Luminescent κ-Carrageenan-Based Electrolytes Containing Neodymium Triflate.

In recent years, the synthesis of polymer electrolyte systems derived from biopolymers for the development of sustainable green electrochemical devices has attracted great attention. Here electrolytes based on the red seaweeds-derived polysaccharide κ-carrageenan (κ-Cg) doped with neodymium triflate (NdTrif3) and glycerol (Gly) were obtained by means of a simple, clean, fast, and low-cost procedure. The aim was to produce near-infrared (NIR)-emitting materials with improved thermal and mechanical properties, and enhanced ionic conductivity. Cg has a particular interest, due to the fact that it is a renewable, cost-effective natural polymer and has the ability of gelling in the presence of certain alkali- and alkaline-earth metal cations, being good candidates as host matrices for accommodating guest cations. The as-synthesised κ-Cg-based membranes are semi-crystalline, reveal essentially a homogeneous texture, and exhibit ionic conductivity values 1⁻2 orders of magnitude higher than those of the κ-Cg matrix. A maximum ionic conductivity was achieved for 50 wt.% Gly/κ-Cg and 20 wt.% NdTrif3/κ-Cg (1.03 × 10-4, 3.03 × 10-4, and 1.69 × 10-4 S cm-1 at 30, 60, and 97 °C, respectively). The NdTrif-based κ-Cg membranes are multi-wavelength emitters from the ultraviolet (UV)/visible to the NIR regions, due to the κ-Cg intrinsic emission and to Nd3+, 4F3/2→4I11/2-9/2.

Restoration over time and sustainability of Schinus terebinthifolius Raddi.

The success of recovery programs on degraded areas is dependent on the genetic material to be used, which should present heterozygosity and genetic diversity in native and recovered populations. This study was carried out to evaluate the model efficiency to enable the recovery of a degraded area of the Lower São Francisco, Sergipe, Brazil. The target species for this study was Schinus terebinthifolius Raddi. Three populations were analyzed, the recovered area, seed-tree source population, and native tree population border established to the recovered area. The random amplified polymorphic DNA (RAPD) markers were used for diversity analysis. Genetic structure was estimated to evaluate the level of genetic variability existent in each population. There was no correlation between the spatial distribution and the genetic distances for all trees of the recovered area. The heterozygosity present in the recovered population was higher than the native tree population. The seed-tree source population presents genetic bottlenecks. Three clusters were suggested (ΔK = 3) with non-genetic structure. High intra-population genetic variability and inter-population differentiation are present. However, gene flow may also introduce potentially adaptive alleles in the populations of the recovered area, and the native population is necessary to ensure the sustainability and maintenance of the populations by allelic exchange.

Purification of plant complex protein extracts in non-denaturing conditions by in-solution isoelectric focusing.

An alternative approach for plant complex protein extracts pre-purification by in-solution isoelectric focusing in non-denaturing conditions is presented. The separation of biologically active proteins, in narrow ranges of isoelectric point (pI) was obtained by a modified OFFGEL electrophoresis. Two different water-soluble protein extracts from Phragmites leaves were fractionated into 24 fractions within a 3-10 pI range at 10 °C in the absence of denaturing/reducing agents. One-dimensional electrophoretic analysis revealed different protein distribution patterns and the effective fractionation of both protein extracts. Peroxidase activity of each fraction confirmed that proteins remained active and pre-purification occurred. Biological triplicates assured the needed reproducibility.

A comparative framework of the Erythrina velutina tree species in reforested land and native populations.

Erythrina velutina Willd. (Fabaceae: Papillionoideae) is a pioneer species found in tropical and subtropical regions of the world that has medicinal properties and that is used in reforestation projects. This species is rare in some areas of northeastern Brazil. This study aimed to characterize and compare genetic structures of natural and restored populations of E. velutina, with a focus on the selection of tree seeds. A total of 108 individuals from five natural populations and one restored population were analyzed using ISSR markers, resulting in 407 polymorphic fragments. A high rate of polymorphism was observed in the restored population. The highest genetic variability was identified within populations (82%). Genetic bottleneck tests were significant for the Carmópolis/Rosário do Catete and Laranjeiras natural populations along with the Laranjeiras restored population. Genetic distances significantly correlated with spatial distance. Only the restored population retained unique alleles. Similarly, increased genetic distance was observed in individuals of the restored populations compared to the other populations. Observed genetic variation in both natural and restored populations of E. velutina was moderate, thus enabling selection of divergent trees from those trees supplying seeds. Environmental protection and management of these areas is necessary for the maintenance of these individuals and subsequent reproduction. We recommend suggestions for E. velutina conservation, since the restoration model adopted in this study did not promote the development of the specimens until the reproductive stage in a fashion that aims to augment the soil seed bank supply, as is suggested for pioneer species.

