Thermo-solvatochromism in binary mixtures of water and ionic liquids: on the relative importance of solvophobic interactions

The thermo-solvatochromism of 2,6-dibromo-4-[(E)-2-(1-methylpyridinium-4-yl)ethenyl] phenolate, MePMBr(2), has been studied in mixtures of water, W, with ionic liquids, ILs, in the temperature range of 10 to 60 degrees C, where feasible. The objectives of the study were to test the applicability of a recently introduced solvation model, and to assess the relative importance of solute-solvent solvophobic interactions. The ILs were 1-allyl-3-alkylimidazolium chlorides, where the alkyl groups are methyl, 1-butyl, and 1-hexyl, respectively. The equilibrium constants for the interaction of W and the ILs were calculated from density data; they were found to be linearly dependent on N(C), the number of carbon atoms of the alkyl group; van't Hoff equation (log K versus 1/T) applied satisfactorily. Plots of the empirical solvent polarities, E(T) (MePMBr(2)) in kcal mol(-1), versus the mole fraction of water in the binary mixture, chi(w), showed non-linear, i.e., non-ideal behavior. The dependence of E(T) (MePMBr(2)) on chi(w), has been conveniently quantified in terms of solvation by W, IL, and the ""complex"" solvent IL-W. The non-ideal behavior is due to preferential solvation by the IL and, more efficiently, by IL-W. The deviation from linearity increases as a function of increasing N(C) of the IL, and is stronger than that observed for solvation of MePMBr(2) by aqueous 1-propanol, a solvent whose lipophilicity is 12.8 to 52.1 times larger than those of the ILs investigated. The dependence on N(C) is attributed to solute-solvent solvophobic interactions, whose relative contribution to solvation are presumably greater than that in mixtures of water and 1-propanol.

X-ray diffraction data of tibolone Delta(4) isomer (isotibolone)

Tibolone is used for hormone reposition of postmenopause women and isotibolone is considered the major degradation product of tibolone. Isotibolone can also be present in tibolone API raw materials due to some inadequate synthesis. Its presence is then necessary to be identified and quantified in the quality control of both API and drug products. In this work we present the indexing of an isotibolone X-ray diffraction pattern measured with synchrotron light (lambda=1.2407 angstrom) in the transmission mode. The characterization of the isotibolone sample by IR spectroscopy, elemental analysis, and thermal analysis are also presented. The isotibolone crystallographic data are a=6.8066 angstrom, b=20.7350 angstrom, c=6.4489 angstrom, beta=76.428 degrees, V=884.75 angstrom(3), and space group P2(1), rho(o)= 1.187 g cm(-3), Z=2. (C) 2009 International Centre for Diffraction Data. [DOI: 10.1154/1.3257612]

Cloud point extraction to avoid interferences by structured background on nickel determination in plant materials by FAAS

An analytical procedure based on microwave-assisted digestion with diluted acid and a double cloud point extraction is proposed for nickel determination in plant materials by flame atomic absorption spectrometry. Extraction in micellar medium was successfully applied for sample clean up, aiming to remove organic species containing phosphorous that caused spectral interferences by structured background attributed to the formation of PO species in the flame. Cloud point extraction of nickel complexes formed with 1,2-thiazolylazo-2-naphthol was explored for pre-concentration, with enrichment factor estimated as 30, detection limit of 5 mu g L(-1) (99.7% confidence level) and linear response up to 80 mu g L(-1). The accuracy of the procedure was evaluated by nickel determinations in reference materials and the results agreed with the certified values at the 95% confidence level.

The enzymatic nature of fungal bioluminescence

The uncertainty about the possible involvement of a luciferase in fungal bioluminescence has not only hindered the understanding of its biochemistry but also delayed the characterization of its constituents. The present report describes how in vitro light emission can be obtained enzymatically from the cold and hot extracts assay using different species of fungi, which also indicates a common mechanism for all these organisms. Kinetic data suggest a consecutive two-step enzymatic mechanism and corroborate the enzymatic proposal of Airth and Foerster. Finally, overlapping of light emission spectra from the fungal bioluminescence and the in vitro assay confirm that this reaction is the same one that occurs in live fungi.

