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S N Ar reactions were remarkably accelerated using a pretargeting and activating unit based on dynamic covalent chemistry (DCvC). A Cys attack at the C-F bond on the aromatic ring of salicylaldehyde derivatives was only observed upon iminium formation with a neighboring Lys residue of model small peptides. Such self-activation was ascribed to the stronger electron-withdrawing capability of the iminium bond with respect to that of the parent aldehyde that stabilized the transition state of the reaction, together with the higher preorganization of the reactive groups in the cationic aldiminium species. This approach was further applied for the functionalization of two antibodies. In both cases, the presence of the aldehyde group in close proximity to the reactive C-F bond resulted in a noteworthy increase in bioconjugation yields, with excellent chemo-selectivity. Whereas the modification of an IgG1 antibody led to stochastic product distributions, microenvironment selectivity was noted when employing IgG4, in line with the lower number of Lys residues in the hinge region of the latter. Additionally, the postfunctionalization of the modified antibodies was attained through the dynamic covalent exchange of the tethered iminium derivative with hydrazides, representing an unprecedented "tag and modify" selective bioconjugation strategy based on DCvC.

The hypoxic microenvironment is crucial for tumour cell growth and invasiveness. Tumour tissue results from adaptation to reduced oxygen availability. Hypoxia first activates pro-angiogenic signals for alleviation. Pathologic, tumour angiogenesis maintains hypoxia, impairing treatment outcomes. Vessel normalisation requires physioxia. Oxygen delivery by red blood cell (RBC) carrying haemoglobin (Hb) is enhanced by myo-inositol trispyrophosphate (ITPP), an effector of oxygen transport by RBCs. Altering glycolytic activity, it lowers intracellular pH and increases oxygen release from Hb. 31 P NMR tracking of 2,3-diphosphoglycerate (2,3-DPG), allosteric effector of Hb and non-penetrating anion in RBCs, reports on erythrocytes internal environment. 31 P resonances of 2,3-DPG are pH-sensitive, their positions indicate the oxygenation state of RBCs and interactions with effectors such as ITPP. Here we show in vitro and in vivo, that modifying Hb activity through band-3 anion transporter, ITPP enhances oxygen release and controls RBC internal pH. Its blood availability validates applicability of ITPP-based strategies., (© 2025 The Author(s). Journal of Cellular and Molecular Medicine published by Foundation for Cellular and Molecular Medicine and John Wiley & Sons Ltd.)

We disclose the features of a category of reversible nucleophilic aromatic substitutions in view of their significance and generality in dynamic aromatic chemistry. Exchange of sulfur components surrounding arenes and heteroarenes may occur at 25 °C, in a process that one may call a "sulfur dance". These S N Ar systems present their own features, apart from common reversible reactions utilized in dynamic covalent chemistry (DCC). By varying conditions, covalent dynamics may operate to provide libraries of thiaarenes with some selectivity, or conversion of a hexa(thio)benzene asterisk into another one. The reversible nature of S N Ar is confirmed by three methods: a convergence of the products distribution in reversible S N Ar systems, a related product redistribution between two per(thio)benzenes by using a thiolate promoter, and from kinetic/thermodynamic data. A four-component dynamic covalent system further illustrates the thermodynamically-driven formation of a thiacalix[2]arene[2]pyrimidine by sulfur component exchanges. This work stimulates the implementation of reversible S N Ar in aromatic chemistry and in DCC., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Sea urchin eggs are covered with layers of extracellular matrix, namely, the vitelline layer (VL) and jelly coat (JC). It has been shown that sea urchin eggs' JC components serve as chemoattractants or ligands for the receptor on the fertilizing sperm to promote the acrosome reaction. Moreover, the egg's VL provides receptors for conspecific sperm to bind, and, to date, at least two sperm receptors have been identified on the surface of sea urchin eggs. Interestingly, however, according to our previous work, denuded sea urchin eggs devoid of the JC and VL do not fail to become fertilized by sperm. Instead, they are bound and penetratedby multiple sperm, raising the possibility that an alternative pathway independent of the VL-residing sperm receptor may be at work. In this research, we studied the roles of the JC and VL using intact and denuded eggs and the synthetic polyamine BPA-C8. BPA-C8 is known to bind to the negatively charged macromolecular complexes in the cells, such as the JC, VL, and the plasma membrane of echinoderm eggs, as well as to the actin filaments in fibroblasts. Our results showed that, when added to seawater, BPA-C8 significantly repressed the Ca 2+ wave in the intact P. lividus eggs at fertilization. In eggs deprived of the VL and JC, BPA-C8 binds to the plasma membrane and increases fibrous structures connecting microvilli, thereby allowing the denuded eggs to revert towards monospermy at fertilization. However, the reduced Ca 2+ signal in denuded eggs was nullified compared to the intact eggs because removing the JC and VL already decreased the Ca 2+ wave. BPA-C8 does not cross the VL and the cell membrane of unfertilized sea urchin eggs to diffuse into the cytoplasm at variance with the fibroblasts. Indeed, the jasplakinolide-induced polymerization of subplasmalemmal actin filaments was inhibited in the eggs microinjected with BPA-C8, but not in the ones bath-incubated with the same dose of BPA-C8.