Selection index using the graphical area applied to sugarcane breeding.

This study aimed to develop a multivariate selection index based on the graphical area of a polygon formed by standardized values, also known as radar chart. This methodology may be used to assist selection of superior genotypes in sugarcane breeding programs. Seven technological traits in 37 sugarcane genotypes were evaluated. An area index (AI) was constructed and the resulting polygon areas were used to rank genotypes under selection. In this study, we propose the use of restricted maximum likelihood to estimate genetic parameters and mixed model equations to predict genotypic and breeding values. The area of each polygon was calculated for phenotypic, genotypic, and estimated breeding values. Thereby, the genotypes with larger area can be selected based on a detailed a posteriori evaluation of the radar charts. The proposed AI can be adjusted based on the breeders' specific interests, it is perfectly useful in other crops, and may also be applied to studies on genotype-environment interactions. Moreover, AI is a powerful tool that can evaluate trait stability of genotypes based on slight differences in the area formed by each genotype. Hence, this method is easy to apply and shows great potential for use in sugarcane breeding programs as well as in other breeding programs.

Relationship among physiological quality, heterosis, and amylase gene expression in maize seeds.

In this study, we analyzed heterosis, amylase enzyme gene expression, and the physiological quality of maize seeds with different genotypes and sizes, which were subjected to aging and not subjected to aging. We used seeds from 2 maize lines that differed with regard to physiological quality, the hybrid, and the reciprocal hybrid; they were classified into 2 sizes and were subjected to aging and not subjected to aging. Physiological quality was assessed by performing tests for germination, emergence, emergence speed index, and artificial aging. Expressions of the genes alpha amylase B73, alpha amylase (LOC542522), isoamylase mRNA clone 353244, and the endogenous controls ubiquitin and alcohol dehydrogenase in the seeds were studied using quantitative real-time-polymerase chain reaction. We observed heterosis for seed quality and for expression of amylase genes in the genotypes studied. We found no difference in seed quality between large and small seeds.

Fabrication of low-cost thermo-optic variable wave plate based on waveguides patterned on di-ureasil hybrids.

An integrated variable wave plate device based on a thermo-optic (TO) effect was fabricated by patterning a waveguide channel through direct UV laser writing on the surface of sol-gel derived organic-inorganic hybrid (di-ureasil) films. The di-ureasil layer is stable up to 250 °C and has a high TO coefficient calculated as -(4.9 ± 0.5) × 10(-4) °C(-1) at 1550 nm. The waveguide temperature was tuned, inducing optical phase retardation between the transverse electric and transverse magnetic modes, resulting in a controllable wave plate. A maximum phase retardation of 77 ° was achieved for a waveguide induced temperature increase of 5 °C above room temperature, with a power consumption of 0.4 W. The thermal linear retardation coefficient was calculated to be 19 ± 1 °/ °C.

Luminescent DNA- and agar-based membranes.

Luminescent materials containing europium ions are investigated for different optical applications. They can be obtained using bio-macromolecules, which are promising alternatives to synthetic polymers based on the decreasing oil resources. This paper describes studies of the DNA- and Agar-europium triflate luminescent membranes and its potential technological applications are expanded to electroluminescent devices. Polarized optical microscopy demonstrated that the samples are birefringent with submicrometer anisotropy. The X-ray diffraction analysis revealed predominantly amorphous nature of the samples and the atomic force microscopy images showed a roughness of the membranes of 409.0 and 136.1 nm for the samples of DNA10Eu and Agar1.11Eu, respectively. The electron paramagnetic resonance spectra of the DNA(n)Eu membranes with the principal lines at g ≈ 2.0 and g ≈ 4.8 confirmed uniform distribution of rare earth ions in a disordered matrix. Moreover, these strong and narrow resonance lines for the samples of DNA(n)Eu when compared to the Agar(n)Eu suggested a presence of paramagnetic radicals arising from the DNA matrix. The emission spectra suggested that the Eu3+ ions occupy a single local environment in both matrices and the excitation spectra monitored around the Eu emission lines pointed out that the Eu3+ ions in the Agar host were mainly excited via the broad band component rather than by direct intra-4f(6) excitation, whereas the opposite case occurred for the DNA-based sample.

