The role of the steps in the cleavage of the C-C bond during ethanol oxidation on platinum electrodes

Ethanol oxidation has been studied on stepped platinum single crystal electrodes in acid media using electrochemical and Fourier transform infrared (FTIR) techniques. The electrodes used belong to two different series of stepped surfaces: those having (111) terraces with (100) monoatomic steps and those with (111) terraces with (110) monoatomic steps. The behaviors of the two series of stepped surfaces for the oxidation of ethanol are very different. On the one hand, the presence of (100) steps on the (111) terraces provides no significant enhancement of the activity of the surfaces. On the other hand, (110) steps have a double effect on the ethanol oxidation reaction. At potentials below 0.7 V, the step catalyzes the C-C bond cleavage and also the oxidation of the adsorbed CO species formed. At higher potentials, the step is not only able to break the C-C bond, but also to catalyze the oxidation of ethanol to acetic acid and acetaldehyde. The highest catalytic activity from voltammetry for ethanol oxidation was obtained with the Pt(554) electrode.

Sisal, sugarcane bagasse and microcrystalline celluloses: Influence of the composition of the solvent system N,N-dimethylacetamide/lithium chloride on the solubility and acetylation of these polysaccharides

The present work describes an investigation concerning the acetylation of celluloses extracted from short-life-cycle plant sources (i.e. sugarcane bagasse and sisal fiber) as well as microcrystalline cellulose. The acetylation was carried out under homogeneous conditions using the solvent system N,N-dimethylacetamide/lithium chloride. The celluloses were characterized, and the characterizations included an evaluation of the amount of hemicellulose present in the materials obtained from lignocellulosics sources (sugarcane and sisal). The amount of LiCl was varied and its influence on the degree of acetate substitution was analyzed. It was found that the solvent system composition and the nature of the cellulose influenced both the state of chain dissolution and the product characteristics. The obtained results demonstrated the importance of developing specific studies on the dissolution process as well as on the derivatization of celluloses from various sources.

Mechanism and model of the oscillatory electro-oxidation of methanol

A mechanism for the kinetic instabilities observed in the galvanostatic electro-oxidation of methanol is suggested and a model developed. The model is investigated using stoichiometric network analysis as well as concepts from algebraic geometry (polynomial rings and ideal theory) revealing the occurrence of a Hopf and a saddle-node bifurcation. These analytical solutions are confirmed by numerical integration of the system of differential equations. (C) 2010 American Institute of Physics

Solution structure of the human signaling protein RACK1

Background: The adaptor protein RACK1 (receptor of activated kinase 1) was originally identified as an anchoring protein for protein kinase C. RACK1 is a 36 kDa protein, and is composed of seven WD repeats which mediate its protein-protein interactions. RACK1 is ubiquitously expressed and has been implicated in diverse cellular processes involving: protein translation regulation, neuropathological processes, cellular stress, and tissue development. Results: In this study we performed a biophysical analysis of human RACK1 with the aim of obtaining low resolution structural information. Small angle X-ray scattering (SAXS) experiments demonstrated that human RACK1 is globular and monomeric in solution and its low resolution structure is strikingly similar to that of an homology model previously calculated by us and to the crystallographic structure of RACK1 isoform A from Arabidopsis thaliana. Both sedimentation velocity and sedimentation equilibrium analytical ultracentrifugation techniques showed that RACK1 is predominantly a monomer of around 37 kDa in solution, but also presents small amounts of oligomeric species. Moreover, hydrodynamic data suggested that RACK1 has a slightly asymmetric shape. The interaction of RACK1 and Ki1/57 was tested by sedimentation equilibrium. The results suggested that the association between RACK1 and Ki-1/57(122-413) follows a stoichiometry of 1:1. The binding constant (KB) observed for RACK1-Ki-1/57(122-413) interaction was of around (1.5 +/- 0.2) x 10(6) M(-1) and resulted in a dissociation constant (KD) of (0.7 +/- 0.1) x 10(-6) M. Moreover, the fluorescence data also suggests that the interaction may occur in a cooperative fashion. Conclusion: Our SAXS and analytical ultracentrifugation experiments indicated that RACK1 is predominantly a monomer in solution. RACK1 and Ki-1/57(122-413) interact strongly under the tested conditions.