Stable and efficient green hybrid light-emitting diodes (HLEDs) were fabricated from a highly emissive Mg(II)-tetraphenyl ethylene derivative metal-organic framework embedded in a polystyrene matrix (Mg-TBC MOF@PS). The photoluminescence quantum yield (ϕ) of the material, >80%, remains constant upon polymer embedment. The resulting HLEDs featured high luminous efficiencies of >50 lm W -1 and long lifetimes of >380 h, making them among the most stable MOF-based HLEDs. The significance of this work relies on the combination of many features, such as the abundance of the metal ion, the straightforward scalability of the synthetic protocol, the great ϕ reached upon phosphor fabrication, and the state-of-the-art HLED performances.

Introduction: COVID-19 acutely shocked both socio-economic and food systems in 2020. We investigated the impact of COVID-19 on production and consumption of gardened produce, backyard poultry, wild game and fish, and foraged mushrooms, berries, and other plants in New York State, aiming to understand crisis influenced food choice and motivations, including food security., Methods: We conducted an online, cross-sectional survey in October-December 2020 with a convenience sample of participants ( n = 505) with an interest in gardening, poultry rearing, foraging, hunting, and/or fishing from six counties in upstate New York. We recruited through the New York Department of Environmental Conservation, Cornell Cooperative Extension, and other relevant email and social media pages., Results: Across the wild and backyard food production strategies, 4.0-14.3% of respondents reported engaging for the first time and 39.6-45.7% reported increased production (a little or a lot more), and 31.6-42.7% of respondents' production was the same as the previous year. Consumption of foods produced was widespread, including fruit and vegetables (97.6% of producers also consumed), backyard eggs (92.7%), and foraged foods (93.8%). For meats, a majority consumed backyard poultry meat (51.2%), wild-caught fish (69.7%), and wild game they hunted (80.1%). The frequency of consumption of fruit and vegetables (average of 13.5 times/month) and eggs (16.4 times/month) was very high, while average consumption of poultry meat, foraged foods, fish, and wild game ranged from 3.1 to 5.8 times/month. The number of respondents who reported "have more control over food availability" as motivation to produce all wild and backyard foods increased from 2019 to 2020 ( p < 0.05 - p < 0.001). There was also a significant relationship between experiences of COVID-19 related hardship (i.e., food insecurity, income loss) with gardening and poultry-rearing ( p ≤ 0.05), but not with other production methods or with consumption of wild and backyard foods., Discussion: Our findings help to locate wild and backyard foods within COVID-19 impacted food environments, and describe food security as a particularly relevant motivation, among others, reported by respondents in 2020. Given this, New York State service providers can use these findings to tailor current future support for households exerting control over their own food environments with wild and backyard foods, allowing the state to be better prepared for future crises., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Coffin-Schmitt, Clements, Marshall, Liu, Trombitas, Wang, Yuan, Safi, Hanson and Fiorella.)

In starfish, the addition of the hormone 1-methyladenine (1-MA) to immature oocytes (germinal vesicle, GV-stage) arrested at the prophase of the first meiotic division induces meiosis resumption (maturation), which makes the mature eggs able to respond to the sperm with a normal fertilization response. The optimal fertilizability achieved during the maturation process results from the exquisite structural reorganization of the actin cytoskeleton in the cortex and cytoplasm induced by the maturing hormone. In this report, we have investigated the influence of acidic and alkaline seawater on the structure of the cortical F-actin network of immature oocytes of the starfish ( Astropecten aranciacus ) and its dynamic changes upon insemination. The results have shown that the altered seawater pH strongly affected the sperm-induced Ca 2+ response and the polyspermy rate. When immature starfish oocytes were stimulated with 1-MA in acidic or alkaline seawater, the maturation process displayed a strong dependency on pH in terms of the dynamic structural changes of the cortical F-actin. The resulting alteration of the actin cytoskeleton, in turn, affected the pattern of Ca 2+ signals at fertilization and sperm penetration.