Distribution and behavior of manganese in the Alto do Paranapanema Basin

This paper reports manganese (Mn) fractionation in samples collected from the water column and sediments in an environmental protection area in the Alto do Paranapanema Basin (Sao Paulo State, Brazil). The three locations studied showed equivalent Mn levels, with moderate seasonal differences (p < 0.05). The sediment samples contained five Mn species (p < 0.05): iron and manganese (hydr)oxides > Mn bound to carbonates approximate to exchangeable Mn approximate to Mn bound to silicates > Mn bound to organic matter (p < 0.05). The water samples contained three species (p < 0.05): particulate Mn > labile Mn approximate to non-labile Mn. The data suggest that Mn has a natural origin (Enrichment Factor EF < 2; Geoaccumulation Index I(geo) < 0) and moderate environmental risk (Risk Assessment Code RAC similar to 30%). At the same time, under certain conditions some manganese species could be present in a state of equilibrium between the water column and sediment. These results could provide a basis for Mn management in the Alto do Paranapanema Basin.

Knoop Microhardness and FT-Raman Spectroscopic Evaluation of a Resin-Based Dental Material Light-Cured by an Argon Ion Laser and Halogen Lamp: An in Vitro Study

Objective: The purpose of this study was to evaluate in vitro the Knoop microhardness (Knoop hardness number [KHN]) and the degree of conversion using FT-Raman spectroscopy of a light-cured microhybrid resin composite (Z350-3M-ESPE) Vita shade A3 photopolymerized with a halogen lamp or an argon ion laser. Background Data: Optimal polymerization of resin-based dental materials is important for longevity of restorations in dentistry. Materials and Methods: Thirty specimens were prepared and inserted into a disc-shaped polytetrafluoroethylene mold that was 2.0 mm thick and 3 mm in diameter. The specimens were divided into three groups (n = 10 each). Group 1 (G1) was light-cured for 20 sec with an Optilux 501 halogen light with an intensity of 1000 mW/cm(2). Group 2 (G2) was photopolymerized with an argon laser with a power of 150 mW for 10 sec, and group 3 (G3) was photopolymerized with an argon laser at 200 mW of power for 10 sec. All specimens were stored in distilled water for 24 h at 37 degrees C and kept in lightproof containers. For the KHN test five indentations were made and a depth of 100 mu m was maintained in each specimen. One hundred and fifty readings were obtained using a 25-g load for 45 sec. The degree of conversion values were measured by Raman spectroscopy. KHN and degree of conversion values were obtained on opposite sides of the irradiated surface. KHN and degree of conversion data were analyzed by one-way ANOVA and Tukey tests with statistical significance set at p < 0.05. Results: The results of KHN testing were G1 = 37.428 +/- 4.765; G2 = 23.588 +/- 6.269; and G3 = 21.652 +/- 4.393. The calculated degrees of conversion (DC%) were G1 = 48.57 +/- 2.11; G2 = 43.71 +/- 3.93; and G3 = 44.19 +/- 2.71. Conclusions: Polymerization with the halogen lamp ( G1) attained higher microhardness values than polymerization with the argon laser at power levels of 150 and 200 mW; there was no difference in hardness between the two argon laser groups. The results showed no statistically significant different degrees of conversion for the polymerization of composite samples with the two light sources tested.

