe formation process experimentally and by means of Monte Carlo simulations. We report on samples of CLCs that present, after the wetting transition, a stripe/fringe formation occurring either through a nucleation process or homogeneously across the cell. These patterns depend on the ratio of the pitch to thickness of the layer, elastic anisotropy, and anchoring strength. Although such process is well documented for CLCs under applied field, we show here that similar textural transitions occur in thin layers mediated by the weak anchoring at the CLC-isotropic interface; it happens for values of pitch to thickness ratio much smaller than the ones reported in field driven situation. The Monte Carlo method takes action in simulating the experimentally observed textures by using a pairwise additive potential model for CLCs. A qualitative comparison with the experimental phenomena is possible to be made in which both the stripes formation and their behavior agree with the experiments.

Ricinus communis is an important oilseed crop, which is widely used by traditional communities due to its medicinal properties. The extracts obtained from this plant are used to treat rhinitis, chest inflammation, bronchitis, dental caries, scabies, skin diseases, and infections in the digestive apparatus. Despite all its medicinal properties, there is a lack of studies that apply advanced chemical profiling techniques to characterize the chemical diversity of these extracts. The objective of this study was to apply a detailed multiplatform-based metabolite profiling approach to identify antioxidant and antimicrobial compounds in R. communis extracts. Leaf, stem and root extracts were obtained by maceration in hexane, ethyl acetate and ethanol. Antioxidant activity was assessed by the 2,2-diphenyl-1-picrylhydrazyl radical scavenging assay and total phenolic compounds were quantified by Folin-Ciocalteu method. Antimicrobial activity was assessed against Bacillus subtilis, B. cereus, Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Salmonela choleraesuis, Candida albicans and C. glabrata. Nuclear magnetic resonance, liquid chromatography–mass spectrometry, and gas chromatography–mass spectrometry were used to characterize the chemical profile of the extracts. The antioxidant activity (IC50) of the extracts ranged from 31.73 ± 2.59 to 571.74 ± 45.92 μg mL−1, whereas total phenolic content varied from 16.96 ± 0.30 to 135.06 ± 1.69 mg GAE/g of extract. Extracts obtained with ethanol showed the greatest antioxidant activity, the highest total phenolic content, along with the most promising antimicrobial properties. For example, the ethanolic extract of the leaves showed antimicrobial activity against P. aeruginosa, S. choleraesius, and C. albicans, whereas the ethanol extract of the roots showed antimicrobial activity against P. aeruginosa and C. albicans. Three metabolites were annotated and quantified by NMR, 54 by LC–MS, and 36 by GC–MS, which included alkaloids, fatty acids, terpenes, phenolic compounds, steroids and carotenoid derivatives. The ethanol extract of the leaves showed high levels of the alkaloid ricinine, which seems to contribute for the activities of this extract. This approach allowed us to identify antioxidant and antimicrobial present in R. communis extracts. Therefore, providing important leads into the discovery of new active compounds and possibly to the development of new pharmaceuticals.

The distorted tetrahedral [V(OAd)4] alkoxide (OAd = 1-adamantoxide, complex 1) is the first homoleptic, mononuclear vanadium(IV) alkoxide to be characterized in the solid state by X-ray diffraction analysis. The compound crystallizes in the cubic P43n space group with two highly disordered, crystallographically independent molecules in the asymmetric unit. Spin Hamiltonian parameters extracted from low temperature X- and Q-band electron paramagnetic resonance (EPR) experiments performed for polycrystalline samples of 1, both in the concentrated (bulk) form and diluted in the diamagnetic [Ti(OAd)4] analogue, reveal a fully axial system with gz < gx, gy and Az ≫ Ax, Ay. Complex 1 has also been characterized by alternate current susceptometry with varying temperature (3–30 K) and static magnetic field (up to 8.5 T), showing field-induced slow relaxation of the magnetization with relaxation times ranging from ca. 3 ms at 3 K to 0.02–0.03 ms at 30 K, in line with relevant results described recently for other ...

Consumer concerns about synthetic additives is increasing and it can be interesting to apply natural antioxidants with antimicrobial properties. Developing a packing material composed by a natural polymer, such as bacterial nanocellulose membrane (BNCm) loaded with nisin may be applied as a method to keep food quality and to inhibit growth of microbial contaminants. For this reason, the aim of this study was to evaluate antimicrobial activity of BNCm loaded with nisin. Antimicrobial activity of nisin, utilizing or not EDTA solution,was assessed by minimal inhibitory concentration and agar diffusion assay, utilizing Staphylococcus aureus, Escherichia coli, and Pseudomonas aeruginosa. Antioxidant activity and physico-chemical properties were also evaluated. For the MIC evaluation, the combination of nisin solution with EDTA showed a synergistic effect. Concerning E. coli nisin with EDTA 20–40 mM, MIC was 31.25 μg/mL. Concerning P. aeruginosa nisin with EDTA 10–20 mM, MIC was 125 μg/mL. Concerning S. aureus nisin with EDTA 10 mM, MIC was 15.63 μg/mL, two times lower than without EDTA. The BNCm antimicrobial activity for E. coli, by agar diffusion assay, was observed when nisin was loaded at 250 or 500 μg/mL with EDTA 10 or 20 mM. However, for S. aureus, the antimicrobial activity was observed for BNCm loaded with nisin 15 μg/mL with 10 mM EDTA. For P. aeruginosa, antimicrobial activity was not observed. Nisin exhibited significant antimicrobial and antioxidant activity. The results provide evidence that BNCm loaded with nisin is a promising control strategy to prevent microorganism contamination.