The edge effect, triggered by habitat fragmentation, alters forest microclimates and influences the life cycle of plants. Phenology may indicate the first changes in phenological patterns in response to the effects of climate change. Climate regulates the phenology of ferns and climatic triggers influence plants in tropical and subtropical regions differently. This study analyzed and compared the phenology of fern communities of three sub-areas - natural edge, artificial edge, and forest interior - of a fragment of Araucaria Forest in the Floresta Nacional de São Francisco de Paula, Rio Grande do Sul, Brazil, and its relationship with meteorological, astronomical, and edaphic variables. Abiotic and edaphic data were monitored concomitantly with phenological data (leaf renewal and senescence and sporangia formation) in each sub-area over a biennium. Temperature, air humidity, and soil moisture, which undergo changes with the edge effect, influenced edge plants. Leaf renewal was the main phenophase showing strong indication of changes in vegetative patterns in natural and artificial edge communities. Among the communities, that of the artificial edge signaled phenological changes that could compromise the development of ferns if effects intensify over time. In this respect, the phenology of artificial edge ferns differed from that of plants growing in originally natural formations (natural edge and forest interior), showing that exogenous transformations represent a new environmental situation for ferns to develop., (© 2022. The Author(s) under exclusive licence to International Society of Biometeorology.)

The vitelline layer (VL) of a sea urchin egg is an intricate meshwork of glycoproteins that intimately ensheathes the plasma membrane. During fertilization, the VL plays important roles. Firstly, the receptors for sperm reside on the VL. Secondly, following cortical granule exocytosis, the VL is elevated and transformed into the fertilization envelope (FE), owing to the assembly and crosslinking of the extruded materials. As these two crucial stages involve the VL, its alteration was expected to affect the fertilization process. In the present study, we addressed this question by mildly treating the eggs with a reducing agent, dithiothreitol (DTT). A brief pretreatment with DTT resulted in partial disruption of the VL, as judged by electron microscopy and by a novel fluorescent polyamine probe that selectively labelled the VL. The DTT-pretreated eggs did not elevate the FE but were mostly monospermic at fertilization. These eggs also manifested certain anomalies at fertilization: (i) compromised Ca 2+ signaling, (ii) blocked translocation of cortical actin filaments, and (iii) impaired cleavage. Some of these phenotypic changes were reversed by restoring the DTT-exposed eggs in normal seawater prior to fertilization. Our findings suggest that the FE is not the decisive factor preventing polyspermy and that the integrity of the VL is nonetheless crucial to the egg's fertilization response.

A team of interdisciplinary researchers undertook a mixed methods, participatory epidemiology (PE) based study as part of a pilot project for localized control of Peste des petits ruminants (PPR), a small ruminant disease of high socio-economic impact. Mixed methods research combines qualitative and quantitative methods, allowing iterative comparison of results to arrive at a more comprehensive and informed outcome. In this study, the use of PE and a household survey (HHS) resulted in contradictory results. However, the mixed methods approach also facilitated the detection and the explanation of bias in the HHS, which may have gone undetected and unexplored had only one method been used. Results show that logistical constraints leading to a failure to apply key aspects of the sampling strategy led to problematic gender/ethnic composition of the HHS sample population. Additionally, while PE findings on local disease and terminology were integrated during HHS development and training, there is apparent measurement error related to enumerator bias in HHS results, possibly due to insufficient respondent understanding or a lack of analytic clarity. The extensive nature of the PE, surveillance methodologies used in the initial site assessment, and formative research for the HHS allowed for a critical analysis and interpretation of HHS results as well as reflection on the research process. The findings of this paper underscore the (1) flexibility and utility of participatory methods, (2) the importance of mixed methods research in designing health interventions, and (3) the necessity of tight integration of study design with team planning for implementation of research in environments such as Karamoja, Uganda. If all three are to be achieved not only researchers but funders must provide these space and structure beginning in the study design phase. These findings are relevant in many places, but have particular importance for international, interdisciplinary teams working from various on-and-off-site locations with traditional or indigenous knowledge systems., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Herbivory is an interaction with great impact on plant communities since relationships between herbivores and plants are fundamental to the distribution and abundance of species over time and space. The aim of this study was to monitor the rate of leaf expansion in the tree fern Cyathea phalerata and evaluate the damage caused by herbivores to leaves of different ages and whether such damage is related to temperature and precipitation. The study was performed in a subtropical Atlantic Forest fragment located in the municipality of Caraá, in the northeast hillside of Rio Grande do Sul state, in southern Brazil. We monitored 24 mature individuals of C. phalerata with croziers in a population of approximately 50 plants. Leaf expansion rate, percentage of damaged leaves and leaf blade consumption rate by herbivory were calculated. Monthly means for temperature and accumulated rainfall were calculated from daily data. Croziers of C. phalerata were found to expand rapidly during the first and second months after emergence (3.98 cm day-1; 2.91 cm day-1, respectively). Damage caused by herbivory was observed in all of the monitored leaves, but none of the plants experienced complete defoliation. The highest percentage (57%) of damaged leaves was recorded at 60 days of monitoring, and also the highest monthly consumption rate of the blade (6.04%) occurred with young, newly-expanded leaves, while this rate remained between 1.50 and 2.21% for mature leaves. Rates of monthly leaf consumption and damaged leaves showed positive and strong relationship with each other and with temperature. The rapid leaf expansion observed for C. phalerata can be considered a phenological strategy to reduce damage to young leaves by shortening the developmental period and accelerating the increase of defenses in mature leaves.

