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.

Polifosfatos em detergentes em pó comerciais

A didactic experiment is proposed in order to identify inorganic phosphates in home laundry detergents by ascending paper chromatography. Chemical principles related with hard water are also investigated. The role of polyphosphates in detergent formulations is discussed and the softening of hard water by sodium tripolyphosphate is illustrated. Several chemical concepts, related to the daily experience of the students, can be explored in post-lab discussions.

On line pre-concentration for simultaneous determination of low molecular weight organic acids and inorganic anions in Amazonian river water samples employing ion chromatography with conductivity detection

An ion chromatography procedure, employing an IonPac AC15 concentrator column was used to investigate on line preconcentration for the simultaneous determination of inorganic anions and organic acids in river water. Twelve organic acids and nine inorganic anions were separated without any interference from other compounds and carry-over problems between samples. The injection loop was replaced by a Dionex AC15 concentrator column. The proposed procedure employed an auto-sampler that injected 1.5 ml of sample into a KOH mobile phase, generated by an Eluent Generator, at 1.5 mL min-1, which carried the sample to the chromatographic columns (one guard column, model AG-15, and one analytical column, model AS15, with 250 x 4mm i.d.). The gradient elution concentrations consisted of a 10.0 mmol l-1 KOH solution from 0 to 6.5 min, gradually increased to 45.0 mmol l-1 KOH at 21 min., and immediatelly returned and maintained at the initial concentrations until 24 min. of total run. The compounds were eluted and transported to an electro-conductivity detection cell that was attached to an electrochemical detector. The advantage of using concentrator column was the capability of performing routine simultaneous determinations for ions from 0.01 to 1.0 mg l-1 organic acids (acetate, propionic acid, formic acid, butyric acid, glycolic acid, pyruvate, tartaric acid, phthalic acid, methanesulfonic acid, valeric acid, maleic acid, oxalic acid, chlorate and citric acid) and 0.01 to 5.0 mg l-1 inorganic anions (fluoride, chloride, nitrite, nitrate, bromide, sulfate and phosphate), without extensive sample pretreatment and with an analysis time of only 24 minutes.

Spatial-temporal variation of dissolved inorganic material in the Amazon basin

The Amazon River basin is important in the contribution of dissolved material to oceans (4% worldwide). The aim of this work was to study the spatial and the temporal variability of dissolved inorganic materials in the main rivers of the Amazon basin. Data from 2003 to 2011 from six gauging stations of the ORE-HYBAM localized in Solimões, Purus, Madeira and Amazon rivers were used for this study. The concentrations of Ca2+, Na+, K+, Mg2+, Cl-, SO4 -2, HCO3 - and SiO2 were analyzed. At the stations of Solimões and Amazon rivers, the concentrations of Ca2+, Mg2+, HCO3 - and SO4 -2 had heterogeneous distribution over the years and did not show seasonality. At the stations of Madeira river, the concentration of these ions had seasonality inversely proportional to water discharge (dilution-concentration effect). Similar behavior was observed for the concentrations of Cl- and Na+ at the stations of the Solimões, Amazon and Madeira rivers, indicating almost constant release of Cl- and Na+ fluxes during the hydrological cycle. K+ and SiO2 showed almost constant concentrations throughout the years and all the stations, indicating that their flows depend on the river discharge variation. Therefore, the temporal variability of the dissolved inorganic material fluxes in the Solimões and Amazon rivers depends on the hydro-climatic factor and on the heterogeneity of the sources. In the Madeira and Purus rivers there is less influence of these factors, indicating that dissolved load fluxes are mainly associated to silicates weathering. As the Solimões basin contributes approximately 84% of the total flux of dissolved materials in the basin and is mainly under the influence of a hydro-climatic factor, we conclude that the temporal variability of this factor controls the temporal variability of the dissolved material fluxes of the Amazon basin.

Effect of water and citrate solubility on agronomic effectiveness of acidulated phosphates in three consecutive corn crops

In the process of phosphate rock acidulation, several impure P compounds may be formed along with the desirable Ca and NH4 phosphates. Such compounds normally reduce the content of water-soluble P and thus the agronomic effectiveness of commercial fertilizers. In order to study this problem, a greenhouse experiment consisting of three consecutive corn crops was conducted in samples of a Red-Yellow Latosol (Typical Hapludox) in a completely randomized design (6 x 2 x 2), with four replicates. Six commercial fertilizers were added to 2 kg of soil at a rate of 70 mg kg-1 P, based on the content of soluble P in neutral ammonium citrate plus water (NAC + H2O) of the fertilizers. Fertilizer application occurred either in the original form or leached to remove the water-soluble fraction, either by mixing the fertilizer with the whole soil in the pots or with only 1 % of its volume. The corn plants were harvested 40 days after emergence to determine the shoot dry matter and accumulated P. For the first crop and localized application, the elimination of water-soluble P from the original fertilizers resulted in less bioavailable P for the plants. For the second and third crops, the effects of P source, leaching and application methods were not as evident as for the first, suggesting that the tested P sources may have similar efficiencies when considering successive cropping. The conclusion was drawn that the water-insoluble but NAC-soluble fractions of commercial P fertilizers are not necessarily inert because they can provide P in the long run.

