Sharing is living: The role of habitat heterogeneity in the coexistence of closely related species.

In biologically diverse ecosystems, an essential process to support competing species to coexist is ecological differentiation. Habitat heterogeneity is, hence, important in establishing species abundance and richness, favoring the coexistence of species due to habitat partition. In this context, shading and species thermal tolerance can be good factors to elucidate the role of habitat heterogeneity in the habitat partition among closely related species. Herein, we study shading effects in microhabitat selection, behavior, and physiological limitation on two species of fiddler crabs (Leptuca leptodactyla and Leptuca uruguayensis). Indeed, shading conditions influenced fiddler crabs species proportion over time, with L. leptodactyla more associated with nonshaded/warmer areas while the L. uruguayensis to shaded/cooler ones. They also adjusted their behavior differently from each other to deal with thermal stress. Finally, we have demonstrated that these effects are related to species' physiological limitations. We conclude that biologically diverse ecosystems, such as intertidal regions from estuaries (e.g., mudflats and mangroves), support the coexistence between closely related species by reducing competition due to habitat partition.

Phylogeographic Structure within the Fiddler Crabs Leptuca thayeri and Uca maracoani (Brachyura, Ocypodidae) along the Tropical West Atlantic.

Most fiddler crabs have an extended planktonic larval phase, potentially maintaining gene flow among widely separated populations, in the absence of marine barriers. Such marine barriers could be long coastal stretches without suitable habitat, freshwater plumes caused by large river mouths, or strong currents. Typically, fiddler crabs inhabit mangrove habitats, and as mangroves tend to have a patchy distribution, it is important to gather information on the connectivity between neighboring mangroves and recognize local endemisms. To detect potential genetic differentiation among mangrove-dwelling populations of Leptuca thayeri and Uca maracoani along several thousand kilometers of a tropical coastline, mtDNA sequences of different populations from Brazil and two Caribbean islands were analyzed and compared. As shown in previous studies with fiddler crabs, Brazilian populations are genetically indiscernible, and our data suggest the absence of long-standing gene flow barriers in the two studied species along the Brazilian coast. This includes both sides of the postulated biogeographic barriers corresponding to the split of the Central South Equatorial Current and to the Amazon River freshwater plume. In contrast, conspecific individuals from the Greater Antilles carried different haplotypes, suggesting a biogeographical barrier between Brazil and the Caribbean, apparently having limited gene flow between both regions for extended time periods.

Treatment and characterization of biomass of soybean and rice hulls using ionic liquids for the liberation of fermentable sugars.

We investigated the changes in the physical structure of cellulose recovered from soybean and rice hulls treated with the ionic liquids 1-butyl-3-methylimidazolium chloride ([bmim][Cl]) and 1-butyl-3-methylimidazolium acetate ([bmim][Ac]). The characterization was carried out by a combination of thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Regenerated cellulose from soybean hull showed loss of crystallinity and high structural disruption caused by both ionic liquid treatments as compared to the untreated material. In contrast, rice hull presented only a small structural disruption when treated with [bmim][Ac] and was practically unaffected by [bmim][Cl], showing that this biomass residue is recalcitrance towards physico-chemical treatments, possibly as a consequence of its high composition content in silica. These results suggest the use of soybean hull as a substrate to be treated with ionic liquids in the preparation of lignocellulosic hydrolysates to be used in second-generation ethanol production, whereas other methods should be considered to treat rice hull biomass.

Point-of-care testing for measuring haemolymph glucose in invertebrates is not a valid method.

Blood glucose is widely used as a physiological parameter for vertebrates and invertebrates. However, its measurement in the field is often difficult due to the need for expensive and non-portable equipment. Point-of-care (POC) devices, originally intended for human use, are increasingly being used for measuring blood parameters of animals in the field. In this regard, POC glucose meters are becoming valuable tools for conservation physiologists, as glucose can be a useful indicator of stress response. In invertebrates, the use of POC glucose meters is still scarce, and no study yet has evaluated their usability in crustaceans and molluscs. We tested if a POC device can be used to measure haemolymph glucose in two widely used models, Leptuca thayeri and Perna perna, compared with a standard laboratory method. The device was unable to measure glucose in P. perna haemolymph due to equipment inaccuracy and low glucose concentration in this species (10.13 ± 6.25 mg/dL). Additionally, despite the device being capable of measuring glucose in L. thayeri haemolymph, Bland-Altman plots showed a strong bias and wide limits of agreement, and Lin's concordance correlation coefficient showed a weak concordance between methods. When simulating experimental conditions, POC results differed from those found using the standard method. We conclude that POC glucose meters are unsuitable for assessing glucose in mussels and should not be used in crabs as results are inaccurate.