Enhanced Eu3+ emission in aqueous phosphotungstate colloidal systems: stabilization of polyoxometalate nanostructures.

Luminescent Eu(3+)-containing polyphosphate-tungstate aqueous colloidal systems were prepared and studied as a function of the relative polyphosphate-tungstate content. In polyphosphate-rich solutions, Eu(3+) ions occupy cagelike sites composed of phosphate groups from the metaphosphate chains. In these sites, an average number of 0.5 water molecule coordinates to an Eu(3+) ion and the (5)D(0) emission quantum efficiency is 0.22. Tungstate addition leads to important modifications in neighboring Eu(3+) leading to coordination sites in the aqueous medium where metal ions are completely hidden from interactions with solvent molecules. Transmission electron microscopy results clearly show W-rich nanoparticles with sizes between 5 and 10 nm for all tungstate relative concentrations. For high tungstate relative contents (above 30 mol %), spectroscopic results suggest the presence of Eu(3+) in polyoxometalate (POM)-like sites by comparison with the well-known decatungstoeuropate [EuW(10)O(36)](9-) structure. These new aqueous colloids display surprisingly high (5)D(0) emission quantum efficiencies of ca 80% because of the strong ligand field provided by tungstate POM ligands and the complete absence of water molecules from the Eu(3+) first coordination shell.

Activity and shelter-related behavior in Rhodnius prolixus: The role of host odours.

Triatomine bugs are considered nocturnal insects that feed on the blood of vertebrates and remain hidden inside narrow shelters during daylight hours. Nevertheless, it is not clear whether these insects become active and leave their shelters on a daily basis, less frequently or, even fortnightly. Activity patterns were studied in Rhodnius prolixus Stål, 1859 (Hemiptera: Triatominae) associated with shelters to evaluate whether the decision to leave a shelter depends on bug starvation and the presence of host odours. Experiments were conducted with groups of 5th instar nymphs released in an experimental arena offering an artificial shelter consisting of a piece of corrugated cardboard positioned in its centre. Results indicate that host odours promoted a significant increase in shelter related activity, i.e. shelter-leaving or entering movements, and also in bug locomotion. This increase could only be observed with bugs starved for 30 or 60 days, but not for 21 days. Most R. prolixus nymphs that left shelters and engaged in locomotory activity were starved and in the presence of host odours. Even though R. prolixus is mostly considered a very active and "aggressive" triatomine, our results contradict this perspective and suggest that its main strategy regarding hosts is to wait and carefully evaluate feeding chances before becoming exposed. This behavioural strategy might have arisen through their evolution in palm trees in association with a diverse fauna that may impose predation risks.

Interconvertable modular framework and layered lanthanide(III)-etidronic acid coordination polymers.

Isostructural modular microporous Na2[Y(hedp)(H2O)0.67] and Na4[Ln2(hedp)2(H2O)2].nH2O (Ln = La, Ce, Nd, Eu, Gd, Tb, Er) framework-type, and layered orthorhombic [Eu(H2hedp)(H2O)2].H2O and Na0.9[Nd0.9Ge0.10(Hhedp)(H2O)2], monoclinic [Ln(H2hedp)(H2O)].3H2O (Ln = Y, Tb), and triclinic [Yb(H2hedp)].H2O coordination polymers based on etidronic acid (H5hedp) have been prepared by hydrothermal synthesis and characterized structurally by (among others) single-crystal and powder X-ray diffraction and solid-state NMR. The structure of the framework materials comprises eight-membered ring channels filled with Na+ and both free and lanthanide-coordinated water molecules, which are removed reversibly by calcination at 300 degrees C (structural integrity is preserved up to ca. 475 degrees C), denoting a clear zeolite-type behavior. Interesting photoluminescence properties, sensitive to the hydration degree, are reported for Na4[Eu2(hedp)2(H2O)2].H2O and its fully dehydrated form. The 3D framework and layered materials are, to a certain extent, interconvertable during the hydrothermal synthesis stage via the addition of HCl or NaCl: of the 3D framework Na4[Tb2(hedp)2(H2O)2].nH2O, affords layered [Tb(H2hedp) (H2O)].3H2O, whereas layered [Tb(H2hedp)(H2O)2].H2O reacts with sodium chloride yielding a material similar to Na4[Tb2(hedp)2(H2O)2].nH2O. In layered [Y(H2hedp)(H2O)].3H2O, noncoordinated water molecules are engaged in cooperative water-to-water hydrogen-bonding interactions, leading to the formation of a (H2O)13 cluster, which is the basis of an unprecedented two-dimensional water network present in the interlayer space.