Dynamic light scattering and optical absorption spectroscopy study of pH and temperature stabilities of the extracellular hemoglobin of Glossoscolex paulistus

The extracellular hemoglobin of Glossoscolex paulistus (HbGp) is constituted of subunits containing heme groups, monomers and trimers, and nonheme structures, called linkers, and the whole protein has a minimum molecular mass near 3.1 x 10(6) Da. This and other proteins of the same family are useful model systems for developing blood substitutes due to their extracellular nature, large size, and resistance to oxidation. HbGp samples were studied by dynamic light scattering (DLS). In the pH range 6.0-8.0, HbGp is stable and has a monodisperse size distribution with a z-average hydrodynamic diameter (D-h) of 27 +/- 1 nm. A more alkaline pH induced an irreversible dissociation process, resulting in a smaller D-h of 10 +/- 1 nm. The decrease in D-h suggests a complete hemoglobin dissociation. Gel filtration chromatography was used to show unequivocally the oligomeric dissociation observed at alkaline pH. At pH 9.0, the dissociation kinetics is slow, taking a minimum of 24 h to be completed. Dissociation rate constants progressively increase at higher pH, becoming, at pH 10.5, not detectable by DILS. Protein temperature stability was also pH-dependent. Melting curves for HbGp showed oligomeric dissociation and protein denaturation as a function of pH. Dissociation temperatures were lower at higher pH. Kinetic studies were also performed using ultraviolet-visible absorption at the Soret band. Optical absorption monitors the hemoglobin autoxidation while DLS gives information regarding particle size changes in the process of protein dissociation. Absorption was analyzed at different pH values in the range 9.0-9.8 and at two temperatures, 25 degrees C and 38 degrees C. At 25 degrees C, for pH 9.0 and 9.3, the kinetics monitored by ultraviolet-visible absorption presents a monoexponential behavior, whereas for pH 9.6 and 9.8, a biexponential behavior was observed, consistent with heme heterogeneity at more alkaline pH. The kinetics at 38 degrees C is faster than that at 25 degrees C and is biexponential in the whole pH range. DLS dissociation rates are faster than the autoxidation dissociation rates at 25 degrees C. Autoxiclation and dissociation processes are intimately related, so that oligomeric protein dissociation promotes the increase of autoxidation rate and vice versa. The effect of dissociation is to change the kinetic character of the autoxidation of hemes from monoexponential to biexponential, whereas the reverse change is not as effective. This work shows that DLS can be used to follow, quantitatively and in real time, the kinetics of changes in the oligomerization of biologic complex supramolecular systems. Such information is relevant for the development of mimetic systems to be used as blood substitutes.

Mechanistic studies of the 'blue' Cu enzyme, bilirubin oxidase, as a highly efficient electrocatalyst for the oxygen reduction reaction

The 'blue copper' enzyme bilirubin oxidase from Myrothecium verrucaria shows significantly enhanced adsorption on a pyrolytic graphite 'edge' (PGE) electrode that has been covalently modified with naphthyl-2-carboxylate functionalities by diazonium coupling. Modified electrodes coated with bilirubin oxidase show electrocatalytic voltammograms for the direct, four-electron reduction of O(2) by bilirubin oxidase with up to four times the current density of an unmodified PGE electrode. Electrocatalytic voltammograms measured with a rapidly rotating electrode (to remove effects of O(2) diffusion limitation) have a complex shape (an almost linear dependence of current on potential below pH 6) that is similar regardless of how PGE is chemically modified. Importantly, the same waveform is observed if bilirubin oxidase is adsorbed on Au(111) or Pt(111) single-crystal electrodes (at which activity is short-lived). The electrocatalytic behavior of bilirubin oxidase, including its enhanced response on chemically-modified PGE, therefore reflects inherent properties that do not depend on the electrode material. The variation of voltammetric waveshapes and potential-dependent (O(2)) Michaelis constants with pH and analysis in terms of the dispersion model are consistent with a change in rate-determining step over the pH range 5-8: at pH 5, the high activity is limited by the rate of interfacial redox cycling of the Type 1 copper whereas at pH 8 activity is much lower and a sigmoidal shape is approached, showing that interfacial electron transfer is no longer a limiting factor. The electrocatalytic activity of bilirubin oxidase on Pt(111) appears as a prominent pre-wave to electrocatalysis by Pt surface atoms, thus substantiating in a single, direct experiment that the minimum overpotential required for O(2) reduction by the enzyme is substantially smaller than required at Pt. At pH 8, the onset of O(2) reduction lies within 0.14 V of the four-electron O(2)/2H(2)O potential.