The effect of different membranes, membrane modules, feed temperatures, flow rates and solute concentrations on the permeate flux and salt rejection in direct contact membrane distillation (DCMD) was first studied with synthetic seawater and compared to distilled water. After optimizing these operating conditions, DCMD was tested with real feed samples, namely river water (RW-R), seawater (SW-R), and a secondary effluent from a municipal wastewater treatment plant (MW-R). The permeate flux achieved with MW-R was significantly lower than those obtained with the other feed samples. Two membrane module configurations (H-cell and W-cell) were then studied using SW-S, spiking diphenhydramine (DP) as model organic pollutant in some experiments. The H-cell performed better in terms of permeate quality for the same volume of permeate collected. A long experiment (500 h) was conducted with SW-R employing a larger H-cell. Severe fouling was observed, but high rejections of ion species (> 99%) were recorded together with complete rejections of pharmaceuticals (diclofenac, azithromycin, clarithromycin and erythromycin) detected in SW-R at 9.53-73.53 ng L-1 (detection limits < 0.16 ng L-1). Colonies of Escherichia colt or enterococci were not detected in 100 mL of permeate (distillate) solution, complying with the European Directive for drinking water.

Schiff-base ligands L1 and L2 containing fluorene as fluorophore were synthesized thorough condensation of salicylaldehyde and 2,6-diformyl 4-methylphenol with 6-(9-fluorenyl)-1,4,8,11-tetraazaundecane-5,7-dione, respectively. A comprehensive spectroscopic analysis was performed by elemental analysis, ESI-MS, 1H and 13C NMR, FTIR, EPR, UV–Vis and emission spectroscopies. Ligand L1 binds copper(II) to form [Cu2(L1)2]·2H2O that crystallizes in orthorhombic system and space group P21/n. Assignments to the UV–Vis and EPR spectra allowed access to Jahn–Teller stabilization energies (EJT) at 6345 and 5435 cm−1 for complexes [Cu2(L1)2]·2H2O and [Cu2(L2)](ClO4)4·4H2O, respectively, and to their corresponding spin orbit coupling constants λ = −428 and −398 cm−1. The EPR spectrum of [Cu2(L2)](ClO4)4·4H2O in the solid state showed a half-field ΔmS = ±2 transition, supporting the dicopper composition. The fluorenyl copper(II) derivatives demonstrated a moderate binding to ct-DNA than the fluorenyl-ligand molecule following the increasing order of (Kb): L1

Species distribution models (SDM) have been broadly used in ecology to address theoretical and practical problems. Currently, there are two main approaches to generate SDMs: (i) correlative, which is based on species occurrences and environmental predictor layers and (ii) process-based models, which are constructed based on species' functional traits and physiological tolerances. The distributions estimated by each approach are based on different components of species niche. Predictions of correlative models approach species realized niches, while predictions of process-based are more akin to species fundamental niche. Here, we integrated the predictions of fundamental and realized distributions of the freshwater turtle Trachemys dorbigni. Fundamental distribution was estimated using data of T. dorbigni's egg incubation temperature, and realized distribution was estimated using species occurrence records. Both types of distributions were estimated using the same regression approaches (logistic regression and support vector machines), both considering macroclimatic and microclimatic temperatures. The realized distribution of T. dorbigni was generally nested in its fundamental distribution reinforcing theoretical assumptions that the species' realized niche is a subset of its fundamental niche. Both modelling algorithms produced similar results but microtemperature generated better results than macrotemperature for the incubation model. Finally, our results reinforce the conclusion that species realized distributions are constrained by other factors other than just thermal tolerances.

Climate change is not only a major threat to biodiversity, it is also a big challenge to the development of conservation strategies. Scientists and practitioners need to select or avoid areas at greatest risk for species protection, i.e., acting in a proactive or a reactive manner. This proactive/reactive dichotomy takes a particular formulation under the likely changes in climate. Selecting for low-risk areas (usually referred to as climate refugia) is supposed to protect more species with a greater guarantee of their long-term persistence. As a consequence, populations at greatest risk are left unprotected and probably committed to extinction. On the other hand, managing species in high-risk areas is more expensive than setting aside areas of climate refugia and encompasses a set of uncertainties, which makes highly-threatened species more costly and difficult to save. Here, we combine ecological niche models and metrics of climate change to develop spatial conservation schemes for mammals in the Brazilian Amazon. These schemes efficiently identify networks of high-risk and refugia priority areas within species current and future distributions, while complementing the protection already achieved by the Amazon’s network of protected areas (PAs). We found that, on average, 25% of mammal distribution is already represented in the established network of PAs. Also, 26% of high-risk and 17% of refugia priority areas overlap with indigenous lands. In addition, species distributions were found mostly in high-risk, compared to in refugia priority areas. We highlight that the strategy to be employed does not necessarily should be binary and a mix of both strategies would guarantee the protection of a larger number of species.