Constructed wetland treatment system in textile industry and sustainable development.

This study focuses on the evaluation of the adequacy and sustainability of a constructed wetland (CW), with vertical flow (VF) design to treat a strongly coloured textile wastewater.Secondly an accidental AO7 overloaded discharge (700 mg l(-1)) was studied. A set of three similar VFCW beds (3x1 m2), operating in series, allowed also the efficient treatment of the AO7 heavy loaded wastewaters. The treated effluent quality enables water reuse for irrigation purposes or within the process.

Responses of Euglossine Bees (Hymenoptera, Apidae, Euglossina) to an Edge-Forest Gradient in a Large Tabuleiro Forest Remnant in Eastern Brazil.

Euglossine fauna of a large remnant of Brazilian Atlantic forest in eastern Brazil (Reserva Natural Vale) was assessed along an edge-forest gradient towards the interior of the fragment. To test the hypotheses that the structure of assemblages of orchid bees varies along this gradient, the following predictions were evaluated: (i) species richness is positively related to distance from the forest edge, (ii) species diversity is positively related to distance from the edge, (iii) the relative abundance of species associated with forest edge and/or open areas is inversely related to the distance from edge, and (iv) relative abundance of forest-related species is positively related to distance from the edge. A total of 2264 bees of 25 species was assessed at five distances from the edge: 0 m (the edge itself), 100 m, 500 m, 1000 m and 1500 m. Data suggested the existence of an edge-interior gradient for euglossine bees regarding species diversity and composition (considering the relative abundance of edge and forest-related species as a proxy for species composition) but not species richness.

A quantitative proteomic approach to highlight Phragmites sp. adaptation mechanisms to chemical stress induced by a textile dyeing pollutant.

Phragmites sp. is present worldwide in treatment wetlands though the mechanisms involved in the phytoremediation remain unclear. In this study a quantitative proteomic approach was used to study the prompt response and adaptation of Phragmites to the textile dyeing pollutant, Acid Orange 7 (AO7). Previously, it was demonstrated that AO7 could be successfully removed from wastewater and mineralized in a constructed wetland planted with Phragmites sp. This azo dye is readily taken up by roots and transported to the plant aerial part by the xylem. Phragmites leaf samples were collected from a pilot scale vertical flow constructed wetland after 0.25, 3.25 and 24.25h exposure to AO7 (400mgL-1) immediately after a watering cycle used as control. Leaf soluble protein extraction yielded an average of 1560 proteins in a broad pI range (pH3-10) by two-dimensional gel electrophoresis. A time course comparative analysis of leaf proteome revealed that 40 proteins had a differential abundance compared to control (p<0.05) within a 3.25h period. After 24.25h in contact with AO7, leaf proteome was similar to control. Adaptation to AO7 involved proteins related with cellular signalling (calreticulin, Ras-related protein Rab11D and 20S proteasome), energy production and conversion (adenosine triphosphate synthase beta subunit) carbohydrate transport and metabolism (phosphoglucose isomerase, fructose-bisphosphate aldolase, monodehydroascorbate reductase, frutockinase-1 and Hypothetical protein POPTR_0003s12000g and the Uncharacterized protein LOC100272772) and photosynthesis (sedoheptulose-1,7-bisphosphatase and ferredoxin-NADP+ reductase). Therefore, the quantitative proteomic approach used in this work indicates that mechanisms associated with stress cell signalling, energy production, carbohydrate transport and metabolism as well as proteins related with photosynthesis are key players in the initial chemical stress response in the phytoremediation process of AO7.

Encapsulation of a [Dy(OH2)8](3+) cation: magneto-optical and theoretical studies of a caged, emissive SMM.

The first supramolecular cage formed by three benzo-15-crown-5 macrocycles encapsulating a [Dy(OH2)8](3+) guest cation is reported, with the Dy(iii) centre exhibiting local pseudo square antiprismatic D4d symmetry. The anisotropy barrier extracted from ac susceptibility studies, emission spectroscopy and ab initio calculations reveals that the second excited state Kramers doublet plays a key role in the magnetization dynamics due to the Ising character and near coparallel nature of the ground and first excited Kramers doublets.

Eu3+ coordination in an organic/inorganic hybrid matrix with methyl end-capped short polyether chains.