The design of catalytic proteins with functional sites capable of specific chemistry is gaining momentum and a number of artificial enzymes have recently been reported, including hydrolases, oxidoreductases, retro-aldolases, and others. Our goal is to develop a peptide ligase for robust catalysis of amide bond formation that possesses no stringent restrictions to the amino acid composition at the ligation junction. We report here the successful completion of the first step in this long-term project by building a completely de novo protein with predefined acyl transfer catalytic activity. We applied a minimalist approach to rationally design an oxyanion hole within a small cavity that contains an adjacent thiol nucleophile. The N-terminus of the α-helix with unpaired hydrogen-bond donors was exploited as a structural motif to stabilize negatively charged tetrahedral intermediates in nucleophilic addition-elimination reactions at the acyl group. Cysteine acting as a principal catalytic residue was introduced at the second residue position of the α-helix N-terminus in a designed three-α-helix protein based on structural informatics prediction. We showed that this minimal set of functional elements is sufficient for the emergence of catalytic activity in a de novo protein. Using peptide- α thioesters as acyl-donors, we demonstrated their catalyzed amidation concomitant with hydrolysis and proved that the environment at the catalytic site critically influences the reaction outcome. These results represent a promising starting point for the development of efficient catalysts for protein labeling, conjugation, and peptide ligation.

Riparian forests present biotic and abiotic factors that influence environmental dissimilarity, which reflect specific fern distribution. The purpose of this this study was to evaluate the environmental heterogeneity associated to the terrestrial fern communities in riparian forest remnants in the grasslands southern half of Rio Grande do Sul state . We sampled ten 5×5 m plots in each site (AI, AII and AIII), totaling 30 plots. In each plot, fern species were inventoried and vegetative, microclimatic and edaphic parameters were collected. A total of 24 species were surveyed in the three riparian forest remnants, distributed in 19 genera and 10 families. The Principal Components Analysis (PCA) showed that plots of AI had the highest temperature and aluminum values, while humidity was the lowest, which was reflected in the decrease of ferns richness. Soil moisture and air humidity were variables more related to the plots of AII and AII, indicating that these plants were favored in these environments. The floristic identity characteristic of each site suggests that many species are dependent to certain local environmental conditions. In this sense, even in very geographically close sites, riparian remnants deserve conservation attention, since they are capable of harboring high diversity in this grassland phytophysiognomy in southern Brazil. The results of this integrated study, with vegetation, climatic, and edaphic parameters, suggest, as expected, that ferns categorically respond to the heterogeneity shown by riparian environments, even when fragments are geographically very close to each other.

Climate regulates the fern phenology and climatic triggers influence plants from tropical and subtropical regions differently. Ferns depend on climate to regulate their life cycle, because they do not require animal interaction to reproduce. Through the pioneering study of the phenology of Araucaria forest understory in subtropical climate of Brazil, our main aims were (i) to verify which climatic variables influenced the phenological pattern of the community, (ii) to identify the differences in seasonality of ferns in distinct climatic zones of Brazil, and (iii) to compare the phenological pattern of ferns growing in other subtropical regions of the world. In an Araucaria forest fragment, we monitored the phenology of the fern community (leaf production, leaf senescence, and sporangium formation) over 2 years. At the same time, we collected photoperiod, temperature, and precipitation data. Ferns phenology was classified as continuous, discontinuous, regular, and irregular. Our results showed photoperiod and mean temperature as the best predictors for phenology. The reproductive event was seasonal, and the fern community presented themselves as continuous, irregular (activity index), and regular (intensity index) phenophases. Unlike ferns from tropical regions that generally regulate themselves by the rainfall, some ferns in a non-seasonal environment have seasonal behavior in their phenophases due to the greater amplitude of photoperiod and temperature. The community showed the same pattern of leaf production observed in populations of other subtropical regions in the world. This behavior represented the biological response of the vegetation dynamics in relation to the climatic variability of subtropical environment.