Testing the dear enemy relationship in fiddler crabs: Is there a difference between fighting conspecific and heterospecific opponents?

Reduction of aggressiveness toward familiar neighbors, when compared to aggressiveness toward unfamiliar strangers, can decrease the costs of territory defense. This phenomenon is known as the "dear enemy effect". Individuals may shift their aggressiveness toward neighbors or strangers from the same or different species, depending on the relative threat associated with different opponents. Therefore, a reduced level of aggressiveness between heterospecific neighbors is expected in relation to conspecific intruders, since the latter compete not only for territory, but also for mates. Herein we investigated the occurrence of the dear enemy effect in territorial fights between conspecific pairs of Leptuca leptodactyla and heterospecific pairs of L. leptodactyla versus Leptuca uruguayensis. Across both conspecific and heterospecific fights, medium- and high-intensity fight components were more used in resident-stranger than in resident-neighbor fights. Thus, residents showed a dear enemy response, regardless of opponent species. Moreover, conspecific fights induced a greater number of low- and medium-intensity fight components than did fights between heterospecifics, both neighbors and strangers. Finally, conspecific resident-stranger fights took longer than heterospecific resident-stranger fights. Our results indicate that fiddler crabs adjust their territorial response according to the species and resident status of intruders, consistent with the risks posed by different intruder types.

New strategy to obtain high surface area anatase nanotube/AuNP photocatalyst.

Anatase nanotubes with high surface area (ca. 350 m2 g-1), containing gold nanoparticles, were successfully obtained from trititanate nanotubes, prepared by a template-free hydrothermal method, and calcined at 450 °C. The high surface area and tubular morphology were attained due to the presence of ionic silsesquioxane, which acts as anti-sintering agent for titania during calcination process, by forming a thin silica coating between anatase nanotubes. Additionally, the ionic silsesquioxane also acts as stabilizing and adhesion agent for gold nanoparticles on the surface of anatase nanotubes. The influence of the ionic silsesquioxane on the morphological and textural properties of anatase nanotubes was studied in three different moments during the synthesis: before, after and before/after nanotubes were rolled up. The photocatalytic activity of the nanotube samples was evaluated by hydrogen generation showing remarkable enhancement in hydrogen production and stability of catalyst when compare with the bare anatase sample and commercial P-25.

Contrasting Patterns of Clinal Genetic Diversity and Potential Colonization Pathways in Two Species of Western Atlantic Fiddler Crabs.

Fiddler crabs (Brachyura, Ocypodidae), like many other marine organisms, disperse via planktonic larvae. A lengthy pelagic larval duration is generally assumed to result in genetic connectivity even among distant populations. However, major river outflows, such as of the Amazon or Orinoco, or strong currents may act as phylogeographic barriers to ongoing gene flow. For example, the Mona Passage, located between Puerto Rico and Hispaniola, has been postulated to impair larval exchange of several species. In this study, Cox1 mtDNA data was used to analyze population genetic structure of two fiddler crab species from the western Atlantic, comparing the continental coastline and Caribbean islands. The results indicate genetic homogeneity in Minuca rapax among Atlantic (continental) populations (Suriname, Brazil), whereas Caribbean populations show significantly restricted gene flow among the constituent islands and towards continental populations. Our data support the hypothesis of the Mona Passage hindering larval exchange. Contrastingly, Caribbean Leptuca leptodactyla populations appear to be devoid of detectable variation, while Atlantic-continental (i.e. Brazilian) populations show much higher haplotype and nucleotide diversities and display slight genetic differentiation among populations within the Atlantic region, though not statistically significant. Both species show a pronounced divergence between regions, supporting the presence of a phylogeographic barrier.

Chitosan crosslinked with genipin as support matrix for application in food process: Support characterization and ß-D-galactosidase immobilization.

In order to develop safer processes for the food industry, we prepared a chitosan support with the naturally occurring crosslinking reagent, genipin, for enzyme. As application model, it was tested for the immobilization of ß-D-galactosidase from Aspergillus oryzae. Chitosan particles were obtained by precipitation followed by adsorption of the enzyme and crosslinking with genipin. The particles were characterized by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis (TGA). The immobilization of the enzyme by crosslinking with genipin provided biocatalysts with satisfactory activity retention and thermal stability, comparable with the ones obtained with the traditional methodology of immobilization using glutaraldehyde. ß-D-Galactosidase-chitosan-genipin particles were applied to galactooligosaccharides synthesis, evaluating the initial lactose concentration, pH and temperature, and yields of 30% were achieved. Moreover, excellent operational stability was obtained, since the immobilized enzyme maintained 100% of its initial activity after 25 batches of lactose hydrolysis. Thus, the food grade chitosan-genipin particles seem to be a good alternative for application in food process.

