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.

Dynamics of feeding and defecation in Triatoma vitticeps (Stal, 1859) (Hemiptera, Reduviidae, Triatominae) and its potential in the transmission of Trypanosoma cruzi

Adults of Triatoma vitticeps infected by flagellates similar to Trypanosoma cruzi are frequently captured by the inhabitants of rural areas in the Brazilian state of Espírito Santo. The dynamics of feeding and defecation were observed in three groups of adult triatomines, consisting of sylvatic T. vitticeps and laboratory-reared specimens of this species and T. infestans. Triatomines were observed from the moment they were presented with an immobilized chicken as a bloodmeal source until 240 min after feeding had ended. Mean times between the end of feeding and defecation for T. infestans, wild T. vitticeps and laboratory-reared specimens of the latter species were 1.2, 21.1, and 64 min respectively. All T. infestans defecated within 10 min of feeding, while only 29.9 of wild and 52.8% laboratory-reared specimens of T. vitticeps did so within this period. These results may explain the low efficiency of T. vitticeps in T. cruzi transmission to man. The shorter time between feeding and defecation in laboratory-reared T. vitticeps may indicate a change in behaviour of this species as a result of adaptation to an artificial environment.

Biomass production and phosphorus use of forage grasses fertilized with two phosphorus sources

A major constraint to agricultural production in acid soils of tropical regions is the low soil P availability, due to the high adsorption capacity, low P level in the source material and low efficiency of P uptake and use by most of the modern varieties grown commercially. This study was carried out to evaluate the biomass production and P use by forage grasses on two soils fertilized with two P sources of different solubility. Two experiments were carried out, one for each soil (Cambisol and Latosol), using pots filled with 4 dm³ soil in a completely randomized design and a 4 x 2 factorial scheme. The treatments consisted of a combination of four forage plants (Brachiaria decumbens, Brachiaria brizantha, Pennisetum glaucum and Sorghum bicolor) with two P sources (Triple Superphosphate - TSP and Arad Reactive Phosphate - ARP), with four replications. The forage grasses were harvested at pre-flowering, when dry matter weight and P concentrations were measured. Based on the P concentration and dry matter production, the total P accumulation was calculated. With these data, the following indices were calculated: the P uptake efficiency of roots, P use efficiency, use efficiency of available P, use efficiency of applied P and agronomic efficiency. The use of the source with higher solubility (TSP) resulted, generally, in higher total dry matter and total P accumulation in the forage grasses, in both soils. For the less reactive source (ARP), the means found in the forage grasses, for use efficiency and efficient use of available P, were always higher when grown in Latosol, indicating favorable conditions for the solubility of ARP. The total dry matter of Brachiaria brizantha was generally higher, with low P uptake, accumulation and translocation, which indicated good P use efficiency for both P sources and soils. The forage plants differed in the P use potential, due to the sources of the applied P and of the soils used. Less than 10 % of the applied P was immobilized in the forage dry matter. Highest values were observed for TSP, but this was not reflected in a higher use efficiency of P from this source.

Phosphatase activity in sandy soil influenced by mycorrhizal and non-mycorrhizal cover crops

Cover crops may difffer in the way they affect rhizosphere microbiota nutrient dynamics. The purpose of this study was to evaluate the effect of mycorrhizal and non-mycorrhizal cover crops on soil phosphatase activity and its persistence in subsequent crops. A three-year experiment was carried out with a Typic Quartzipsamment. Treatments were winter species, either mycorrhizal black oat (Avena strigosa Schreb) or the non-mycorrhizal species oilseed radish (Raphanus sativus L. var. oleiferus Metzg) and corn spurry (Spergula arvensis L.). The control treatment consisted of resident vegetation (fallow in the winter season). In the summer, a mixture of pearl millet (Pennisetum americanum L.) with sunnhemp (Crotalaria juncea L.) or with soybean (Glycine max L.) was sown in all plots. Soil cores (0-10 cm) and root samples were collected in six growing seasons (winter and summer of each year). Microbial biomass P was determined by the fumigation-extraction method and phosphatase activity using p-nitrophenyl-phosphate as enzyme substrate. During the flowering stage of the winter cover crops, acid phosphatase activity was 30-35 % higher in soils with the non-mycorrhizal species oilseed radish, than in the control plots, regardless of the amount of P immobilized in microbial biomass. The values of enzyme activity were intermediate in the plots with corn spurry and black oat. Alkaline phosphatase activity was 10-fold lower and less sensitive to the treatments, despite the significant relationship between the two phosphatase activities. The effect of plant species on the soil enzyme profile continued in the subsequent periods, during the growth of mycorrhizal summer crops, after completion of the life cycle of the cover crops.