Influence of soil pH on inorganic phosphorus sorption and desorption in a humid brazilian Ultisol

Liming is a common practice to raise soil pH and increase phosphorus (P) bioavailability in tropical regions. However, reports on the effect of liming on P sorption and bioavailability are controversial. The process of phosphorus desorption is more important than P sorption for defining P bioavailability. However few studies on the relationship between soil pH and P desorption are available, and even fewer in the tropical soils. The effects of soil pH on P sorption and desorption in an Ultisol from Bahia, Brazil, were investigated in this study. Phosphorus sorption decreased by up to 21 and 34 % with pH increases from 4.7 to 5.9 and 7.0, respectively. Decreasing Langmuir K parameter and decreasing partition coefficients (Kd) with increasing pH supported this trend. Phosphorus desorption was positively affected by increased soil pH by both the total amount of P desorbed and the ratio of desorbed P to initially sorbed P. A decreased K parameter and increased Kd value, particularly at the highest pH value and highest P-addition level, endorsed this phenomenon. Liming the soil had the double effect of reducing P sorption (up to 4.5 kg ha-1 of remaining P in solution) and enhancing P desorption (up to 2.7 kg ha-1 of additionally released P into solution).

Nitrogen application timing and soil inorganic nitrogen dynamics under no-till oat/maize sequential cropping

The timing of N application to maize is a key factor to be considered in no-till oat/maize sequential cropping. This study aimed to evaluate the influence of pre-planting, planting and sidedress N application on oat residue decomposition, on soil N immobilisation and remineralisation and on N uptake by maize plants in no-till oat/maize sequential cropping. Undisturbed soil cores of 10 and 20 cm diameter were collected from the 0-15 cm layer of a no-till Red Latossol, when the oat cover crop was in the milk-grain stage. Two greenhouse experiments were conducted simultaneously. Experiment A, established in the 10 cm diameter cores and without plant cultivation, was used to asses N dynamics in soil and oat residues. Experiment B, established in the 20 cm diameter cores and with maize cultivation, was used to assess plant growth and N uptake. An amount of 6.0 Mg ha-1 dry matter of oat residues was spread on the surface of the cores. A rate of 90 kg N ha-1 applied as ammonium sulphate in both experiments was split in pre-planting, planting and sidedress applications as follows: (a) 00-00-00 (control), (b) 90-00-00 (pre-planting application, 20 days before planting), (c) 00-90-00 (planting application), (d) 00-30-60 (split in a planting and a sidedress application 31 days after emergence), (e) 00-00-00* (control, without oat residue) and (f) 90-00-00* (pre-planting application, without oat residue). The N concentration and N content in oat residues were not affected during decomposition by N fertilisation. Most of the fertiliser NH4+-N was converted into NO3--N within 20 days after application. A significant decrease in NO3--N contents in the 0-4 cm layer was observed in all treatments between 40 and 60 days after the oat residue placement on the soil surface, suggesting the occurrence of N immobilisation in this period. Considering that most of the inorganic N was converted into NO3- and that no immobilisation of the pre planting fertiliser N occurred at the time of its application, it was possible to conclude that pre-planting applied N was prone to losses by leaching. On the other hand, with split N applications, maize plants showed N deficiency symptoms before sidedress application. Two indications for fertiliser-N management in no-till oat/maize sequential cropping could be suggested: (a) in case of split application, the sidedress should be earlier than 30 days after emergence, and (b) if integral application is preferred to save field operations, this should be done at planting.

