METHANE DRY REFORMING OVER Ni SUPPORTED ON PINE SAWDUST ACTIVATED CARBON: EFFECTS OF SUPPORT SURFACE PROPERTIES AND METAL LOADING

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Chemical characterization and infrared spectroscopy of soil organic matter from two southern brazilian soils

Soil organic matter from the surface horizon of two Brazilian soils (a Latosol and a Chernosol), in bulk samples (in situ SOM) and in HF-treated samples (SOM), was characterized by elemental analyses, diffuse reflectance (DRIFT) and transmission Fourier transform infrared spectroscopy (T-FTIR). Humic acids (HA), fulvic acids (FA) and humin (HU) isolated from the SOM were characterized additionally by ultraviolet-visible spectroscopy (UV-VIS). After sample oxidation and alkaline treatment, the DRIFT technique proved to be more informative for the detection of "in situ SOM" and of residual organic matter than T-FTIR. The higher hydrophobicity index (HI) and H/C ratio obtained in the Chernosol samples indicate a stronger aliphatic character of the organic matter in this soil than the Latosol. In the latter, a pronounced HI decrease was observed after the removal of humic substances (HS). The weaker aliphatic character, the higher O/C ratio, and the T-FTIR spectrum obtained for the HU fraction in the Latosol suggest the occurrence of surface coordination of carboxylate ions. The Chernosol HU fraction was also oxygenated to a relatively high extent, but presented a stronger hydrophobic character in comparison with the Latosol HU. These differences in the chemical and functional group composition suggest a higher organic matter protection in the Latosol. After the HF treatment, decreases in the FA proportion and the A350/A550 ratio were observed. A possible loss of FA and condensation of organic molecules due to the highly acid medium should not be neglected.

Immersion enthalpy variation of surface-modified mineral activated carbon in lead (II) aqueous solution adsorption: the relation between immersion enthalpy and adsorption capacity

An activated carbon was obtained by chemical activation with phosphoric acid, CM, from a mineral carbon. Afterwards, the carbon was modified with 2 and 5 molL-1, CMox2 and CMox5 nitric acid solutions to increase the surface acid group contents. Immersion enthalpy at pH 4 values and Pb2+ adsorption isotherms were determined by immersing activated carbons in aqueous solution. The surface area values of the adsorbents and total pore volume were approximately 560 m².g-1 and 0.36 cm³g-1, respectively. As regards chemical characteristics, activated carbons had higher acid sites content, 0.92-2.42 meq g-1, than basic sites, 0.63-0.12 meq g-1. pH values were between 7.4 and 4.5 at the point of zero charge, pH PZC. The adsorbed quantity of Pb2+ and the immersion enthalpy in solution of different pH values for CM activated carbon showed that the values are the highest for pH 4, 15.7 mgg-1 and 27.6 Jg-1 respectively. Pb2+ adsorption isotherms and immersion enthalpy were determined for modified activated carbons and the highest values were obtained for the activated carbon that showed the highest content of total acid sites on the surface.

Effects of environmental factors on community structure of Leptophlebiidae (Insecta, Ephemeroptera) in Cerrado streams, Brazil

We analyzed the effects of environmental factors on abundance, species richness, and functional group richness of Leptophlebiidae in 16 sampling points along four Cerrado streams. Across three periods of 2005, we collected 5,492 larvae from 14 species in stream bed substrate. These species belong to three functional feeding groups: scrapers, filtering collectors and shredders. The abundance and species richness were not affected by water quality, but habitat quality related to presence of riparian vegetation had positive effects on the abundance of shredders. Our results add important information on the natural history of the species and functional groups of aquatic insects and also provide relevant data for the monitoring and conservation of streams in the Brazilian Cerrado.

Genesis of textural contrasts in subsurface soil horizons in the Northern Pantanal-Brazil

The Pantanal region can be characterized as a quaternary floodplain with predominant sedimentation in the form of alluvial fans. In the geomorphologic and sedimentary evolution, the avulsion process is inherent to this depositional system and its dynamics, together with surface water floods, influence soil sedimentation on this plain. The knowledge and differentiation of these two events can contribute to a better understanding of the variability of soil properties and distribution under the influence of these sedimentation processes. Therefore, this study investigated the genesis of soils in the Northern Pantanal with textural contrasts in deeper horizons and their relationship with the depositional system dynamics. We analyzed four soil profiles in the region of Barão de Melgaço, Mato Grosso State, Brazil (RPPN SESC Pantanal). Two profiles were sampled near the Rio Cuiabá (AP1 and AP4) and two near the Rio São Lourenço (AP10 and AP11). In AP11, the horizons contrast in particle size between the profile basis and the surface. In AP1, AP4 and AP10, the horizons overlaying the sand layer have similar particle size properties, mainly in terms of sand distribution. In the first case, floods (surface water) seem to have originated the horizons and layers with contrasting texture. In the second case, avulsion is the most pronounced process. Therefore, the two modes can form soils with contrasting texture that are discriminable by soil morphology, based on the distinct features associated to the specific sedimentation processes.