Development of active biofilms of quinoa (Chenopodium quinoa W.) starch containing gold nanoparticles and evaluation of antimicrobial activity.

Active biofilms of quinoa (Chenopodium quinoa, W.) starch were prepared by incorporating gold nanoparticles stabilised by an ionic silsesquioxane that contains the 1,4-diazoniabicyclo[2.2.2]octane chloride group. The biofilms were characterised and their antimicrobial activity was evaluated against Escherichiacoli and Staphylococcusaureus. The presence of gold nanoparticles produces an improvement in the mechanical, optical and morphological properties, maintaining the thermal and barrier properties unchanged when compared to the standard biofilm. The active biofilms exhibited strong antibacterial activity against food-borne pathogens with inhibition percentages of 99% against E. coli and 98% against S. aureus. These quinoa starch biofilms containing gold nanoparticles are very promising to be used as active food packaging for the maintenance of food safety and extension of the shelf life of packaged foods.

Silver nanoparticle-ionic silsesquioxane: a new system proposed as an antibacterial agent.

Spherical silver nanoparticles with an average size of ca. 5 nm were synthesized in aqueous medium using a charged silsesquioxane containing a quaternary ammonium group, the bridged 1,4-diazoniabicyclo[2.2.2]octane nitrate, as a stabilizer and size controller. For the first time this system was synthesized and applied as an antibacterial agent and its activity was confirmed with excellent results. The new system shows high stability, which can be confirmed by the unchanged UV-Vis band even one year later. The magnitude of the zeta-potential (ζ) (+24.7 mV) indicated electrostatic contribution for the silver nanoparticles stability and the signal showed that the nanoparticles have a positively charged surface. In vitro antibacterial tests were performed against E. coli, P. aeruginosa and S. aureus bacteria, and the minimum concentrations of silver in the nanoparticle form for complete inhibition of bacteria were 0.60, 1.1 and 2.0 µg mL-1, respectively. These values are very low when compared to the previous reports, making this system very promising. The cytotoxicity assay showed that these silver nanoparticles are safe for mammalian cells at the studied concentrations.

Burrow morphology of Uca uruguayensis and Uca leptodactylus (Decapoda: Ocypodidae) from a subtropical mangrove forest in the western Atlantic.

The continuous excavation of burrows by fiddler crabs generates bioturbation in the sediment, which can be estimated from burrow morphology. The aim of the present study was to describe the burrow morphology of Uca uruguayensis and U. leptodactylus and its relationship with demography of resident individuals and to estimate the level of bioturbation in the sediment generated by each species. For all individuals from each of the 2 species, sex was determined and the carapace width (CW; mm) measured. Burrows were characterized according to burrow diameter (BD; mm), maximum burrow depth (MBD; mm) and burrow volume (BV; cm(3) ). The density of each species in the study area was also evaluated. In both species, the males were larger and occupied burrows with higher BV compared to females. Differences between sexes in relation to the burrow characteristics might reflect sexual dimorphism within the group and are probably related to the fact that males use the burrows for mating. BD and BV showed significant positive relationships with the size of resident crabs. The amount of sediment removed per burrow was estimated from mean BV: 10.78 cm(3) of sediment/burrow for U. uruguayensis and 12.38 cm(3) of sediment/burrow for U. leptodactylus. Despite the density and depth differences between the 2 species, the similarity in burrow volume suggests that U. uruguayensis and U. leptodactylus present the same importance in terms of the bioturbation process. Burrow morphology is highly associated with characteristics of the occupant, although extrinsic factors should also be considered, and its description can provide estimates on the bioturbation generated by Uca species in mangrove forests.

Effect of the support size on the properties of ß-galactosidase immobilized on chitosan: advantages and disadvantages of macro and nanoparticles.

The effect of the support size on the properties of enzyme immobilization was investigated by using chitosan macroparticles and nanoparticles. They were prepared by precipitation and ionotropic gelation, respectively, and were characterized by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), transmission electron microscopy (TEM), light scattering analysis (LSA), and N(2) adsorption-desorption isotherms. ß-Galactosidase was used as a model enzyme. It was found that the different sizes and porosities of the particles modify the enzymatic load, activity, and thermal stability of the immobilized biocatalysts. The highest activity was shown by the enzyme immobilized on nanoparticles when 204.2 mg protein·(g dry support)(-1) were attached. On the other hand, the same biocatalysts presented lower thermal stability than macroparticles. ß-Galactosidase immobilized on chitosan macro and nanoparticles exhibited excellent operational stability at 37 °C, because it was still able to hydrolyze 83.2 and 75.93% of lactose, respectively, after 50 cycles of reuse.