Forest edges typically exhibit higher luminosity and lower humidity than the forest interior, resulting in an abiotic gradient. However, the degree of abiotic difference can be affected from the type of the matrix, influencing the selection of species. We compared the floristic and phytosociological structure of understory communities of ferns and lycophytes of the edge and interior of three forest sites influenced by different types of surrounding matrices (natural field, Pinus plantation, and cultivation of crops). In the region of Araucaria Forest, in Rio Grande do Sul, Brazil, twelve 10 × 10 m plots were selected at the edge and interior of each site, totaling 72 plots and to evaluate the phytosociological contrast, using as a parameter coverage and species richness per plot to evaluate this contrast. We recorded a total of 38 species in the studied areas, distributed in 15 families. The results show that the edge effect acts at different intensities in the analyzed sites. In the site with unnatural matrix, the composition was more homogeneous both in the edges and in the interiors and presented lower richness, showing a more pronounced and deep impact. Already in the site with natural matrix surroundings, although the border also presents low richness, the interior was about 3x richer. Based on our results, we concluded that fern conservation efforts should focus on fragments of Araucaria Forest inserted in the natural field, because the conversion of natural field into Pinus planting and cultivation of crops decreases ferns species both in the edges and forest interiors of the studied fragments, besides altering the phytosociological structure leading the communities to simplification.

Dicksonia sellowiana Hook. (Dicksoniaceae) is target of extractive exploitation and is threatened with extinction. We analyzed the population structure, the spatial distribution pattern of D. sellowiana and its relationship with environmental parameters within three fragments of Araucaria Forest in Rio Grande do Sul, Brazil. The fragments are of different sizes, namely, large (H1LF) with 246 ha, medium (H2MF) with 57 ha and small (H3SF) with 5.2 ha. Within each site, 1 ha was delimited, divided into 100 subplots (100 m2), of which 20 were selected with a draw. In each subplot, counting of the individuals, the registration of the caudice height and the coverage of leaves (SC) (m2), measurements of photosynthetically active radiation (PAR), canopy opening degree (CO), soil moisture (SM) and litter thickness (LT). The temperature (T) was measured inside each site. A total of 792 plants were sampled, of which 551 were concentrated in H1LF, 108 in H2MF and 133 in H3SF. An average of 1320 ha-1 individuals were estimated. Of the total including the three fragments, 96.9% of the individuals are in the first class of height (up to 0.8 m), indicating a great potential of population development. The spatial distribution pattern (AI) was aggregated in the three populations and the plants presented a heterogeneous total coverage, between 4.73 m2 (H2MF) and 2,223.47 m2 (H1LF). The highest values ​​of SC and SM were more related to the distribution of individuals in H1LF whereas the opposite was recorded in H2MF. The highest values ​​of PAR, LT and CO correlated with the distribution of D. sellowiana in H3SF. In addition to revealing that the H1LF population is among the most dense in southern Brazil, the results demonstrated a significant structural distinction between the interior populations of the fragments, in spite of them being located near to one another and being part of the same natural field matrix.

Specimens of Leptogium collected in ten localities from the State of Rio Grande do Sul were studied. Sixteen species were found of 28 records mentioned to the state, which represents around 57% of the Leptogium diversity known for Rio Grande do Sul. Leptogium exaratum is proposed as a new species. Leptogium atlanticum, L. milligranum and L. vesiculosum are reported for the first time to the state. The lectotype of L. javanicum is reported here and detailed descriptions are provided to the examined specimens. An identification key is showed with all the 28 mentioned species of Leptogium. It is the first published taxonomic key for Leptogium from Rio Grande do Sul, the State with the highest diversity of this genus in Brazil.

Epiphytes are hyper-diverse and one of the frequently undervalued life forms in plant surveys and biodiversity inventories. Epiphytes of the Atlantic Forest, one of the most endangered ecosystems in the world, have high endemism and radiated recently in the Pliocene. We aimed to (1) compile an extensive Atlantic Forest data set on vascular, non-vascular plants (including hemiepiphytes), and lichen epiphyte species occurrence and abundance; (2) describe the epiphyte distribution in the Atlantic Forest, in order to indicate future sampling efforts. Our work presents the first epiphyte data set with information on abundance and occurrence of epiphyte phorophyte species. All data compiled here come from three main sources provided by the authors: published sources (comprising peer-reviewed articles, books, and theses), unpublished data, and herbarium data. We compiled a data set composed of 2,095 species, from 89,270 holo/hemiepiphyte records, in the Atlantic Forest of Brazil, Argentina, Paraguay, and Uruguay, recorded from 1824 to early 2018. Most of the records were from qualitative data (occurrence only, 88%), well distributed throughout the Atlantic Forest. For quantitative records, the most common sampling method was individual trees (71%), followed by plot sampling (19%), and transect sampling (10%). Angiosperms (81%) were the most frequently registered group, and Bromeliaceae and Orchidaceae were the families with the greatest number of records (27,272 and 21,945, respectively). Ferns and Lycophytes presented fewer records than Angiosperms, and Polypodiaceae were the most recorded family, and more concentrated in the Southern and Southeastern regions. Data on non-vascular plants and lichens were scarce, with a few disjunct records concentrated in the Northeastern region of the Atlantic Forest. For all non-vascular plant records, Lejeuneaceae, a family of liverworts, was the most recorded family. We hope that our effort to organize scattered epiphyte data help advance the knowledge of epiphyte ecology, as well as our understanding of macroecological and biogeographical patterns in the Atlantic Forest. No copyright restrictions are associated with the data set. Please cite this Ecology Data Paper if the data are used in publication and teaching events., (© 2019 The Authors. Ecology © 2019 The Ecological Society of America.)