Towards a universal sampling protocol for soil biotas in the humid tropics

This paper reviews the methods for the inventory of below-ground biotas in the humid tropics, to document the (hypothesized) loss of soil biodiversity associated with deforestation and agricultural intensification at forest margins. The biotas were grouped into eight categories, each of which corresponded to a major functional group considered important or essential to soil function. An accurate inventory of soil organisms can assist in ecosystem management and help sustain agricultural production. The advantages and disadvantages of transect-based and grid-based sampling methods are discussed, illustrated by published protocols ranging from the original "TSBF transect", through versions developed for the alternatives to Slash-and-Burn Project (ASB) to the final schemes (with variants) adopted by the Conservation and Sustainable Management of Below-ground Biodiversity Project (CSM-BGBD). Consideration is given to the place and importance of replication in below-ground biological sampling and it is argued that the new sampling protocols are inclusive, i.e. designed to sample all eight biotic groups in the same field exercise; spatially scaled, i.e. provide biodiversity data at site, locality, landscape and regional levels, and link the data to land use and land cover; and statistically robust, as shown by a partial randomization of plot locations for sampling.

Principais métodos de síntese de amidinas

The amidine functional group is found in a wide range of natural products and is biologically active against several pathogens. In addition, amidines have long been regarded as useful intermediates in the synthesis of heterocyclic compounds. Consequently, a great number of methods have been developed for the preparation of amidines. Pinner's method is the most commonly used. Conventional methods include: - the addition of metal amides or amines to nitriles, the addition of amines to imido esters and the condensation of amides with amines in the presence of halogenating reagents. In this report, the main methods for synthesis of amidines will be described.

Desenvolvimento de abordagem objetivando a síntese da 3-desidroxi-4-metoxi-tubastrina

We report the synthesis of amino(2-hydroxy-2-(4-methoxyphenyl)ethylamino)methaniminium (14) as a direct precursor of a tubastrine derivative (3-dehydroxy-4-methoxytubastrine). The synthetic steps involved functional group interconversions starting from 1-(4-methoxyphenyl)ethanone to obtain the guanidine-protected derivative 13. Tentative dehydration of 13 with SiOH-adsorbed CuSO4 resulted in guanidine deprotection only. This was an unexpected result, since there are no reports of CuSO4.SiOH as Boc-deprotecting of guanidines. The product 14 was obtained in five steps and 5.4 % overall yield, and constitutes a direct precursor of 3-dehydroxy-4-methoxytubastrine.

Metátese de olefinas aplicada ao fechamento de anéis: uma ferramenta poderosa para a síntese de macrociclos naturais

For a quarter of a century, metathesis has become indispensable for the synthesis of natural and non-natural products, particularly of biologically active compounds. This review illustrates through a maximum of appropriate examples the power and the versatility of the metathesis ring-closure (RCM) reaction as a key ring-closure methodology for the synthesis of natural macrocycles. Its high functional group compatibility as well as the possibility of further transformations makes this reaction a powerful tool in the cases where the structural framework and function requirements are difficult to meet.

Determinação da constante de dissociação (Ka) do captopril e da nimesulida: experimentos de química analítica para o curso de farmácia

This paper presents the determination of the dissociation constant (Ka) of captopril and nimesulide as contextualized experiments to teach chemical concepts to students of Pharmacy. Captopril is an antihypertensive drug, which presents high water-solubility and weak acid properties. The pKa of carboxylic acid group of captopril is 3.7. Nimesulide is a non-steroidal anti-inflammatory drug sparingly soluble in water. It is weakly acidic (pKa ≈ 6.5) because of its methanesulfonamide functional group. The pKa of captopril was determined by potentiometric titration with NaOH 2.0 x 10-2 moL L ¹. The pKa of nimesulide was determined by using spectrophotometry and photometric titration. The experimental values of pKa of both drugs are in very good agreement with those from literature

Ecological distribution of stream macroalgae in different spatial scales using taxonomic and morphological groups