Mobility of inorganic and organic phosphorus forms under different levels of phosphate and poultry litter fertilization in soils

The eutrophication of aquifers is strongly linked to the mobility of P in soils. Although P mobility was considered irrelevant in a more distant past, more recent studies have shown that P, both in organic (Po) and inorganic forms (Pi), can be lost by leaching and eluviation through the soil profile, particularly in less weathered and/or sandier soils with low P adsorption capacity. The purpose of this study was to determine losses of P forms by leaching and eluviation from soil columns. Each column consisted of five PVC rings (diameter 5 cm, height 10 cm), filled with two soil types: a clayey Red-Yellow Latosol and a sandy loam Red-Yellow Latosol, which were exposed to water percolation. The soils were previously treated with four P rates (as KH2PO4 ) to reach 0, 12.5, 25.0 and 50 % of the maximum P adsorption capacity (MPAC). The P source was homogenized with the whole soil volume and incubated for 60 days. After this period the soils were placed in the columns; the soil of the top ring was mixed with five poultry litter rates of 0, 20, 40, 80, and 160 t ha-1 (dry weight basis). Treatments consisted of a 4 x 5 x 2 factorial scheme corresponding to four MPAC levels, five poultry litter rates, two soils, with three replications, arranged in a completely randomized block design. Deionized water was percolated through the columns 10 times in 35 days to simulate about 1,200 mm rainfall. In the leachate of each column the inorganic P (reactive P, Pi) and organic P forms (unreactive P, Po) were determined. At the end of the experiment, the columns were disassembled and P was extracted with the extractants Mehlich-1 (HCl 0.05 mol L-1 and H2SO4 0.0125 mol L-1) and Olsen (NaHCO3 0.5 mol L-1; pH 8.5) from the soil of each ring. The Pi and Po fractions were measured by the Olsen extractant. It was found that under higher poultry litter rates the losses of unreactive P (Po) were 6.4 times higher than of reactive P (Pi). Both the previous P fertilization and increasing poultry litter rates caused a vertical movement of P down the soil columns, as verified by P concentrations extracted by Mehlich-1 and NaHCO3 (Olsen). The environmental critical level (ECL), i.e., the P soil concentration above which P leaching increases exponentially, was 100 and 150 mg dm-3 by Mehlich-1 and 40 and 60 mg dm-3 by Olsen, for the sandy loam and clay soils, respectively. In highly weathered soils, where residual P is accumulated by successive crops, P leaching through the profile can be significant, particularly when poultry litter is applied as fertilizer.

Nitrogen dynamics in soil management systems. I - flux of inorganic nitrogen (NH4+ and NO3-)

In agricultural systems the N-NH4+ and N-NO3- contents is significantly affected by soil management. This study investigated the dynamics of inorganic nitrogen (N; NH4+ and NO3-) in an experimental evaluation of soil management systems (SMSs) adopted in 1988 at the experimental station of the ABC Foundation in Ponta Grossa, in the Central South region of the State of Paraná. The objective of this study was to evaluate the changes in N-NH4+ and N-NO3- flux in the surface layer of a Red Latosol arising from SMSs over a 12-month period. The experiment was arranged in a completely randomized block design in split plots, in three replications. The plots consisted of the following SMSs: 1) conventional tillage (CT); 2) minimum tillage (MT); 3) no-tillage with chisel plow every three years (NT CH); and 4) continuous no-tillage (CNT). To evaluate the dynamics of inorganic N, the subplots represented samplings (11 sampling times, T1 - T11). The ammonium N (N-NH4+) and nitric N (N-NO3-) contents were higher in systems with reduced tillage (MT and NT CH) and without tillage (CNT) than in the CT system. In the period from October 2003 to February 2004, the N-NH4+ was higher than the N-NO3- soil content. Conversely, in the period from May 2004 to July 2004, the N-NO3- was higher than the N-NH4+ content. The greatest fluctuation in the N-NH4+ and N-NO3- contents occurred in the 0-2.5 cm layer, and the highest peak in the N-NH4+ and N-NO3- concentrations occurred after the surface application of N. Both N-NH4+ and N-NO3- were strongly correlated with the soil organic C content, which indicated that these properties vary together in the system.

Forms of inorganic phosphorus in soil under different long term soil tillage systems and winter crops

The cultivation of crops with different capacity of P uptake and use under long-term soil tillage systems can affect the distribution of P cycling and inorganic forms in the soil, as a result of higher or lower use efficiency of P applied in fertilizers. The purpose of this study was to evaluate the effect of long-term cultivation of different winter species under tillage systems on the distribution of inorganic P forms in the soil. In 1986, the experiment was initiated with six winter crops (blue lupin, hairy vetch, oat, oilseed radish, wheat and fallow) on a Rhodic Hapludox in southwestern Paraná, under no-tillage (NT) and conventional tillage (CT). The application of phosphate fertilizer in NT rows increased inorganic P in the labile and moderately labile forms, and soil disturbance in CT redistributed the applied P in the deeper layers, increasing the moderately labile P concentration in the subsurface layers. Black oat and blue lupin were the most efficient P-recyclers and under NT, they increased the labile P content in the soil surface layers.