Simultaneous determination of Cr, Fe, Ni and V in crude oil by emulsion sampling graphite furnace atomic absorption spectrometry

In this work a simple and reliable method for the simultaneous determination of Cr, Fe, Ni and V in crude oil, using emulsion sampling graphite furnace atomic absorption spectrometry is proposed. Under the best conditions, sample masses around 50 mg were weighed in polypropylene tubes and emulsified in a mixture of 0.5% (v v(-1)) hexane + 6% (m v(-1)) Triton X-100 (R). Considering the compromised conditions, the pyrolysis an atomization temperatures for the simultaneous determination of Cr, Fe, Ni and V were 1400 degrees C and 2500 degrees C, respectively. Aliquots of 20 mu L of reference solution and sample emulsion were co-injected into the graphite tube with 10 mu L of 1.0 g L(-1) Mg(NO(3))(2) as chemical modifier. The detection limits (n = 10, 3 sigma) and characteristic masses were, respectively: 0.07 mu g g(-1) and 19 pg for Cr; 2.15 mu g g(-1) and 31 pg for Fe; 1.25 mu g g(-1) and 44 pg for Ni; and 1.15 mu g g(-1) and 149 pg for V. The reliability of the proposed method was checked by fuel oil Standard Reference Material (SRMTriton X-100 (R) 1634c - NIST) analysis. The concentrations found presented no statistical differences compared to the certified values at 95% confidence level.

New genes of Xanthomonas citri subsp citri involved in pathogenesis and adaptation revealed by a transposon-based mutant library

Background: Citrus canker is a disease caused by the phytopathogens Xanthomonas citri subsp. citri, Xanthomonas fuscans subsp. aurantifolli and Xanthomonas alfalfae subsp. citrumelonis. The first of the three species, which causes citrus bacterial canker type A, is the most widely spread and severe, attacking all citrus species. In Brazil, this species is the most important, being found in practically all areas where citrus canker has been detected. Like most phytobacterioses, there is no efficient way to control citrus canker. Considering the importance of the disease worldwide, investigation is needed to accurately detect which genes are related to the pathogen-host adaptation process and which are associated with pathogenesis. Results: Through transposon insertion mutagenesis, 10,000 mutants of Xanthomonas citri subsp. citri strain 306 (Xcc) were obtained, and 3,300 were inoculated in Rangpur lime (Citrus limonia) leaves. Their ability to cause citrus canker was analyzed every 3 days until 21 days after inoculation; a set of 44 mutants showed altered virulence, with 8 presenting a complete loss of causing citrus canker symptoms. Sequencing of the insertion site in all 44 mutants revealed that 35 different ORFs were hit, since some ORFs were hit in more than one mutant, with mutants for the same ORF presenting the same phenotype. An analysis of these ORFs showed that some encoded genes were previously known as related to pathogenicity in phytobacteria and, more interestingly, revealed new genes never implicated with Xanthomonas pathogenicity before, including hypothetical ORFs. Among the 8 mutants with no canker symptoms are the hrpB4 and hrpX genes, two genes that belong to type III secretion system (TTSS), two hypothetical ORFS and, surprisingly, the htrA gene, a gene reported as involved with the virulence process in animal-pathogenic bacteria but not described as involved in phytobacteria virulence. Nucleic acid hybridization using labeled cDNA probes showed that some of the mutated genes are differentially expressed when the bacterium is grown in citrus leaves. Finally, comparative genomic analysis revealed that 5 mutated ORFs are in new putative pathogenicity islands. Conclusion: The identification of these new genes related with Xcc infection and virulence is a great step towards the understanding of plant-pathogen interactions and could allow the development of strategies to control citrus canker.

Chemical analyses confirm a rare case of seed dispersal by bees

It has been suggested that dispersal of seeds of Coussapoa asperifolia magnifolia could have endozoochoric dispersal by frugivorous birds and monkeys because the fruits are red when ripe, or exozoochoric dispersal, because the exocarp is mucilaginous and sticky. However, our field observations showed only stingless bees collecting the exocarp with seeds of C. asperifolia magnifolia, which are used for building and repairing their nests, from which the plants sprout. This paper aimed to determine the fruit chemical composition, since we postulated that C. asperifolia magnifolia is neither consumed by birds nor monkeys due to being very sticky and apparently resinous. Apolar extract analyses revealed the fruits are not resinous but extremely rich in waxes ( mainly esterified triglycerides), and polar extract analyses revealed the sugar content to be close to the sensorial minimum level. This probably accounts for why only stingless bees are seen visiting fruits and dispersing seeds.