PLANKTON-CAUGHT ZOEAL STAGES AND MEGALOPA OF THE LOBSTER SHRIMP AXIUS SERRATUS (DECAPODA: AXIIDAE) FROM THE BAY OF FUNDY, CANADA, WITH A SUMMARY OF AXIIDEAN AND GEBIIDEAN LITERATURE ON LARVAL DESCRIPTIONS

Wild-caught larvae, attributed to the lobster shrimp Arius serratus, consisting of two zoeal stages and a decapodid (megalopa), are described in detail. Parentage of larvae was ascertained based on geographic distribution of axiideans and gebiideans (= former thalassinideans) within the study area and close morphological resemblance to other congeneric larval stages. Larvae of A. serratus represent the first described 'thalassinidean' larvae from Canadian Atlantic waters and the first for Axiidae within the northwest Atlantic. Among axiidean larvae, those of A. serratus most closely resemble larvae of A. stirhynchus from the eastern Atlantic. Distinct features include the spination of the pleon that set A. serratus zoeae apart from those of most other 'thalassinideans' but that, in combination with a telson very similar to Homarus americanus, contributes to the general resemblance of A. serratus larvae to those of the American lobster. The primary distinction between these taxa is the presence of a chela on the third pereiopod in the latter that is not present in the former. In view of these appendages being prone to loss or damage, other characters that separate these taxa are listed and discussed. Given the uncertain status of some taxa within Axiidae and limited detailed information of larvae with certain parentage, difficulties in delineating the family based on larvae persist, as they do for cladistic analyses using adult morphology and molecular approaches.

Phylogeny and Taxonomy of the Neotropical Thepytus (Lepidoptera: Lycaenidae: Theclinae)

The Neotropical lycaenid hairstreak genus Thepytus Robbins and its eight species are revised. Species treatments summarize nomenclature, distribution, habitat, behavior, and diagnostic traits, as well as noting why each species is considered distinct under a biological species concept. An identification key for males and a checklist are included. Beatheclus Balint & Dahners new synonym is synonymized with Thepytus, and Theppus beatrizae (Balint & Dahners) is a new combination. Other nomenclatural actions include the description of Thepytus jennifer Busby & Robbins new species. Thepytus nancyana Busby & Robbins new species, and Thepytus carmen Robbins & Duarte new species. A lectotype is designated or Thecla thyrea Hewitson, 1867, to ensure stability of this name. A phylogenetic analysis based on 22 coded morphological characters yields one equal weight most parsimonious 39-step tree. Implied weighting does not change the tree topology. Unambiguous changes in elevation optimized on the cladogram show that a montane lineage of Thepytus colonized the lowlands in at least one instance. The use of T. echelta (Hewitson) as a biological control agent for Psittacanthus (Loranthaceae) is discussed.

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.

Tidal-amplitude rhythms of larval release: variable departure from presumed optimal timing among populations of the mottled shore crab

It is widely assumed that optimal timing of larval release is of major importance to offspring survival, but the extent to which environmental factors entrain synchronous reproductive rhythms in natural populations is not well known. We sampled the broods of ovigerous females of the common shore crab Pachygrapsus transversus at both sheltered and exposed rocky shores interspersed along a so-km coastline, during four different periods, to better assess inter-population differences of larval release timing and to test for the effect of wave action. Shore-specific patterns were consistent through time. Maximum release fell within 1 day around syzygies on all shores, which matched dates of maximum tidal amplitude. Within this very narrow range, populations at exposed shores anticipated hatching compared to those at sheltered areas, possibly due to mechanical stimulation by wave action. Average departures from syzygial release ranged consistently among shores from 2.4 to 3.3 days, but in this case we found no evidence for the effect of wave exposure. Therefore, processes varying at the scale of a few kilometres affect the precision of semilunar timing and may produce differences in the survival of recently hatched larvae. Understanding the underlying mechanisms causing departures from presumed optimal release timing is thus important for a more comprehensive evaluation of reproductive success of invertebrate populations.

