Produção científica da área da Química no desenvolvimento da oceanografia no Brasil

This paper analyses the scientific contribution of chemists and of the Brazilian Chemical Society (SBQ) and its publications to the development of Oceanography in Brazil, as well as major drivers of this participation. A total of 528 articles were analyzed. Most articles (72%) originated in research groups not associated with graduate programs in oceanography. Nearly 50% dealt with the contamination of the marine environment, followed by chemical process studies (32%) and analytical methods development (15%). SBQ journals contributed with 78 articles (14.7% of the total), and rank 1st (QN) and 2nd (JBCS) among scientific journals publishing the analyzed articles.

Potentiometric and conductimetric studies of chemical equilibria for pyridoxine hydrochloride in aqueous solutions: simple experimental determination of pKa values and analytical applications to pharmaceutical analysis

The combination of two low-cost classical procedures based on titrimetric techniques is presented for the determination of pyridoxine hydrochloride in pharmaceuticals samples. Initially some experiments were carried out aiming to determine both pKa1 and pKa2 values, being those compared to values of literature and theoretical procedures. Commercial samples containing pyridoxine hydrochloride were electrochemically analysed by exploiting their acid-base and precipitation reactions. Potentiometric titrations accomplished the reaction between the ionizable hydrogens present in pyridoxine hydrochloride, being NaOH used as titrant; while the conductimetric method was based on the chemical precipitation between the chloride of pyridoxine hydrochloride molecule and Ag+ ions from de silver nitrate, changing the conductivity of the solution. Both methods were applied to the same commercial samples leading to concordant results when compared by statistical tests (95 and 98% confidence levels). Recoveries ranging from 99.0 to 108.1% were observed, showing no significant interference on the results.

Studies of chemical and enzymatic characteristics of Yacon (Smallanthus sonchifolius) and its flours

Due to the importance of studies on yacon related to health, its in natura pulp, in natura peel, pulp flour, and peel flour were chemically analyzed in terms of its centesimal composition, specific minerals, total dietary fiber and fractions, pH, total soluble solids, total titratable acidity, tannins, oxalic acid, and nitrate. The polyphenoloxidase and peroxidase enzymatic activities were evaluated for in natura pulp and peel only. Yacon pulp and peel flour presented average yield of 7.94% and 10.86%, respectively. The in natura pulp presented a higher moisture and carboydrate content and lower lipid, protein, total dietary fiber, and ash than those of the peel flour. The same pattern was observed for pulp flour when compared to peel flour. The highest tannin, nitrate, and oxalic acid levels were found in the peel flour, 15,304.5 mg.kg-1, 1,578.3 mg.kg-1, and 7,925.0 mg.kg-1 (wet weight), respectively. The polyphenoloxidase and peroxidase enzymes presented higher enzymatic activity in the yacon peel. Based on the results obtained, it can be said that the yacon and its derivatives are important dietary carbohydrate and mineral sources and contain antinutritional substance contents lower than those harmful to health.

Tracer studies in the coffee plant (Coffea arabica L.)

Due to the great importance of coffee to the Brazilian economy, a good deal of the work carried out in the "Laboratório de Isótopos", E. E. A. "Luiz de Queiroz", Piracicaba, S. Paulo, Brazil, was dedicated to the study of some problems involving that plant. The first one was designed to verify a few aspects of the control of zinc deficiency which is common in many types of soils in Brazil. An experiment conducted in nutrient solution showed that the leaf absorption of the radiozinc was eight times as high as the root uptake; the lower surface of the leaves is particularly suited for this kind of absorption. Among the heavy metal micronutrients, only iron did not affect the absorption of the radiozinc; manganese, copper, and molybdenum brought about a decrease of fifty per cent in total uptake. In another pot experiment in which two soils typical of the coffee growing regions were used, namely, a sandy soil called "arenito de Bauru" and a heavy one, "terra roxa", only O.l and 0.2 per cent of the activity supplied to the roots was recovered", respectively. This indicates that under field conditions the farmer should not attempt to correct zinc deficiency by applying zinc salts to the soil: leaf sprays should be used wherever necessary. In order to find out the most suitable way to supply phosphatic fertilizers to the coffee plant, under normal farm conditions, an experiment with tagged superphosphate was carried out with the following methods of distribution of this material: (1) topdressed in a circular area around the trees; (2) placed in the bottom of a 15 cm deep furrow made around the plant; (3) placed in a semicircular furrow, as in the previous treatment; (4) sprayed directly to the leaves. It was verified that in the first case, circa 10 per cent of the phosphorus in the leaves came from the superphosphate; for the other treatments, the results ware, respectively: 2.4, 1.7, and 38.0 per cent. It is interesting to mention that the first and the last methods of distribution were those less used by the farmers; now they are being introduced in many coffee plantations. In a previous trial it was demonstrated that urea sprays were an adequate way to correct nitrogen deficiency under field conditions. An experiment was then set up in which urea-C14 was used to study the metabolism of this fertilizer in coffee leaves. In was verified that in a 9 hours period circa 95 per cent of the urea supplied to the leaves had been absorbed. The distribution of the nitrogen of the urea was followed by standard chemical procedures. On the other hand the fate of the carbonic moiety was studied with the aid of the radiochromatographic technique. Thus, the incorporation of C14 in aminoacids, sugars and organic acids was ascertained. Data obtained in this work gave a definite support to the idea that in coffee leaves, as in a few other higher plants, a mechanism similar to the urea cycle of animals does exist.