Ionic silica based hybrid material containing the pyridinium group used as an adsorbent for textile dye.

The present study reports the development of an ionic silica based hybrid material containing the cationic pyridinium group, which was employed for the removal of the Reactive Red 194 textile dye from aqueous solution. Three hybrid material samples were prepared with planned textural and chemical properties, varying the inorganic precursor molar percentage in the sol-gel synthesis. The obtained samples were defined as Py/Si-90, Py/Si-92 and Py/Si-94, where the number specifies the inorganic molar percentage. The hybrid samples were characterized by elemental, infrared, (13)C and (29)Si NMR, N(2) adsorption-desorption isotherms and thermogravimetric analyses. The dye-removing ability of these adsorbents was determined by the batch contact adsorption procedure. Effects such as pH value and adsorbent dosage on the adsorption capacities were studied. Four kinetic models were applied. The adsorption was best fitted to Avrami fractional-order kinetic model for the three hybrid material samples. The kinetic data were also adjusted to an intra-particle diffusion model resulting three linear regions, indicating that the adsorption kinetics follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich and Liu isotherm models. The maximum adsorption capacities were 165.4, 190.3 and 195.9 mg g(-1) for Py/Si-90, Py/Si-92 and Py/Si-94, respectively. Simulated dye-house effluents were used to check the applicability of the proposed adsorbents for effluent treatment. Dye loaded adsorbents were regenerated (>98.2%) by using 0.4 mol L(-1) of NaOH solution as an eluent.

Surfactant-based dispersant for multiwall carbon nanotubes to prepare ceramic composites by a sol-gel method.

A dispersant for multiwall carbon nanotubes (MWCNTs) is proposed that fulfils the requirements of creating a uniform dispersion in the matrix and obtaining a good interface between CNTs and the matrix, and is soluble in generic nonpolar solvents. This dispersant is based on a long chain surfactant, called in this work dabcosil stearate, containing a stearate-based 18-carbon alkyl chain as an anion, and a silsesquioxane containing a bridged, positively charged 1,4-diazoniabicyclo[2.2.2]octane group. It provides not only a very good dispersion medium for the MWCNTs, but also a very good interface between MWCNTs and ceramic matrices, such as alumina and zirconia, prepared by the sol-gel method.

The correlation between subordinate fish eye colour and received attacks: a negative social feedback mechanism for the reduction of aggression during the formation of dominance hierarchies.

Eye darkening has been linked to social status in fish. The subordinate's eyes darken, while the eyes of the dominant fish become pale. Although this phenomenon has been described in salmonid fishes and in the African cichlid Nile tilapia Oreochromis niloticus, it is unclear whether eye darkening correlates with a reduction in aggressive behaviour. Thus, we evaluated the link between social status and eye darkening. We evaluated whether the eye colours of subordinate fish correlate with the frequency of received attacks in a neotropical fish, the pearl cichlid Geophagus brasiliensis. We paired pearl cichlids and quantified both the aggressive behaviour and the eye darkening of each fish. As has been described for Nile tilapia and Atlantic salmon, a clear-cut hierarchical relationship formed, where dominance and subordination were associated with pale and dark eye colours, respectively. Initially, eye colour darkening was positively correlated with the frequency of received attacks; however, a negative association occurred following eye darkening, in which the intensity of aggressive interactions decreased. Thus, fish that initially received a high number of attacks signalled subordination more rapidly and intensely (rapid and dramatic eye darkening), thereby inducing a negative social feedback mechanism that led to reduced aggression.

Synthesis, characterization, and spectroscopic investigation of benzoxazole conjugated Schiff bases.

Two Schiff bases were synthesized by reaction of 2-(4'-aminophenyl)benzoxazole derivatives with 4-N,N-diethylaminobenzaldehyde. UV-visible (UV-vis) and steady-state fluorescence in solution were applied in order to characterize its photophysical behavior. The Schiff bases present absorption in the UV region with fluorescence emission in the blue-green region, with a large Stokes' shift. The UV-vis data indicates that each dye behaves as two different chromophores in solution in the ground state. The fluorescence emission spectra of the dye 5a show that an intramolecular proton transfer (ESIPT) mechanism takes place in the excited state, whereas a twisted internal charge transfer (TICT) state is observed for the dye 5b. Theoretical calculations were performed in order to study the conformation and polarity of the molecules at their ground and excited electronic states. Using density functional theory (DFT) methods at theoretical levels BLYP/Aug-SV(P) for geometry optimizations and B3LYP/6-311++G(2d,p) for single-point energy evaluations, the calculations indicate that the lowest energy conformations are in all cases nonplanar and that the dipole moments of the excited state relaxed structures are much larger than those of the ground state structures, which corroborates the experimental UV-vis absorption results.