Historical carbon emissions and uptake from the agricultural frontier of the Brazilian Amazon

Tropical ecosystems play a large and complex role in the global carbon cycle. Clearing of natural ecosystems for agriculture leads to large pulses of CO(2) to the atmosphere from terrestrial biomass. Concurrently, the remaining intact ecosystems, especially tropical forests, may be sequestering a large amount of carbon from the atmosphere in response to global environmental changes including climate changes and an increase in atmospheric CO(2). Here we use an approach that integrates census-based historical land use reconstructions, remote-sensing-based contemporary land use change analyses, and simulation modeling of terrestrial biogeochemistry to estimate the net carbon balance over the period 1901-2006 for the state of Mato Grosso, Brazil, which is one of the most rapidly changing agricultural frontiers in the world. By the end of this period, we estimate that of the state`s 925 225 km(2), 221 092 km(2) have been converted to pastures and 89 533 km(2) have been converted to croplands, with forest-to-pasture conversions being the dominant land use trajectory but with recent transitions to croplands increasing rapidly in the last decade. These conversions have led to a cumulative release of 4.8 Pg C to the atmosphere, with similar to 80% from forest clearing and 20% from the clearing of cerrado. Over the same period, we estimate that the residual undisturbed ecosystems accumulated 0.3 Pg C in response to CO2 fertilization. Therefore, the net emissions of carbon from Mato Grosso over this period were 4.5 Pg C. Net carbon emissions from Mato Grosso since 2000 averaged 146 Tg C/yr, on the order of Brazil`s fossil fuel emissions during this period. These emissions were associated with the expansion of croplands to grow soybeans. While alternative management regimes in croplands, including tillage, fertilization, and cropping patterns promote carbon storage in ecosystems, they remain a small portion of the net carbon balance for the region. This detailed accounting of a region`s carbon balance is the type of foundation analysis needed by the new United Nations Collaborative Programmme for Reducing Emissions from Deforestation and Forest Degradation (REDD).

Carbon sequestration in agricultural soils in the Cerrado region of the Brazilian Amazon

The introduction of crop management practices after conversion of Amazon Cerrado into cropland influences soil C stocks and has direct and indirect consequences on greenhouse gases (GHG) emissions. The aim of this study was to quantify soil C sequestration, through the evaluation of the changes in C stocks, as well as the GHG fluxes (N(2)O and CH(4)) during the process of conversion of Cerrado into agricultural land in the southwestern Amazon region, comparing no-tillage (NT) and conventional tillage (CT) systems. We collected samples from soils and made gas flux measurements in July 2004 (the dry season) and in January 2005 (the wet season) at six areas: Cerrado, CT cultivated with rice for 1 year (1CT) and 2 years (2CT), and NT cultivated with soybean for 1 year (1NT), 2 years (2NT) and 3 years (3NT), in each case after a 2-year period of rice under CT. Soil samples were analyzed in both seasons for total organic C and bulk density. The soil C stocks, corrected for a mass of soil equivalent to the 0-30-cm layer under Cerrado, indicated that soils under NT had generally higher C storage compared to native Cerrado and CT soils. The annual C accumulation rate in the conversion of rice under CT into soybean under NT was 0.38 Mg ha(-1) year(-1). Although CO(2) emissions were not used in the C sequestration estimates to avoid double counting, we did include the fluxes of this gas in our discussion. In the wet season, CO(2) emissions were twice as high as in the dry season and the highest N(2)O emissions occurred under the NT system. There were no CH(4) emissions to the atmosphere (negative fluxes) and there were no significant seasonal variations. When N(2)O and CH(4) emissions in C-equivalent were subtracted (assuming that the measurements made on 4 days were representative of the whole year), the soil C sequestration rate of the conversion of rice under CT into soybean under NT was 0.23 Mg ha(-1) year(-1). Although there were positive soil C sequestration rates, our results do not present data regarding the full C balance in soil management changes in the Amazon Cerrado. (C) 2008 Elsevier B.V. All rights reserved.