Nutrient relations during an eucalyptus cycle at different population densities

To synchronize nutrient availability with the requirements of eucalyptus during a cultivation cycle, the nutrient flow of this system must be well understood. Essential, for example, is information about nutrient dynamics in eucalyptus plantations throughout a cultivation cycle, as well as impacts on soil nutrient reserves caused by the accumulation and subsequent export of nutrients via biomass. It is also important to quantify the effect of some management practices, such as tree population density (PD) on these fluxes. Some nutrient relations in an experiment with Eucalyptus grandis, grown at different PDs in Santa Barbara, state of Minas Gerais, Brazil, were evaluated for one cultivation cycle. At forest ages of 0.25, 2.5, 4.5, and 6.75 years, evaluations were carried out in the stands at seven different PDs (between 500 and 5,000 trees ha-1) which consisted in chemical analyses of plant tissue sampled from components of the aboveground parts of the tree, from the forest floor and the litterfall. Nutrient contents and allocations of the different biomass components were estimated. In general, there were only small and statistically insignificant effects of PD on the nutrient concentration in trees. With increasing forest age, P, K, Ca and Mg concentrations were reduced in the aboveground components and the forest floor. The magnitud of biochemical nutrient cycling followed the sequence: P > K > N > Mg. At the end of the cycle, the quantities of N, P, Ca and Mg immobilized in the forest floor were higher than in the other components.

Kinetic parameters of soil β-glucosidase response to environmental temperature and moisture regimes

Soil β-glucosidase participates in the final step of cellulose biodegradation. It is significant in the soil C cycle and is used as an indicator of the biological fertility of soil. However, the response of its kinetic parameters to environmental temperature and moisture regimes is not well understood. This study tested the β-glucosidase response in the main agricultural soils (black soil, albic soil, brown soil, and cinnamon soil) of Northeast China. Incubation tests were conducted to measure the kinetic parameters Km, Vmax or Vmax/Km of soil β-glucosidase at environmental temperatures of 10, 20 and 30 ºC and at 10, 20 and 30 % soil moisture content. The insensitive response of the kinetic parameters to temperature changes indicates that soil β-glucosidase was present primarily in immobilized form. The significant response of the kinetic parameters of soil β-glucosidase to soil moisture rather than to environmental temperatures suggests that the catalytic ability of soil β-glucosidase was sensitive to changing soil moisture regimes.

Soil biological attributes in pastures of different ages in a crop-livestock integrated system

The objective of this work was to evaluate the effect of the pasture (Urochloa brizantha) component age on soil biological properties, in a crop-livestock integrated system. The experiment was carried out in a Brazilian savannah (Cerrado) area with 92 ha, divided into six pens of approximately 15 ha. Each pen represented a different stage of the pasture component: formation, P0; one year, P1; two years, P2; three years, P3; and final with 3.5 years, Pf. Samples were taken in the 0-10 cm soil depth. The soil biological parameters - microbial biomass carbon (MBC), microbial biomass respiration (C-CO2), metabolic quotient (qCO2), microbial quotient (q mic), and total organic carbon (TOC) - were evaluated and compared among different stages of the pasture, and between an adjacent area under native Cerrado and another area under degraded pasture (PCD). The MBC, q mic and TOC increased and qCO2 reduced under the different pasture stages. Compared to PCD, the pasture stages had higher MBC, q mic and TOC, and lower qCO2. The crop-livestock integrated system improved soil microbiological parameters and immobilized carbon in the soil in comparison to the degraded pasture.

Assessment on nutrient levels in the aerial biomass of irrigated guava in São Francisco Valley, Brazil

In perennial crops, fertilizers are applied to restore the amount of nutrient removed from the plant by harvesting. Nevertheless, the immobilized nutrient inside the whole plant should be considered. Based on it, the nutrient concentrations in the guava leaf and fruit and the nutrient contents removed by fruits and post-harvest pruning were evaluated in an irrigated orchard, in Petrolina, State of Pernambuco, Brazil. The greatest contents removed by fruits were N and K among the macronutrients, while Fe, Zn and Mn presented higher levels among the micronutrients. More than 60% of the total content of N, P, K, Mg, Fe, and B removed by pruning were immobilized in the leaf and non-marketable fruit.

Projeto e construção de um bioreator para síntese orgânica assimétrica catalisada por saccharomyces cerevisiae (fermento biológico de padaria)

A model for the construction of a simple and cheap apparatus to be used as bioreactor for reactions catalyzed by baker's yeast (Saccharomyces cerevisiae) is described. The bioconversion and separation of cells from products and residual substrates are obtained at the same time. The reactions carried out in this type of reactor are faster than those catalyzed by immobilized cells. Yeast cells can be cultivated in this bioreactor operating with cell recycling at appropriated conditions using glucose and other nutrients.

Organo-gel: um novo sistema para a imobilização de lipases e sua aplicação em síntese orgânica

Lipases have been immobilized in microemulsion-based organogels (MBG's) and successfully utilized for the enantioselective esterification, diesterification and transesterification reactions, in organic solvents at 25ºC. This methodology is described as a new alternative for the use of enzymes in organic solvents. High enzymic stability has been observed. We have also used this methodology for the successful resolution of chiral secondary alcohols. This is a convenient way of using this catalyst in organic solvents which employs small amounts of the enzyme (250mg/mL).