Modulation of the ESIPT emission of benzothiazole type dye incorporated in silica-based hybrid materials.

A set of silica-based hybrid material samples was obtained, with different molar fractions of tetraethylorthosilicate and dimethyldimethoxysilane, as inorganic and organic sol-gel precursors, respectively. The hybrid material was used as a matrix to disperse the 2-(4'-amino-2'-hydroxyphenyl)benzothiazole, a fluorophore with large Stokes shift caused by an excited state intramolecular proton transfer phenomena (ESIPT). UV-vis and steady-state fluorescence in the solid state were applied in order to characterize the photophysical behavior of the dye. The set of samples was characterized by infrared spectroscopy, elemental analysis, and N(2) isotherms. The fluorescent pyrene dye was used as a probe for local polarity environment. For the first time, a modulation in the ESIPT fluorescence emission was achieved, being correlated to the methyl organic content of the hybrid matrix. The equilibrium between the conformers in the ground state is affected by changes in the matrix hydrophobicity. The replacement of silanol groups by methyl groups on matrix surface decreases the hydrogen bond capacity with the dye stabilizing the ESIPT conformer, in spite of the normal conformers, which will present a short wavelength emission band.

Nanocapsule@xerogel microparticles containing sodium diclofenac: a new strategy to control the release of drugs.

The aim of this work was to evaluate the potentiality to control the drug release of a new architecture of microparticles organized at the nanoscopic scale by assembling polymeric nanocapsules at the surface of drug-loaded xerogels. Xerogel was prepared by sol-gel method using sodium diclofenac, as hydrophilic drug model, and coated by spray-drying. After coating, the surface areas decreased from 82 to 28 m(2)/g, the encapsulation efficiency was 71% and SEM analysis showed irregular microparticles coated by the nanocapsules. Formulation showed satisfactory gastro-resistance presenting drug release lower than 3% (60 min) in acid medium. In water, the pure drug dissolved 92% after 5 min, uncoated drug-loaded xerogel released 60% and nanocapsule coated drug-loaded xerogel 36%. After 60 min, uncoated drug-loaded xerogel released 82% and nanocapsule coated drug-loaded xerogel 62%. In conclusion, the new system was able to control the release of the hydrophilic drug model.

Anisotropic self-organization of hybrid silica based xerogels containing bridged positively charged 1,4-diazoniabicycle[2.2.2]octane chloride group.

Anisotropic self-organized hybrid silica based xerogels were obtained. The ordered structure was imposed by the double charged 1,4-diazoniabicycle[2.2.2]octane chloride group bonded in a bridged way. This was confirmed by the presence of well defined X-ray diffraction peaks corresponding to an interplanar distance with the same length estimated for the organic bridged groups. The material was characterized by elemental analysis using CHN technique and the chloride ion was analyzed by a potentiometric titration. (13)C and (29)Si CP MAS solid state NMR spectroscopy and thermogravimetric analysis were also performed. The material that can be obtained in the form of powders and transparent monoliths or films, is thermally stable up to 260 degrees C and the samples with high organic content presented birefringence properties.

Carbon nanotube/silica composites obtained by sol-gel and high-pressure techniques.

The successful incorporation of functionalized single-walled carbon nanotubes (f-SWCNTs) into a silica matrix prepared by the sol-gel method is reported herein. SWCNTs produced through catalytic chemical-vapor deposition (CCVD) have been purified and functionalized with sulfuric, nitric and hydrochloric acids to ensure a good dispersion in an aqueous solution. The nanotube composites are prepared using three concentrations of f-SWCNTs (0.025, 0.050 and 0.075 wt%.) in a silica matrix, resulting in translucent monoliths after gelation. Dense, crack-free and hard compacts are obtained by high-pressure processing at 7.7 GPa and room temperature. Compared to the pure silica compact, compacts containing 0.025 and 0.050 wt% f-SWCNTs show an increased toughness of about 54% and 69%, respectively. The influence of f-SWCNTs on some microstructural aspects of the silica matrix has been studied using nitrogen adsorption/desorption isotherms. Raman spectroscopy has been applied to analyze the effect of the silica matrix and high-pressure compaction on the f-SWCNTs incorporated into the silica matrix. These measurements showed that f-SWCNTs remained in the silica matrix under pressure, suggesting an important interaction with the matrix.