Flow injection analysis of paracetamol using a biomimetic sensor as a sensitive and selective amperometric detector

This work describes the coupling of a biomimetic sensor to a flow injection system for the sensitive determination of paracetamol. The sensor was prepared as previously described in the literature (M. D. P. T. Sotomayor, A. Sigoli, M. R. V. Lanza, A. A. Tanaka and L. T. Kubota, J. Braz. Chem. Soc., 2008, 19, 734) by modifying a glassy carbon electrode surface with a Nafion (R) membrane doped with iron tetrapyridinoporphyrazine (FeTPyPz), a biomimetic catalyst of the P450 enzyme. The performance of the sensor for paracetamol detection was investigated and optimized in a flow injection system (FIA) using a wall jet electrochemical cell. Under optimized conditions a wide linear response range (1.0 x 10(-5) to 5.0 x 10(-2) mol L(-1)) was obtained, with a sensitivity of 2579 (+/- 129) mu A L mu mol(-1). The detection and quantification limits of the sensor for paracetamol in the FIA system were 1.0 and 3.5 mu mol L(-1), respectively. The analytical frequency was 51 samples h(-1), and over a period of five days (320 determinations) the biosensor maintained practically the same response. The system was successfully applied to paracetamol quantification in seven pharmaceutical formulations and in water samples from six rivers in Sao Paulo State, Brazil.

Nanogravimetric and voltammetric studies of a Pt-Rh alloy surface and its behavior for methanol oxidation

This paper describes the preparation of a Pt-Rh alloy surface electrodeposited on Pt electrodes and its electrocatalytic characterization for methanol oxidation. The X-ray photoelectronic spectroscopy ( XPS) results demonstrate that the surface composition is approximately 24 at-% Rh and 76 % Pt. The cyclic voltammetry (CV) and electrochemical quartz crystal (EQCN) results for the alloy were associated, for platinum, to the well known profile in acidic medium. For Rh, on the alloy, the generation of rhodium hydroxide species (Rh(OH)(3) and RhO(OH)(3)) was measured. During the successive oxidation-reduction cycles the mass returns to its original value, indicating the reversibility of the processes. It was not observed rhodium dissolution during the cycling. The 76/24 at % Pt-Rh alloy presented singular electrocatalytic activity for methanol electrooxidation, which started at more negative potentials compared to pure Pt (70 mV). During the sweep towards more negative potentials, there is only weak CO re-adsorption on both Rh and Pt-Rh alloy surfaces, which can be explained by considering the interaction energy between Rh and CO.

Política externa chilena e espectro ideológico político-partidário: um estudo sobre a Câmara dos Deputados (2002-2006)

The influence of political parties on decisions made by members of Congress is a hotly debated issue in political science. In foreign policy, which is usually considered nonpartisan, the matter is even more inconclusive. The current study analyzes all the roll-call votes taken on foreign policy issues in the 2002-2006 legislature of the Chilean Chamber of Deputies. After tracing a spatial map of foreign policy preferences among Chilean Deputies using the Nominate statistical package, we concluded that the ideology of the legislator's political party is a predictive factor for his or her foreign policy behavior. Our findings indicate that the way Chilean legislators structure their preferences on foreign policy issues does not differ significantly from the way they shape their domestic policy preferences.