Sedimentary Organic Matter in Cores of the Cananeia-Iguape Lagoonal-Estuarine System, Sao Paulo State, Brazil

Sedimentary organic matter is a good tool for environmental evaluation where the sediments are deposited. We determined the elemental and C- and N-isotopic compositions of 211 sub-surface sediment samples from 13 cores (ranging from 18 to 46cm), collected in the Cananeia-Iguape estuarine-lagoonal system. The aim of this research is to evaluate the environmental variations of this tropical coastal micro-tidal system over the last decades, through SOM distribution. The studied parameters show differences between the cores located in the northern (sandy-silt sediments) and southern (sand and silty-sand) portions. The whole area presents a mixed organic matter origin signature (local mangrove plants: < -25.6 parts per thousand PDB/ phytoplancton delta(13)C values: -19.4 parts per thousand PDB). The northern cores, which submitted higher sedimentation deposition (1.46cm year(-1)), are more homogenous, presenting lower delta(13)C (< -25.2 parts per thousand PDB) and higher C/N values (in general >14), directly related to the terrestrial input from Ribeira de Iguape River (24,000 km(2) basin). The southern portion presents lower sedimentation rates (0.38cm year(-1)) and is associated to a small river basin (1,340 km(2)), presenting values Of delta(13)C: -25.0 to 23.0 parts per thousand PDB and of C/N ratio: 11 to 15. In general, the elemental contents in the 15 cores may be considered from low to medium (< 2.0% C - < 0.1% N), compared to similar environments. Although a greater marine influence is observed in the southern system portion, the majority of the cores present an elevated increase of continental deposition, most likely related to the strong silting process that the area has been subjected to since the 1850s, when an artificial channel was built linking, directly, the Ribeira River to the estuarine-lagoonal system.

Discharge-calcium concentration relationships in streams of the Amazon and Cerrado of Brazil: soil or land use controlled

Stream discharge-concentration relationships are indicators of terrestrial ecosystem function. Throughout the Amazon and Cerrado regions of Brazil rapid changes in land use and land cover may be altering these hydrochemical relationships. The current analysis focuses on factors controlling the discharge-calcium (Ca) concentration relationship since previous research in these regions has demonstrated both positive and negative slopes in linear log(10)discharge-log(10)Ca concentration regressions. The objective of the current study was to evaluate factors controlling stream discharge-Ca concentration relationships including year, season, stream order, vegetation cover, land use, and soil classification. It was hypothesized that land use and soil class are the most critical attributes controlling discharge-Ca concentration relationships. A multilevel, linear regression approach was utilized with data from 28 streams throughout Brazil. These streams come from three distinct regions and varied broadly in watershed size (< 1 to > 10(6) ha) and discharge (10(-5.7)-10(3.2) m(3) s(-1)). Linear regressions of log(10)Ca versus log(10)discharge in 13 streams have a preponderance of negative slopes with only two streams having significant positive slopes. An ANOVA decomposition suggests the effect of discharge on Ca concentration is large but variable. Vegetation cover, which incorporates aspects of land use, explains the largest proportion of the variance in the effect of discharge on Ca followed by season and year. In contrast, stream order, land use, and soil class explain most of the variation in stream Ca concentration. In the current data set, soil class, which is related to lithology, has an important effect on Ca concentration but land use, likely through its effect on runoff concentration and hydrology, has a greater effect on discharge-concentration relationships.

Determination of the geographical origin of Brazilian wines by isotope and mineral analysis

In the present research, we studied wines from three different south Brazilian winemaking regions with the purpose of differentiating them by geographical origin of the grapes. Brazil`s wide territory and climate diversity allow grape cultivation and winemaking in many regions of different and unique characteristics. The wine grape cultivation for winemaking concentrates in the South Region, mainly in the Serra GaA(0)cha, the mountain area of the state of Rio Grande do Sul, which is responsible for 90% of the domestic wine production. However, in recent years, two new production regions have developed: the Campanha, the plains to the south and the Serra do Sudeste, the hills to the southeast of the state. Analysis of isotopic ratios of (18)O/(16)O of wine water, (13)C/(12)C of ethanol, and of minerals were used to characterize wines from different regions. The isotope analysis of delta(18)O of wine water and minerals Mg and Rb were the most efficient to differentiate the regions. By using isotope and mineral analysis, and discrimination analysis, it was possible to classify the wines from south Brazil.