Plant lectins, chemical and biological aspects

Lectins, carbohydrate-binding proteins of non-immune origin, that agglutinate cells or precipitate polysaccharides and glycoconjugates, are well distributed in nature, mainly in the Plant Kingdom. The great majority of the plante lectins are present in seed cotyledons where they are found in the cytoplasm or int he protein bodies, although they have also been found in roots, stems and leaves. Due to their peculiar properties, the lectins are used as a tool both for analytical and preparative purposes in biochemistry, cellular biology, immunology and related areas. In agriculture and medicine the use of lectins greatly improved in the last few years. The lextins, with few exceptions, are glycoproteins, need divalent cations to display full activity and are, in general, oligomers with variable molecular weight. Although the studies on lectins have completed a century, their role in nature is yet ynknown . Several hypotheses on their physiological functions have been suggested. Thus, lectins could play important roles in defense against pathogens, plant-microorganism symbiosis, cell organization, embryo morphogenesis, phagocytosis, cell wall elongation, pollen recognition and as reserve proteins. A brief review on the general properties and roles of the lectins is given.

Evaluation of Chemical and Physical-morphological Factors as Potential Determinants of Biomphalaria pfeifferi (Krauss, 1848) Distribution

This study was carried out in five sites along a small perennial river system in south-central Tanzania, which had been identified as the focus for transmission of intestinal schistosomiasis in the area. Malacological surveys preceding the study showed a focal distribution of Biomphalaria pfeifferi, intermediate host snail of Schistosoma mansoni, the snails being present in three sites but absent from the other two sites. The objective of this study was to evaluate to what extent chemical and/or physical-morphological factors determine the distribution of B. pfeifferi between these five sites. It was found that none of the chemical constituents in the waters examined were outside the tolerance range of B. pfeifferi snails. Moreover, the composition of water from B. pfeifferi-free sites was not different from that in those sites where snails occurred. Furthermore, none of the physical-morphological constituents seemed likely to be a determinant for the absence of B. pfeifferi. In view of these findings, and those of previous studies, it is concluded that the focal distribution of B. pfeifferi cannot be associated with a single environmental factor and is rather the result of more complex interactions of habitat factors

The use of biodiversity as source of new chemical entities against defined molecular targets for treatment of malaria, tuberculosis, and T-cell mediated diseases: a review

