The relative stabilities of the alkali [M ⊂ 222]+ cryptates (M = Na, K, Rb and Cs) in the gas phase and in solution (80:20 v/v methanol:water mixture) at 298 K, are computed
using a combination of ab initio quantum-chemical calculations (HF/6-31G and MP2/6-31+G*//HF/6-31+G*) and explicit-solvent
Monte Carlo free-energy simulations. The results suggest that the relative stabilities of the cryptates in solution are due
to a combination of steric effects (compression of large ions within the cryptand cavity), electronic effects (delocalization
of the ionic charge onto the cryptand atoms) and solvent effects (dominantly the ionic dessolvation penalty). Thus, the relative
stabilities in solution cannot be rationalized solely on the basis of a simple match or mismatch between the ionic radius
and the cryptand cavity size as has been suggested previously. For example, although the [K ⊂ 222]+ cryptate is found to be the most stable in solution, in agreement with experimental data, it is the [Na ⊂ 222]+ cryptate that is the most stable in the gas phase. The present results provide further support to the notion that the solvent
in which supramolecules are dissolved plays a key role in modulating molecular recognition processes.
Figure Alkali cryptates [M ⊂ 222]+ (M = Na, K, Rb and Cs) relative stabilities in gas and methanol:water solution: solvent effects
and molecular recognition
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
Paracoccidioides brasiliensis is an important fungal pathogen. The disease it causes, paracoccidioidomycosis (PCM), ranges from localized pulmonary infection to systemic processes that endanger the life of the patient. Paracoccidioides brasiliensis adhesion to host tissues contributes to its virulence, but we know relatively little about molecules and the molecular mechanisms governing fungal adhesion to mammalian cells. Triosephosphate isomerase (TPI: EC 5.3.1.1) of P. brasiliensis (PbTPI) is a fungal antigen characterized by microsequencing of peptides. The protein, which is predominantly expressed in the yeast parasitic phase, localizes at the cell wall and in the cytoplasmic compartment. TPI and the respective polyclonal antibody produced against this protein inhibited the interaction of P. brasiliensis to in vitro cultured epithelial cells. TPI binds preferentially to laminin, as determined by peptide inhibition assays. Collectively, these results suggest that TPI is required for interactions between P. brasiliensis and extracellular matrix molecules such as laminin and that this interaction may play an important role in the fungal adherence and invasion of host cells. 相似文献
Life on Earth is supported by an infinite number of interactions among organisms. Species interactions in these networks are influenced by latitude, evolutionary history and species traits. We performed a global‐scale literature analysis to build up a database of interactions between anuran communities and their preys, from a wide range of geographical areas, using a network approach. For this purpose, we compiled a total of 55 weighted anuran–prey interaction networks, 39 located in the tropics and 16 in temperate areas. We tested the influence of latitude, as well as anuran taxonomic, functional and phylogenetic richness on network metrics. We found that anuran–prey networks are not nested, exhibit low complementary specialization and modularity and high connectance when compared to other types of networks. The main effects on network metrics were related to latitude, followed by anuran taxonomic, functional and phylogenetic richness, a pattern similar to the emerging in mutualistic networks. Our study is the first integrated analysis of the structural patterns in anuran–prey antagonistic interaction networks in different parts of the world. We suggest that different processes, mediated mainly by latitude, are modeling the architecture of anuran–prey networks across the globe. 相似文献
Human impacts can affect the soil properties through erosion and leaching, the ecosystem functions and, consequently, the capacity of a forest to regenerate. Here, we determine the effects of forest disturbance and succession on selected soil chemical properties using two different approaches, before‐after‐control‐impact (BACI) and space‐for‐time (SFT) substitution, and the threatened Atlantic Forest biome as model. We assessed with BACI the long‐term (37‐year) effects of clear cutting on soil properties by comparing data from two topsoil surveys (1978–2017) divided into two treatments: a preserved old growth forest (control) and an adjacent forest that was experimentally cleared with full tree removal (clear‐cut). We examined with SFT the relationship between stand age and soil properties using soil data from three old growth and 13 s growth forests ranging from 7 to 33 years. We found no significant differences between treatments for any soil property or significant changes in phosphorus, potassium, and calcium + magnesium over time. In contrast, pH increased and aluminum decreased in both areas. No relation was found between forest age and most of soil properties, with the exception of potassium which returned to old growth forest levels after 20 years of natural succession, and pH. BACI indicated that deforestation of old growth forest caused no significant effects on soil chemical properties after 37 years of regeneration. SFT demonstrated that soil properties did not change significantly during forest regeneration on formerly disturbed lands. Our findings indicate that natural nutrient‐depleted lowland forests were overall resistant to deforestation followed by passive regeneration at landscape scale. Abstract in Portuguese is available with online material. 相似文献