Anthropic activities such as the emission of pollutants resulting from industrial and agropastoral activities promote several changes in urban and forest areas. Lichens are organisms that are used in air quality evaluations due to their sensitivity to these changes. The aim of this study is to analyze the presence of morphophysiological damages and the metal concentration in samples of the lichen Parmotrema tinctorum, in urban and forest areas, checking for possible parameter variations between these areas, in the different matrices and seasons in the Southern region of Brazil. Six areas were selected (urban and forest), assigned to the rural/urban and urban/industrial matrices belonging to the watershed of the Rio dos Sinos, Brazil. The following parameters were analyzed: Index of photobiont vitality (IPV), photosynthetic pigments (chlorophyll, carotene, and pheophytin) and metals (Cu, Cr, Zn, Pb, and Ni) in the thallus of the lichen. The data were analyzed by an ANOVA one way, Pearson correlation test, and principal component analysis (PCA). Variations in the morphophysiological parameters were recorded in all the areas revealing significant differences. The lowest IPV values and highest concentration of metals were recorded in the urban environment, while low chlorophyll levels were found in the forest areas. The PCA showed a distinction between the areas and the season. The level of urbanization, vehicle traffic, and the weather conditions might have influenced the results. The use of P. tinctorum, the index of photobiont vitality and chlorophyll and pheophytin content, has proved to be an efficient tool to diagnose the air quality in the areas analyzed, allowing its use as a model in air monitoring studies, both in urban and forest areas, as well as in distinct matrices in the subtropical region.

This study aimed to assess the chemical composition of the rainwater in three areas of different environmental impact gradients in Southern Brazil using the receptor model EPA Positive Matrix Factorization (EPA PMF 5.0). The samples were collected in a bulk sampler, from October 2012 to August 2014, in three sampling sites along with the Sinos River Basin: Caraá, Taquara, and Campo Bom. The major ions NH 4 + , Na + , K + , Ca 2+ , Mg 2+ , F - , Cl - , NO 3 - , SO 4 2- , and pH were analyzed, as well as identify the main emission sources. The most abundant cations and anions were Ca 2+ , Na + , Cl - , and SO 4 2- , respectively. The mean pH value in the Sinos River Basin during the study period was 6.07 ± 0.49 (5.13-7.05), which suggests inputs of alkaline species into the atmosphere. The most important neutralizing agents of sulfuric and nitric acids in the Sinos River Basin are Ca 2+ (NF = 1.36) and NH 4 + (NF = 0.57). The source apportionment provided by the EPA PMF 5.0 resulted in four factors, which demonstrate the influence of anthropogenic and natural sources, in the form of (a) industry/combustion of fossil fuels (F - and SO 4 2- ), (b) marine contribution (Na + and Cl - ), (c) crustal contribution (K + , Ca 2+ , and NO 3 - ), and (d) agriculture/livestock (NH 4 + ). Therefore, this study allows a more appropriate understanding of factors that contribute to rainwater chemical composition and also to possible changes in air quality.

Climate is one of the main factors that affect plant behavior. The phenology of Guarea macrophylla Vahl, which is a small tree used for reforestation of degraded areas, was monitored for 18 months in a riparian forest at the Schmidt Stream, Campo Bom, in the state of Rio Grande do Sul, southern Brazil. Vegetative (leaf fall and leaf flushing) and reproductive events were observed, with the latter divided into flowering (flower buds and anthesis) and fruiting (unripe, ripening and ripe fruit). Phenological events were related to temperature, photoperiod and precipitation and their seasonality was verified by circular statistical analysis. Vegetative phenophases were continuous; they were not related to climate factors and presented low intensity, emphasizing the perennial aspect of the species. Flowering occurred during spring and summer. Both flower buds and anthesis were related to temperature and photoperiod. Fruiting was constant and went through all stages of development. Unripe fruits developed during the months with the lowest photoperiod and ripen more intensely in winter, on colder days. Ripe fruit became available for dispersal in spring, in times of longer photoperiod and higher temperatures. Except for leaf fall, all other phenological events showed seasonality in their manifestation. The one-month difference between the onsets of the flowering phases observed in this study indicated that local climate changes induced the early occurrence of this phenophase.