The modern approach to the development of new chemical entities against complex diseases, especially the neglected endemic diseases such as tuberculosis and malaria, is based on the use of defined molecular targets. Among the advantages, this approach allows (i) the search and identification of lead compounds with defined molecular mechanisms against a defined target (e.g. enzymes from defined pathways), (ii) the analysis of a great number of compounds with a favorable cost/benefit ratio, (iii) the development even in the initial stages of compounds with selective toxicity (the fundamental principle of chemotherapy), (iv) the evaluation of plant extracts as well as of pure substances. The current use of such technology, unfortunately, is concentrated in developed countries, especially in the big pharma. This fact contributes in a significant way to hamper the development of innovative new compounds to treat neglected diseases. The large biodiversity within the territory of Brazil puts the country in a strategic position to develop the rational and sustained exploration of new metabolites of therapeutic value. The extension of the country covers a wide range of climates, soil types, and altitudes, providing a unique set of selective pressures for the adaptation of plant life in these scenarios. Chemical diversity is also driven by these forces, in an attempt to best fit the plant communities to the particular abiotic stresses, fauna, and microbes that co-exist with them. Certain areas of vegetation (Amazonian Forest, Atlantic Forest, Araucaria Forest, Cerrado-Brazilian Savanna, and Caatinga) are rich in species and types of environments to be used to search for natural compounds active against tuberculosis, malaria, and chronic-degenerative diseases. The present review describes some strategies to search for natural compounds, whose choice can be based on ethnobotanical and chemotaxonomical studies, and screen for their ability to bind to immobilized drug targets and to inhibit their activities. Molecular cloning, gene knockout, protein expression and purification, N-terminal sequencing, and mass spectrometry are the methods of choice to provide homogeneous drug targets for immobilization by optimized chemical reactions. Plant extract preparations, fractionation of promising plant extracts, propagation protocols and definition of in planta studies to maximize product yield of plant species producing active compounds have to be performed to provide a continuing supply of bioactive materials. Chemical characterization of natural compounds, determination of mode of action by kinetics and other spectroscopic methods (MS, X-ray, NMR), as well as in vitro and in vivo biological assays, chemical derivatization, and structure-activity relationships have to be carried out to provide a thorough knowledge on which to base the search for natural compounds or their derivatives with biological activity.

Influence of tree species on the herbaceous understory and soil chemical characteristics in a silvopastoral system in semi-arid northeastern Brazil

Studies from some semi-arid regions of the world have shown the beneficial effect of trees in silvopastoral systems, by promoting the formation of resource islands and increasing the sustainability of the system. No data are available in this respect for tree species of common occurrence in semi-arid Northeastern Brazil. In the present study, conducted in the summer of 1996, three tree species (Zyziphus joazeiro, Spondias tuberosa and Prosopis juliflora: ) found within Cenchrus ciliaris pastures were selected to evaluate differences on herbaceous understory and soil chemical characteristics between samples taken under the tree canopy and in open grass areas. Transects extending from the tree trunk to open grass areas were established, and soil (0-15 cm) and herbaceous understory (standing live biomass in 1 m² plots) samples were taken at 0, 25, 50, 100, 150 and 200% of the average canopy radius (average radius was 6.6 ± 0.5, 4.5 ± 0.5, and 5.3 ± 0.8 m for Z. joazeiro, P. juliflora, and S. tuberosa , respectively). Higher levels of soil C, N, P, Ca, Mg, K, and Na were found under the canopies of Z. joazeiro and P. juliflora: trees, as compared to open grass areas. Only soil Mg organic P were higher under the canopies of S. tuberosa trees, as compared to open grass areas. Herbaceous understory biomass was significantly lower under the canopy of S. tuberosa and P. juliflora trees (107 and 96 g m-2, respectively) relatively to open grass areas (145 and 194 g m-2). No herbaceous biomass differences were found between Z. joazeiro canopies and open grass areas (107 and 87 g m-2, respectively). Among the three tree species studied, Z. joazeiro was the one that presented the greatest potential for use in a silvopastoral system at the study site, since it had a larger nutrient stock in the soil without negatively affecting herbaceous understory biomass, relatively to open grass areas.

Spatial variability of the chemical, physical and biological properties in lowland cultivated with irrigated rice

In the areas where irrigated rice is grown in the south of Brazil, few studies have been carried out to investigate the spatial variability structure of soil properties and to establish new forms of soil management as well as determine soil corrective and fertilizer applications. In this sense, this study had the objective of evaluating the spatial variability of chemical, physical and biological soil properties in a lowland area under irrigated rice cultivation in the conventional till system. For this purpose, a 10 x 10 m grid of 100 points was established, in an experimental field of the Embrapa Clima Temperado, in the County of Capão do Leão, State of Rio Grande do Sul. The spatial variability structure was evaluated by geostatistical tools and the number of subsamples required to represent each soil property in future studies was calculated using classical statistics. Results showed that the spatial variability structure of sand, silt, SMP index, cation exchange capacity (pH 7.0), Al3+ and total N properties could be detected by geostatistical analysis. A pure nugget effect was observed for the nutrients K, S and B, as well as macroporosity, mean weighted diameter of aggregates, and soil water storage. The cross validation procedure, based on linear regression and the determination coefficient, was more efficient to evaluate the quality of the adjusted mathematical model than the degree of spatial dependence. It was also concluded that the combination of classical with geostatistics can in many cases simplify the soil sampling process without losing information quality.