Soil phosphorus availability and soybean response to phosphorus starter fertilizer

Phosphorus fixation in tropical soils may decrease under no-till. In this case, P fertilizer could be surface-spread, which would improve farm operations by decreasing the time spend in reloading the planter with fertilizers. In the long term, less soluble P sources could be viable. In this experiment, the effect of surface-broadcast P fertilization with both soluble and reactive phosphates on soil P forms and availability to soybean was studied with or without fertilization with soluble P in the planting furrow in a long-term experiment in which soybean was grown in rotation with Ruzigrass (Brachiaria ruziziensis). No P or 80 kg ha-1 of P2O5 in the form of triple superphosphate or Arad reactive rock phosphate was applied on the surface of a soil with variable P fertilization history. Soil samples were taken to a depth of 60 cm and soil P was fractionated. Soybean was grown with 0, 30, and 60 kg ha-1 of P2O5 in the form of triple phosphate applied in the seed furrow. Both fertilizers applied increased available P in the uppermost soil layers and the moderately labile organic and inorganic forms of P in the soil profile, probably as result of root decay. Soybean responded to phosphates applied on the soil surface or in the seed furrow; however, application of soluble P in the seed furrow should not be discarded. In tropical soils with a history of P fertilization, soluble P sources may be substituted for natural reactive phosphates broadcast on the surface. The planting operation may be facilitated through reduction in the rate of P applied in the planting furrow in relation to the rates currently applied.

Ruzigrass affecting soil-phosphorus availability

The objective of this work was to evaluate the effectiveness of ruzigrass (Urochloaruziziensis) in enhancing soil-P availability in areas fertilized with soluble or reactive rock phosphates. The area had been cropped for five years under no-till, in a system involving soybean, triticale/black-oat, and pearl millet. Previously to the five-year cultivation period, corrective phosphorus fertilization was applied once on soil surface, at 0.0 and 80 kg ha-1 P2O5, as triple superphosphate or Arad rock phosphate. After this five-year period, plots received the same corrective P fertilization as before and ruzigrass was introduced to the cropping system in the stead of the other cover crops. Soil samples were taken (0-10 cm) after ruzigrass cultivation and subjected to soil-P fractionation. Soybean was grown thereafter without P application to seed furrow. Phosphorus availability in plots with ruzigrass was compared to the ones with spontaneous vegetation for two years. Ruzigrass cultivation increased inorganic (resin-extracted) and organic (NaHCO3) soil P, as well as P concentration in soybean leaves, regardless of the P source. However, soybean yield did not increase significantly due to ruzigrass introduction to the cropping system. Soil-P availability did not differ between soluble and reactive P sources. Ruzigrass increases soil-P availability, especially where corrective P fertilization is performed.

Molecular mechanics application in inorganic Chemistry

The present paper is a review about basic principles of the molecular mechanics that is the most important tool used in molecular modeling area, and their applications to the calculation of the relative stability and chemical reactivity of organometalic and coordination compounds. We show how molecular mechanics can be successfully applied to a wide variety of inorganic systems.

Nanoparticle-coated organic-inorganic microparticles: experimental design and gastrointestinal tolerance evaluation

The influences of the spray-drying parameters and the type of nanoparticles (nanocapsules or nanospheres) on the characteristics of nanoparticle-coated diclofenac-loaded microparticles were investigated by using a factorial design 3². Gastrointestinal tolerance following oral administration in rats was evaluated. Formulations were selected considering the best yields, the best encapsulation efficiencies and the lowest water contents, presenting surfaces completely coated by nanostructures and a decrease in the surface areas in relation to the uncoated core. In vitro drug release demonstrated the influence of the nanoparticle-coating on the dissolution profiles of diclofenac. Nanocapsule-coated microparticles presented a protective effect on the gastrointestinal mucosa.

A relevante potencialidade dos centros básicos nitrogenados disponíveis em polímeros inorgânicos e biopolímeros na remoção catiônica

This review reports the application of inorganic and organic polymeric materials for cation removal by using nitrogenated basic centers. The data demonstrate the importance of the desired groups when free or immobilized on natural or synthesized inorganic polymers through silanol groups. Thus, the most studied silica gel is followed by natural crysotile and talc polymers, and the synthesized mesopore silicas, talc-like, silicic acids, phosphates and phyllosilicates. The organic natural biopolymeric chitin and cellulose were chemically modified to improve the availability of the amine groups or the reactivity with desirable molecules to enlarge the content of basic centers. The cation removal takes place at the solid/liquid interface and some interactive effects have their thermodynamic data determined.