Richness, coverage and concentration of heavy metals in vascular epiphytes were analyzed in isolated trees along an urbanization gradient in Southern Brazil. A total of 20 phorophytes were sampled in the main street of each site. Concentrations of chromium, cadmium, lead, manganese, nickel and zinc were measured in the leaves of Tillandsia recurvata L. using Graphite Furnace Atomic Absorption Spectrophotometry. A decreasing gradient of epiphyte richness and coverage was observed as urbanization increased. Vehicle fleet and demographic density were the parameters most correlated with the reduction of epiphytic diversity. In T. recurvata, significantly higher values of cadmium, lead and zinc were recorded in the most urbanized areas, and were strongly related to the vehicle fleet and to the demographic density in these sites. The results demonstrated that these parameters could be applied to the diagnosis of environmental quality in urban areas, allowing standardized analyses in other regions., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Plants growing in environments with different atmospheric conditions may present changes in the morphometric parameters of their leaves. Microgramma squamulosa (Kaulf.) de la Sota is a neotropical epiphytic fern found in impacted environments. The aims of this study were to quantitatively compare structural characteristics of leaves in areas with different air quality conditions, and to identify morphometric parameters that are potential indicators of the effects of pollution on these plants. Fertile and sterile leaves growing on isolated trees were collected from an urban (Estância Velha) and a rural (Novo Hamburgo) environment, in Rio Grande do Sul, Brazil. For each leaf type, macroscopic and microscopic analyses were performed on 192 samples collected in each environment. The sterile and fertile leaves showed significantly greater thickness of the midrib and greater vascular bundle and leaf blade areas in the rural environment, which is characterized by less air pollution. The thickness of the hypodermis and the stomatal density of the fertile leaves were greater in the urban area, which is characterized by more air pollution. Based on the fact that significant changes were found in the parameters of both types of leaves, which could possibly be related to air pollutants, M. squamulosa may be a potential bioindicator.

The epiphytic fern Microgramma squamulosa occurs in the Neotropics and shows dimorphic sterile and fertile leaves. The present study aimed to describe and compare qualitatively and quantitatively macroscopic and microscopic structural characteristics of the dimorphic leaves of M. squamulosa, to point more precisely those characteristics which may contribute to epiphytic adaptations. In June 2009, six isolated host trees covered by M squamulosa were selected close to the edge of a semi-deciduous seasonal forest fragment in the municipality of Novo Hamburgo, State of Rio Grande do Sul, Brazil. Macroscopic and microscopic analyzes were performed from 192 samples for each leaf type, and permanent and semi-permanent slides were prepared. Sections were observed under light microscopy using image capture software to produce illustrations and scales, as well as to perform quantitative analyses. Fertile and sterile leaves had no qualitative structural differences, being hypostomatous and presenting uniseriate epidermis, homogeneous chlorenchyma, amphicribal vascular bundle, and hypodermis. The presence of hypodermal tissue and the occurrence of stomata at the abaxial face are typical characteristics ofxeromorphic leaves. Sterile leaves showed significantly larger areas (14.80cm2), higher sclerophylly index (0.13g/cm2) and higher stomatal density (27.75stomata/mm2) than fertile leaves. The higher sclerophylly index and the higher stomatal density observed in sterile leaves are features that make these leaves more xeromorphic, enhancing their efficiency to deal with limited water availability in the epiphytic environment, compared to fertile leaves.

Conversion of macrocyclic imine entities into helical strands was achieved through three- and four-component exchange reactions within constitutionally dynamic libraries. The generation of sequences of the intrinsic helicity codon, based on the hydrazone-pyrimidine fragment obtained by condensation of pyrimidine dialdehyde A with pyrimidine bis-hydrazine B, shifted the equilibrium between all the possible macrocycles and strands towards the full expression (>98%) of helical product [A/B]. Furthermore, it was shown that chain folding accelerated the dynamic exchange reactions among the library members. Lastly, in four-component experiments (involving A, B, E and either C or D), even though the macrocyclic entities ([A/C], [B/E]; [A/D], [B/E]) were the kinetically preferred products, over time dialdehyde A relinquished its initial diamine partners C or D to opt for bis-hydrazine B, which allowed the preferential formation of the helically folded strand. The present results indicate that self-organisation pressure was able to drive the dynamic system towards the selective generation of the strand undergoing helical folding.

A new method of isolating host-independent Bdellovibrio bacteriovorus has been developed. Filtered suspensions of host-dependent cells are dropped in small volumes onto 0.2 microm membranes laid on rich media agar. Significant growth is observed within 1-2 days; these cells were confirmed to be B. bacteriovorus using microscopic observations and PCR.