Abundance of sedentary consumers and sessile organisms along the wave exposure gradient of subtropical rocky shores of the south-west Atlantic

Sedentary consumers play an important role on populations of prey and, hence, their patterns of abundance, distribution and coexistence on shores are important to evaluate their potential influence on ecosystem dynamics. Here, we aimed to describe their spatio-temporal distribution and abundance in relation to wave exposure in the intertidal rocky shores of the south-west Atlantic to provide a basis for further understanding of ecological processes in this system. The abundance and composition of the functional groups of sessile organisms and sedentary consumers were taken by sampling the intertidal of sheltered and moderately exposed shores during a period of one year. The sublittoral fringe of sheltered areas was dominated by macroalgae, while the low midlittoral was dominated by bare rock and barnacles. In contrast, filter-feeding animals prevailed at exposed shores, probably explaining the higher abundance of the predator Stramonita haemastoma at these locations. Limpets were more abundant at the midlittoral zone of all shores while sea urchins were exclusively found at the sublittoral fringe of moderately exposed shores, therefore, adding grazing pressure on these areas. The results showed patterns of coexistence, distribution and abundance of those organisms in this subtropical area, presumably as a result of wave action, competition and prey availability. It also brought insights on the influence of top-down and bottom-up processes in this area.

Foraging by the omnivorous crab Pachygrapsus transversus affects the structure of assemblages on sub-tropical rocky shores

The roles of herbivory and predation in determining the structure and diversity of communities have been tested across most intertidal systems. In contrast, the importance of omnivorous consumers remains untested in many rocky shore communities. We tested the role of a small omnivorous crab in an intertidal food web on rocky shores of the sub-tropical southwest Atlantic. Exclusion of the grapsid crab Pachygrapsus transversus in the field resulted in significant changes in the abundance of functional groups in the sublittoral fringe of sheltered shores, where the dominant cover changed from a suite of macroalgae to an assemblage of filter-feeding animals (ascidians, sponges, mussels). In contrast, limpets, whelks, large crabs and fish did not significantly affect community composition of the assemblage. To examine the omnivorous feeding pattern of P. transversus, we did laboratory experiments to test its foraging behaviour among animal and algal groups. The crab showed selective behaviour, preferring invertebrate groups to macroalgae, and opportunistic behaviour among types of prey within those major groups. According to our results, the role of slow-moving and large fast-moving consumers is apparently negligible compared to the effect of an omnivorous consumer. P. transversus plays an important role in determining the intertidal community composition on these subtropical rocky shores, causing changes in the balance of functional groups and controlling invasive species.

Do plant species influence soil CO(2) and N(2)O fluxes in a diverse tropical forest?

To test whether plant species influence greenhouse gas production in diverse ecosystems, we measured wet season soil CO(2) and N(2)O fluxes close to similar to 300 large (>35 cm in diameter at breast height (DBH)) trees of 15 species at three clay-rich forest sites in central Amazonia. We found that soil CO(2) fluxes were 38% higher near large trees than at control sites >10 m away from any tree (P < 0.0001). After adjusting for large tree presence, a multiple linear regression of soil temperature, bulk density, and liana DBH explained 19% of remaining CO(2) flux variability. Soil N(2)O fluxes adjacent to Caryocar villosum, Lecythis lurida, Schefflera morototoni, and Manilkara huberi were 84%-196% greater than Erisma uncinatum and Vochysia maxima, both Vochysiaceae. Tree species identity was the most important explanatory factor for N(2)O fluxes, accounting for more than twice the N(2)O flux variability as all other factors combined. Two observations suggest a mechanism for this finding: (1) sugar addition increased N(2)O fluxes near C. villosum twice as much (P < 0.05) as near Vochysiaceae and (2) species mean N(2)O fluxes were strongly negatively correlated with tree growth rate (P = 0.002). These observations imply that through enhanced belowground carbon allocation liana and tree species can stimulate soil CO(2) and N(2)O fluxes (by enhancing denitrification when carbon limits microbial metabolism). Alternatively, low N(2)O fluxes potentially result from strong competition of tree species with microbes for nutrients. Species-specific patterns in CO(2) and N(2)O fluxes demonstrate that plant species can influence soil biogeochemical processes in a diverse tropical forest.