Physical and chemical attributes of archaeological soils developed from shell middens in the Região dos Lagos, Rio de Janeiro, Brazil

In prehistoric times, innumerous shell middens, called "sambaquis", consisting mainly of remains of marine organisms, were built along the Brazilian coast. Although the scientific community took interest in these anthropic formations, especially since the nineteenth century, their pedological context is still poorly understood. The purpose of this study was to characterize and identify the physical and chemical changes induced by soil-forming processes, as well as to compare the morphology of shell midden soils with other, already described, anthropogenic soils of Brazil. Four soil profiles developed from shell middens in the Região dos Lagos - RJ were morphologically described and the physical and chemical properties determined. The chemical analysis showed that Ca, Mn, Mg, and particularly P and Zn are indicators of anthropic horizons of midden soils, as in the Amazon Dark Earths (Terras Pretas de Índio). After the deposition of P-rich material, P reaction and leaching can mask or disturb the evidence of in situ man-made strata, but mineralogical and chemical studies of phosphate forms can elucidate the apparent complexity. Lower phosphate-rich strata without direct anthropic inputs indicate P leaching and precipitation in secondary forms. The total and bioavailable contents of Ca, Mg, Zn, Mn, Cu, P, and organic C of midden soils were much higher than of regional soils without influence of ancient human settlements, demonstrating that the high fertility persisted for long periods, at some sites for more than 4000 years. The physical analysis showed that wind-blown sand contributed significantly to increase the sand fraction in the analyzed soils (texture classes sand, sandy loam and sandy clay loam) and that the aeolian sand accumulation occurred simultaneously with the midden formation.

Chemical and microbiological attributes of an oxisol treated with successive applications of sewage sludge¹

Studies on sewage sludge (SS) have confirmed the possibilities of using this waste as fertilizer and/or soil conditioner in crop production areas. Despite restrictions with regard to the levels of potentially toxic elements (PTE) and pathogens, it is believed that properly treated SS with low PTE levels, applied to soil at adequate rates, may improve the soil chemical and microbiological properties. This study consisted of a long-term field experiment conducted on a Typic Haplorthox (eutroferric Red Latosol) treated with SS for seven successive years for maize production, to evaluate changes in the soil chemical and microbiological properties. The treatments consisted of two SS rates (single and double dose of the crop N requirement) and a mineral fertilizer treatment. Soil was sampled in the 0-0.20 m layer and analyzed for chemical properties (organic C, pH, P, K, Ca, Mg, CEC, B, Cu, Fe, Mn, Zn, Cd, Ni, and Pb) and microbiological properties (basal respiration, microbial biomass activity, microbial biomass C, metabolic quotient, microbial quotient, and protease and dehydrogenase enzyme activities). Successive SS applications to soil increased the macro- and micronutrient availability, but the highest SS dose reduced the soil pH significantly, indicating a need for periodic corrections. The SS treatments also affected soil microbial activity and biomass negatively. There were no significant differences among treatments for maize grain yield. After seven annual applications of the recommended sludge rate, the heavy metal levels in the soil had not reached toxic levels.

Chemical and structural characterization of soil humic substances under agroforestry and conventional systems

Studies have proven that the agroforestry systems in the semi-arid region of the State of Ceará, Brazil, induce an increase in soil organic C levels. Notwithstanding, there is no information if this increase also results in qualitative changes in different pools of soil organic matter. The objective of this study was to verify the possible chemical and structural alterations in fulvic and humic acids of a Luvisol in areas adopting agroforestry, traditional intensive cultivation and native forest in a long-term experiment conducted in the semi-arid region of Ceará State, Brazil. The study was conducted in an experimental area of the National Goat Research Center (Embrapa) in Sobral, CE. The following treatments were evaluated: agrosilvopasture (AGP), silvopasture (SILV), intensive cultivation under fallow (ICF), and areas with native forest (NF). Soil fulvic and humic acids fractions were extracted from the 0-6 and 6-12 cm layers and characterized by elemental composition, thermogravimetry and infrared spectroscopy analyses. The elemental composition analysis of humic acids confirmed the data found for fulvic acids, showing reduction in the C, H and N levels, followed by an increase in O contents in the AGP and ICF treatments over SILV and NF. In all treatments, except to SILV in the 0-6 cm layer, the percentage of mass loss was highest (300-600 °C) for humic acids in the thermally most stable region. Despite the similarity between infrared spectra, soil fulvic acids in the SILV treatment extracted from 6-12 cm depth decrease the absorption bands at 1708 and 1408 cm-1 followed by an increase in the absorption band at 1608 cm-1 attributed to aromatic C=C groups. This behavior suggests an increase in the aromatic character of the structure. The AGP and ICF treatments, which increase the soil tilling, favored the maintenance of humic substances with a more aromatic character in the soil than SILV and NF. The less aromatic humic substances in the SILV treatment resulted in an increase of exchange sites of soil organic matter, indicating improved nutrient cycling and maintenance of productivity in the system.