Constitutional dynamics, self-assembly, and helical-folding control are brought together in the efficient Sc(OTf)3/microwave-catalyzed transimination of helical oligohydrazone strands, yielding highly diverse dynamic libraries of interconverting constituents through assembly, dissociation, and exchange of components. The transimination-type mechanism of the ScIII-promoted exchange, as well as its regioselectivity, occurring only at the extremities of the helical strands, allow one to perform directional terminal polymerization/depolymerization processes when starting with dissymmetric strands. A particular library is subsequently brought to express quantitatively [2 x 2] gridlike metallosupramolecular arrays in the presence of ZnII ions by component recombination generating the correct ligand from the dynamic set of interconverting strands. This behavior represents a process of driven evolution of a constitutional dynamic chemical system under the pressure (coordination interaction) of an external effector (metal ions).

Sc(OTf)(3) efficiently catalyzes the self-sufficient transimination reaction between various types of C=N bonds in organic solvents, with turnover frequencies up to 3600 h(-)(1) and rate accelerations up to 6 x 10(5). The mechanism of the crossover reaction in mixtures of amines and imines is studied, comparing parallel individual reactions with coupled equilibria. The intrinsic kinetic parameters for isolated reactions cannot simply be added up when several components are mixed, and the behavior of the system agrees with the presence of a unique mediator that constitutes the core of a network of competing reactions. In mixed systems, every single amine or imine competes for the same central hub, in accordance with their binding affinity for the catalyst metal ion center. More generally, the study extends the basic principles of constitutional dynamic chemistry to interconnected chemical transformations and provides a step toward dynamic systems of increasing complexity.

Purpose: To evaluate the efficacy and safety of atrasentan (ABT-627), an endothelin-A receptor antagonist, in the treatment of asymptomatic, hormone-refractory prostatic adenocarcinoma., Patients and Methods: A double-blind, randomized, placebo-controlled clinical trial of hormone-refractory prostate cancer (HRPCa) patients was conducted in the United States and Europe. Two hundred eighty-eight asymptomatic patients with HRPCa and evidence of metastatic disease were randomly assigned to one of three study groups receiving a once-daily oral dose of placebo, 2.5 mg atrasentan, or 10 mg atrasentan, respectively. Primary end point was time to progression; secondary end points included time to prostate-specific antigen (PSA) progression, bone scan changes, and changes in bone and tumor markers., Results: The three treatment groups were similar in all baseline characteristics. Median time to progression in intent-to-treat (ITT) patients (n = 288) was longer in the 10-mg atrasentan group compared with the placebo group: 183 v 137 days, respectively; (P =.13). Median time to progression in evaluable patients (n = 244) was significantly prolonged, from 129 days (placebo group) to 196 days (10-mg atrasentan group; P =.021). For both ITT and evaluable populations in the 10-mg atrasentan group, median time to PSA progression was twice that of the placebo group (155 v 71 days; P =.002). Patients who received placebo continued to have significant increases from baseline in serum (lactate dehydrogenase [LDH]), a marker of disease burden; elevations in LDH were uniformly attenuated by atrasentan in the ITT population. Headache, peripheral edema, and rhinitis were primary side effects, typically of mild to moderate severity. Quality of life was not adversely affected by atrasentan., Conclusion: Atrasentan is an oral, targeted therapy with favorable tolerability and the potential to delay progression of HRPCa.

From April 1985 to September 1991, 88 patients were operated for a total of 100 thoracobrachial outlet syndromes. The patients were placed in the dorsal supine position, turned 30 degrees towards the contralateral side. The arm was suspended in slight abduction. The access obtained is identical to that obtained with the classical operation. No direct traction or compression is exerted on the pedicles during retraction and the operation requires a single assistant. The composition, indications and results of our series are similar to those reported in the recent literature. We did not observed any immediate or late neurological complications. We conclude that thoracobrachial outlet syndromes can be treated via an axillary approach using mechanical traction and a single assistant without increasing the risk of neurological complications.

The efficacy of 4 therapeutic schedules was compared in March and April 1990 in Brazzaville school children, aged between 6 and 8 years, with parasitaemia of at least 1,000 trophozoites of Plasmodium falciparum per mm3. It was possible to interpret 125 simplified in vivo tests. The results showed that the activity of amodiaquine is still relatively satisfactory. The activity of chloroquine was slightly lower with the schedule of 25 mg/kg but was good at 35 mg/kg. Although these results were obtained in children who were mostly asymptomatic, they show that the use of amino-4-quinolines is still justified, at least in the initial treatment of uncomplicated malaria in semi-immune congolese subjects.