Habitat fragmentation could alter ecological traits including species trophic habits. Here, we used carbon and nitrogen stable isotope ratios to establish differences in isotopic niche width and food resource use between forest fragments and the continuous forest for the phyllostomid frugivorous bat Artibeus lituratus. Using mist nests, we captured bats from two forest fragments and two sites in continuous forest, and sampled from each individual captured three body tissues with contrasting turnover rates (skin, muscle, and liver). Samples were collected between February and March (austral summer) and between August and September (austral winter). In addition, in each sampling site and season we collected potential food resources (fruits and insects) consumed by our A. lituratus. Our findings indicate that A. lituratus had a predominantly omnivorous diet, with high consumption of insects during summer in forest fragments. The increasing consumption of insects in these fragments seems to have led to a wider isotopic niche, in relation to the continuous forest. Because A. lituratus is typically a seed disperser, changes in trophic habits in the forest fragments from frugivory to insectivory may diminish their role in forest regeneration. Abstract in Portuguese is available with online material. 相似文献
The genetic analysis of Brachyplatystoma platynemum individuals sampled from the lower Madeira River reinforces the existence of two structured populations in the Amazon Basin (Madeira and Amazon populations). However, the recapture of an individual from the Amazon population in the Solimões River, which was telemetry-tagged in the Madeira River after the damming, indicates that fish from the Amazon population move between the two river systems. This has not yet been observed, however, in the Madeira River population, which is currently divided and isolated in the lower and upper Madeira River by the construction of two dams. 相似文献
Bait traps are effective and commonly used method in the studies of orchid bees. Important questions in the context of this method, including those related to bait dispersion, how long baits remain attractive, the distance from which males are supposed to be attracted to lures and so on, are still open subjects. Data on the attractiveness of bait traps that have remained in the field during two weeks in a large Atlantic forest preserve are presented. Four main results emerge from the data: (i) the abundance of specimens collected per day decreased in all the attractants as the traps were left on the field; (ii) despite this decrease, the absolute number of individuals collected after eight and fifteen days is remarkably, mostly in eugenol and vanillin baits; (iii) the vast majority of species, 22 of 25, was already collected on the first sample day; (iv) a consistent variation in the relative abundance of individuals collected in each scent as collections were made. We urge that bait traps should not be left in the field beyond what is strictly necessary since there is a real possibility of collecting a significant number of individuals as these traps remain available. 相似文献
Biological Trace Element Research - Predator fish can accumulate high levels of mercury, which qualifies them as potential indicators of this toxic metal. The predatory species Brachyplatystoma... 相似文献
Photosynthesis Research - This study examined whether drought sensitivity in açaí (Euterpe oleracea Mart.) is associated with reductions in photosynthesis and increasing oxidative stress... 相似文献
The objective of this study was to evaluate the effects of different natural ventilation systems and explant types on the growth and volatile compound content of Lippia gracilis cultured in vitro. The treatments consisted of four membrane systems (without membrane, with one, two, and four porous membranes) and two explant types (nodal segments with and without a pair of leaves). The evaluation of growth, photosynthetic pigments and chemical analysis of the volatile fraction were performed at 35 days of cultivation in half strength MS basal medium. Natural ventilation systems significantly influenced the in vitro growth and volatile fraction of L. gracilis. Explants with a pair of leaves obtained the best experimental responses. The natural ventilation system with four membranes provided the best growth parameters and leaf area response of L. gracilis explants with leaves. The photosynthetic pigments decreased with an increase in the number of porous membranes in the culture flask. Variations in the number, content, and profile of volatile compounds under the influence of natural ventilation systems were observed. Major constituents such as ρ-cymene, γ-terpinene, thymol, carvacrol, and E-caryophyllene, regardless of experimental conditions, were identified. The highest carvacrol and thymol contents were observed in plantlets grown in culture flasks with four porous membranes. To maximize the content of carvacrol and thymol from the in vitro culture of L. gracilis, explants with a pair of leaves and four porous membranes in culture flasks are recommended for use.