Optimization of the sampling scheme for maps of physical and chemical properties estimated by kriging

The sampling scheme is essential in the investigation of the spatial variability of soil properties in Soil Science studies. The high costs of sampling schemes optimized with additional sampling points for each physical and chemical soil property, prevent their use in precision agriculture. The purpose of this study was to obtain an optimal sampling scheme for physical and chemical property sets and investigate its effect on the quality of soil sampling. Soil was sampled on a 42-ha area, with 206 geo-referenced points arranged in a regular grid spaced 50 m from each other, in a depth range of 0.00-0.20 m. In order to obtain an optimal sampling scheme for every physical and chemical property, a sample grid, a medium-scale variogram and the extended Spatial Simulated Annealing (SSA) method were used to minimize kriging variance. The optimization procedure was validated by constructing maps of relative improvement comparing the sample configuration before and after the process. A greater concentration of recommended points in specific areas (NW-SE direction) was observed, which also reflects a greater estimate variance at these locations. The addition of optimal samples, for specific regions, increased the accuracy up to 2 % for chemical and 1 % for physical properties. The use of a sample grid and medium-scale variogram, as previous information for the conception of additional sampling schemes, was very promising to determine the locations of these additional points for all physical and chemical soil properties, enhancing the accuracy of kriging estimates of the physical-chemical properties.

Animal manure phosphorus characterization by sequential chemical fractionation, release kinetics and 31P-NMR analysis

Phosphate release kinetics from manures are of global interest because sustainable plant nutrition with phosphate will be a major concern in the future. Although information on the bioavailability and chemical composition of P present in manure used as fertilizer are important to understand its dynamics in the soil, such studies are still scarce. Therefore, P extraction was evaluated in this study by sequential chemical fractionation, desorption with anion-cation exchange resin and 31P nuclear magnetic resonance (31P-NMR) spectroscopy to assess the P forms in three different dry manure types (i.e. poultry, cattle and swine manure). All three methods showed that the P forms in poultry, cattle and swine dry manures are mostly inorganic and highly bioavailable. The estimated P pools showed that organic and recalcitrant P forms were negligible and highly dependent on the Ca:P ratio in manures. The results obtained here showed that the extraction of P with these three different methods allows a better understanding and complete characterization of the P pools present in the manures.

EFFECT OF ALTERNATIVE MULTINUTRIENT SOURCES ON SOIL CHEMICAL PROPERTIES

The current high price of potassium chloride and the dependence of Brazil on imported materials to supply the domestic demand call for studies evaluating the efficiency of alternative sources of nutrients. The aim of this work was to evaluate the effect of silicate rock powder and a manganese mining by-product, and secondary materials originated from these two materials, on soil chemical properties and on brachiaria production. This greenhouse experiment was conducted in pots with 5 kg of soil (Latossolo Vermelho-Amarelo distrófico - Oxisol). The alternative nutrient sources were: verdete, verdete treated with NH4OH, phonolite, ultramafic rock, mining waste and the proportion of 75 % of these K fertilizers and 25 % lime. Mixtures containing 25 % of lime were heated at 800 ºC for 1 h. These sources were applied at rates of 0, 150, 300, 450 and 600 kg ha-1 K2O, and incubated for 45 days. The mixtures of heated silicate rocks with lime promoted higher increases in soil pH in decreasing order: ultramafic rock>verdete>phonolite>mining waste. Applying the mining waste-lime mixture increased soil exchangeable K, and available P when ultramafic rock was incorporated. When ultramafic rock was applied, the release of Ca2+ increased significantly. Mining subproduct released the highest amount of Zn2+ and Mn2+ to the soil. The application of alternative sources of K, with variable chemical composition, altered the nutrient availability and soil chemical properties, improving mainly plant development and K plant uptake, and are important nutrient sources.