We examined the ecological distribution of macroalgal communities in streams using species groups (taxonomic units = algal phyla, and morphological = morphological types) with similar structures and functions instead of the species themselves. The study was conducted from June to July/2007 in two drainage basins located in mid-southern region of Paraná State , Brazil. Evaluations of macroalgal communities took into consideration the following spatial scales: the drainage basin (the Pedras river and Marrecas river basins), shading regime (open and shaded stream segments), mesohabitats (riffles and pools), and microhabitats (sampling units of 0.05m2). A total of 29 taxa (23 subgeneric, one generic, and five vegetative groups) were identified. On these, 12 taxa belong to Chlorophyta, 11 to Cyanobacteria, four to Heterokontophyta, and two to Rhodophyta. The proportions of morphological types were: 24% free filaments, 17.25% mats, tufts, gelatinous colonies, and gelatinous filaments, 7% crusts. In terms of spatial scales, we observed a predominance of Chlorophyta in open stream segments and Cyanobacteria in shaded stream segments, reflecting the loss of competitive advantage of green algae in sites with low energy availability. In the mesohabitats, the morphological types recorded in pools were predominantly poorly adapted to fast currents (free filaments), while those found in riffles (mats, tufts and gelatinous filaments) were highly resistant to fast water flows. As such, the use of species groupings based on algal taxonomy associated with morphological characteristics proved to be useful to understanding the distributions of these organisms in lotic environments.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

INFLUENCE OF MANUFACTURER SIGNATURE ON STORE BRANDS' LOYALTY AND PURCHASE INTENTION

ABSTRACT With today's trend toward higher store concentration, building strong store brands has become a priority for many retailing companies. This study aims to analyze the differences in store brands' purchasing likelihood between store brands with a manufacturer identification - a manufacturer signature - and store brands with no information about the manufacturer, as well as the moderating role of the manufacturer signature on store brands' purchase intention. We carried out multiple group analysis through structural equation modeling. Our findings suggest that store brand image has the most significant influence on loyalty and purchase intention for both types of store brands. Moreover, and contrary to our expectations, we did not find empirical support for the moderating role of manufacturer signature on store brands' purchasing likelihood.

Influence of the support offered to breastfeeding by maternity hospitals

ABSTRACT OBJECTIVE To evaluate whether the support offered by maternity hospitals is associated with higher prevalences of exclusive and predominant breastfeeding. METHODS This is a cross-sectional study including a representative sample of 916 infants less than six months who were born in maternity hospitals, in Ribeirao Preto, Sao Paulo, Southeastern Brazil, 2011. The maternity hospitals were evaluated in relation to their fulfillment of the Ten Steps to Successful Breastfeeding. Data were collected regarding breastfeeding patterns, the birth hospital and other characteristics. The individualized effect of the study factor on exclusive and predominant breastfeeding was analyzed using Poisson multiple regression with robust variance. RESULTS Predominant breastfeeding tended to be more prevalent when the number of fulfilled steps was higher (p of linear trend = 0.057). The step related to not offering artificial teats or pacifiers to breastfed infants and that related to encouraging the establishment of breastfeeding support groups were associated, respectively, to a higher prevalence of exclusive (PR = 1.26; 95%CI 1.04;1.54) and predominant breastfeeding (PR = 1.55; 95%CI 1.01;2.39), after an adjustment was performed for confounding variables. CONCLUSIONS We observed a positive association between support offered by maternity hospitals and prevalences of exclusive and predominant breastfeeding. These results can be useful to other locations with similar characteristics (cities with hospitals that fulfill the Ten Steps to Successful Breastfeeding) to provide incentive to breastfeeding, by means of promoting, protecting and supporting breastfeeding in maternity hospitals.

Cell surface hydrophobicity and adherence of a strain of group B streptococci during the post-antibiotic effect of penicillin

The minimum inhibitory concentration and post-antibiotic effects of an antimicrobial agent are parameters to be taken into consideration when determining its dosage schedules. The in vitro post-antibiotic effects on cell surface hydrophobicity and bacterial adherence were examined in one strain of group B streptococci. Exposure of the microorganism for 2 h at 37 °C to 1 x MIC of penicillin induced a PAE of 1.1 h. The cell surface charge of the Streptococcus was altered significantly during the post-antibiotic phase as shown by its ability to bind to xylene: hydrophobicity was decreased. Bacterial adherence to human buccal epithelial cells was also reduced. The results of the present investigation indicate that studies designed to determine therapeutic regimens should evaluate the clinical significance of aspects of bacterial physiology during the post-antibiotic period.