Fourier Transform mid-infrared (FT-IR), Fourier Transform Raman (FT-Raman) and photoluminescence spectroscopies and Two-Dimensional (2D) Correlation Spectroscopic Analysis were employed to examine the anionic and cationic local environments in mono-urethanesils doped with europium triflate (Eu(CF(3)SO(3))(3)). The hybrid host framework of these materials is composed of a siliceous backbone bonded through urethane linkages to CH(3)-terminated polymer chains containing about 7 OCH(2)CH(2) units. Samples with infinity >/= n (composition) >/=5 (where n = OCH(2)CH(2)/Eu(3+)) were studied. In terms of ionic association, the level of complexity of these xerogels is very high. In all the compounds the triflate ions exist "free", weakly coordinated and forming cross-link separated ion pairs. At 20 >/= n >/= 5, in addition to all these species contact ion pairs occur. In agreement with these conclusions, photoluminescence establishes the presence of three distinct cation local sites (Eu(3+)/O=C(urethane cross-links), Eu(3+)/O-C-C(polyether chains) and weakly coordinated Eu(3+)/CF(3)SO(3)(-) ionic pairs).

Local structure and near-infrared emission features of neodymium-based amine functionalized organic/inorganic hybrids.

Nd(3+)-based organic/inorganic hybrids have potential application in the field of integrated optics. Attractive sol-gel derived di-urea and di-urethane cross-linked poly(oxyethylene) (POE)/siloxane hybrids (di-ureasils and di-urethanesils, respectively) doped with neodymium triflate (Nd(CF(3)SO(3))(3)) were examined by Fourier transform mid-infrared (FT-IR), Raman (FT-Raman), (29)Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) and photoluminescence spectroscopies, and small-angle X-ray scattering (SAXS). The goals of this work were to determine which cation coordinating site of the host matrix (ether oxygen atoms or carbonyl oxygen atoms) is active in each of the materials analyzed, its influence on the nanostructure of the samples and its relation with the photoluminescence properties. The main conclusion derived from this study is that the hydrogen-bonded associations formed throughout the materials play a major role in the hybrids nanostructure and photoluminescence properties.

Evaluation of homologous, heterologous, and affinity conjugates for the serodiagnosis of Toxoplasma gondii and Neospora caninum in maned wolves (Chrysocyon brachyurus).

Use of serological tests in the diagnosis of infectious diseases in wild animals has several limitations, primarily the difficulty of obtaining species-specific reagents. Wild canids, such as maned wolves (Chrysocyon brachyurus), are highly predisposed to infection by Toxoplasma gondii and, to a lesser extent, to Neospora caninum. The aim of the present study was to evaluate homologous, heterologous, and affinity conjugates in enzyme-linked immunosorbent assays (ELISAs) and indirect fluorescent antibody tests (IFATs) for detecting immunoglobulin (Ig) G antibodies against T. gondii and N. caninum in maned wolves. Serum samples were obtained from 59 captive animals in Brazil and tested by ELISA for T. gondii serology and IFAT for N. caninum serology using 3 different enzymatic and fluorescent conjugates: homologous (guinea pig anti-maned wolf IgG-peroxidase and -fluorescein isothiocyanate [FITC]), heterologous (rabbit anti-dog IgG-peroxidase and -FITC), and affinity (protein A-peroxidase and -FITC). Seropositivity to T. gondii was comparable among the homologous (69.5%), heterologous (74.6%), and affinity (71.2%) enzymatic conjugates. A significant positive correlation was found between the antibody levels determined by the 3 enzymatic conjugates. The highest mean antibody levels (ELISA index = 4.5) were observed with the protein A-peroxidase conjugate. The same seropositivity to N. caninum (8.5%) was found with the homologous and heterologous fluorescent conjugates, but protein A-FITC was not able to detect or confirm any positive samples with homologous or heterologous conjugates. Our results demonstrate that homologous, heterologous, and affinity conjugates might be used in ELISA for serological assays of T. gondii in wild canids, whereas for N. caninum infection, only the homologous or heterologous fluorescent conjugates have been shown to be useful.

Speciation of organomercurials in biological and environmental samples by gas chromatography with microwave-induced plasma atomic emission detection.

The applicability of a commercial microwave-induced plasma atomic emission detector with capillary gas chromatography for mercury speciation in environmental samples was examined. The chromatographic conditions were optimized in order to obtain an adequate resolution of the methylmercury peak vs. interfering carbon signals. Under the proposed operational conditions, the detection limit (signal-to-noise ratio = 3) was 1.2 pg with a linear range of 1-40 ng ml-1 (as methylmercury in samples). Certified reference material (DORM-1) was used to evaluate the accuracy. The results of the proposed procedure were compared with those obtained by means of the usual GC method with electron-capture detection.