Determinação de fósforo orgânico em águas de produção petrolífera por ICP- AES e ICP- MS após pré-concentração em coluna de sílica-C18

Results on the optimization of analytical methods for the determination of phosphorus in phosphino-polycarboxylate (PPCA), used frequently as scale inhibitor during oil production, by ICP-AES and ICP-MS are presented. Due to the complex matrix of production waters (brines) and their high concentration in inorganic phosphorus, the separation of organic phosphorus prior to its determination is necessary. In this work, minicolumns of silica immobilized C18 were used. Optimization of the separation step resulted in the following working conditions: (1) prewashing of the column with methanol (80% v/v); (2) use of a flow rate of 5 mL/min and 10 mL/min, respectively, for the preconditioning step and for percolation of the water sample; (3) final elution of organic phosphorus with 7 mL of buffer of H3BO3/NaOH (0.05 M, pH 9) with a flow rate of 1 mL/min. Sample detection limits (3s) for different combinations of nebulizers and spectrometric methods, based on 10 mL water aliquots, are: ICP-AES -Cross flow (47 mg/L) and Ultrasonic (18 mug/L); ICP-MS -Cross flow (1.2 mug/L), Cyclonic (0.7 mug/L) and Ultrasonic (0.5 mug/L). Typical recoveries of organic phosphorus are between 90 and 95% and the repeatability of the whole procedure is better than 10%. The developed methodology was applied successfully to samples from the oil-well NA 46, platform PNA 2, Campos basin, Brazil. Assessment of the PPCA inhibitor was possible at lower concentrations than achieved by current analytical methods, resulting in benefits such as reduced cost of chemicals, postponed oil production and lower environmental impacts.

O relevante papel do agente sililante na modificação de superfícies de polímeros

The applicability of the silylant agents of the general formula Y3Si-R-X, depends on the reactivity of Y group (halide or alcoxide) attached to silicon and the organic function X (halide, amine, thiol, cyanide, etc) in the extreme position of the chain. Both groups are linked together by an organic chain R, containing usually three methylene groups. A series of these agents can be covalently bonded to an inorganic matrix, since the available OH groups are distributed on the surface, making silica gel the most common support. However, other inorganic oxides, zeolites, lamellar inorganic phosphates and chrysotile can also have these agents anchored. Some illustration are presented for immobilized surface in the use as extractors of cations from dilute aqueous or non-aqueous solutions, catalysts agents, ionic exchanged materials, support for enzyme immobilization, chromatographic applications, use in some industrial features and in many other areas. The evolution of this exciting research field to produce new materials, for many tecnological applications, is strongly dependent on the development of a sensible systematic process for the synthesis of a series of new specific silylant agents.

Organo-gel de heptano: diagrama de fases e aplicações sintéticas

The phase diagram formation of microemulsion-based gels composed of an anionic surfactant aerosol-OT sodium bis (2-ethylhexyl)-sulphosuccinate), water, gelatin and an organic solvent is presented for heptane. The stability of this organo- gel, when an enzyme is immobilized is discussed in terms of its reutilization in various esters synthesis.

Imobilização de 8-hidroxiquinoleína em sílica gel. Melhorias na tradicional rota de diazotação

Some modifications made at silanization step and the introduction of r-nitrobenzil bromide as an alternative reagent to the 8-hydroxiquinolein immobilization in silica gel were important points that brought up the reduction of synthesis time, efficency improvement of the immobilization process and better hydrolysis stabilization to the final materials. The caracterization was made by infrared spectroscopy, elementary analysis, complexing capacity and acid-base properties.

Termoquímica na Unicamp: depoimento sobre uma jornada de 25 anos

This article describes the progress of a group of investigation on thermochemistry, which started in 1972. A homemade calorimeter was employed to provide quantitative support to the information on interative effect between lanthanide cations and halides or pseudohalides, in non-aqueous solvents, previously derived from conductometric titrations. However, the features of this instrument were not able to detect the thermal effects. Therefore, the great input to the group came from the acquisition of an LKB commercial apparatus, by the University in 1975. Considering the historical development of the coordination chemistry in Brazil, which was previously dedicated to strutural features of adducts, without focusing the energetic envolved in any coordinationcompound. Since starting the thermochemistry study, numerous masters and doctoral thesis covering more than a hundred adducts and a reasonable number of chelates, were presented systematizing data in order to understand the behavior of this kind of coordination compounds (C. Airoldi and A. P. Chagas, Coord. Chem. Rev. 1992, 119, 29). This knowledge enabled an extension of the study to include some heterogeneous systems formed by natural or synthetic materials like immobilized silica gel, lamellar phosphate, phosphonate or sulphate compounds, clays, polysaccharides, chrysotile, soils, etc. Many students are now engaged as staff members in Universities, Research Instituitions or other private institutions, developing many activities. Due to a multiplying effect on the formation of researchers, the group is now reaching the fourth generation.