Interface Energy Measurement of MgO and ZnO: Understanding the Thermodynamic Stability of Nanoparticles

Nanomaterials have triggered excitement in both fundamental science and technological applications in several fields However, the same characteristic high interface area that is responsible for their unique properties causes unconventional instability, often leading to local collapsing during application Thermodynamically, this can be attributed to an increased contribution of the interface to the free energy, activating phenomena such as sintering and grain growth The lack of reliable interface energy data has restricted the development of conceptual models to allow the control of nanoparticle stability on a thermodynamic basis. Here we introduce a novel and accessible methodology to measure interface energy of nanoparticles exploiting the heat released during sintering to establish a quantitative relation between the solid solid and solid vapor interface energies. We exploited this method in MgO and ZnO nanoparticles and determined that the ratio between the solid solid and solid vapor interface energy is 11 for MgO and 0.7 for ZnO. We then discuss that this ratio is responsible for a thermodynamic metastable state that may prevent collapsing of nanoparticles and, therefore, may be used as a tool to design long-term stable nanoparticles.

Synthesis, characterization and evaluation of phosphorylated resins in the removal of Pb(2+) from aqueous solutions

Phosphinic-derivative poly(styrene-co-divinylbenzene)-based on PS-DVB copolymers with different porosity degrees have been prepared by aromatic electrophilic substitution reaction using PCl(3)/AlCl(3) followed by base-promoted hydrolysis. The phosphorylation reaction was analyzed by infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), and thermogravimetry (TG/DTG). In addition, the phosphorous content of the phosphorylated copolymers was determined by spectrophotometry using the method based on sodium molybdate reactant so that the extension of that modification could be assessed. The performance of the phosphorylated resins in the extraction of Pb(2+) from aqueous solutions in a batch system was also evaluated. The Pb(2+) content was determined by atomic absorption spectrometry (AAS). These materials presented excellent extraction capacity under the contact time of 30 min and pH 6.

Interface excess and polymorphic stability of nanosized zirconia-magnesia

Controlling the phase stability of ZrO2 nanoparticles is of major importance in the development of new ZrO2-based nanotechnologies. Because of the fact that in nanoparticles the surface accounts for a larger fraction of the total atoms, the relative phase stability can be controlled throughout the surface composition, which can be toned by surface excess of one of the components of the system., The objective of this work is to delineate a relationship between surface excess (or solid solution) of MgO relative to ZrO2 and the polymorphic stability of (ZrO2)(1-x) - (MgO), nanopowders, where 0.0 <= x <= 0.6. The nanopowders were prepared by a liquid precursor method at 500 degrees C and characterized by N-2 adsorption (BET), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), and Raman spectroscopy. For pure ZrO2 samples, both tetragonal and monoclinic polymorphs were detected, as expected considering the literature. For MgO molar fractions varying from 0.05 to 0.10, extensive solid solution could not be detected, and a ZrO2 surface energy reduction, caused by Mg surface excess detected by XPS, promoted tetragonal polymorph thermodynamic stabilization with relation to monoclinic. For MgO molar fractions higher than 0.10 and up to 0.40, Mg solid solution could be detected and induced cubic phase stabilization. MgO periclase was observed only at x = 0.6. A discussion based on the relationship between the surface excess, surface energy, and polymorph stability is presented.

The sorption of toxic elements onto natural zeolite, synthetic goethite and modified powdered block carbon

Inorganic elements analyses of Carapicuiba lake reveal that As, Cr, Pb and Mn are above the recommended drinking water standards. The mean total concentrations of toxic elements in surface water decrease in the order Mn > Cr > Pb > As. At elevated concentrations, toxic elements like Cr can accumulate in soils and enter the food chain, leading to serious health hazards and threatening the long-term sustainability of the local ecosystem. Absorbing materials has often been used to improve water quality. In this investigation three types of material were studied: the natural zeolite (mordenite); synthetic goethite and the powdered block carbon modified. The adsorption of Pb(2+) and Mn(2+) onto natural zeolite as a function of their concentrations was studied at 24 degrees C by varying the metal concentration from 100 to 400 mg L(-1) while keeping all other parameters constant. The low-cost zeolites removed Pb from water without any pretreatment at pH values <6. The maximum adsorption attained was as follows: Pb(2+) 78.7% and Mn(2+) 19.6%. The modified powdered block carbon effectively removed As(V) and Cr(VI) while goethite removed more chromate than arsenate in the pH range 5-6. Results of this study will be used to evaluate the application these materials for the treatment of the Carapicuiba lake`s water.

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

This work investigates the formation of self-assembled monolayers (SAMs) of cystamine and cystamine-glutaraldehyde on a screen-printed electrode, and the immobilization of the Tc85 protein (from Trypanosoma cruzi) on these monolayers. The methods used included infrared techniques, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical studies were performed at pH 6.9 in 0.1 mol L(-1) phosphate buffer solution containing Fe(CN)(6)(-3/-4) redox species. The surface coverage (0) of the electrode was 0.10 (cystamine), 0.35 (cystamine-glutaraldehyde) and 0.84 (Tc85). Interpretation of electrochemical impedance spectroscopy results was based on a charge-transfer reaction involving Fe(CN)(6)(-3/-4) species at high frequencies, followed by a diffusion through the monolayers at lower frequencies. Estimates of the electrode surface coverage, active site radius, and distance between two adjacent sites assumed that charge transfer occurred at the active sites, and that there was a planar diffusion of redox species to these sites. (C) 2009 Elsevier B.V. All rights reserved.

Adsorbent new materials and composites produced in a single step

The aim of this work is the production and preliminary characterization of adsorbent new materials useful for sensor development. A new plasma chamber was simulated and designed in order to obtain multiple layers and/or composites in a single step. Plasma deposited organic fluorocompound and hexamethyldisilazane (HMDS) thin films were produced and tested as adsorbent layers. Chemical characterization used ellipsometry, Raman. infrared and X-ray photoelectron spectroscopy. Hydrophobic and oleophobic character were determined by contact angle measurements. Adsorption characteristics were evaluated using quartz crystal microbalance. Not only HMDS but also the fluorocompound can polymerize but intermixing and a double layer are only obtained in very narrow conditions. The films are adsorbent and mildly hydrophobic. Films deposited on a microchromatographic column can be used on sample pretreatment to remove and/or preconcentrate volatile organic Compounds. Therefore, with this approach it is possible to obtain films with different monomers on double layer or composites, with organic/inorganic materials or particles and use them on sample pretreatment for chemical analysis. (C) 2008 Elsevier B.V. All rights reserved.

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.

Acidity and Aluminum Speciation as Affected by Surface Liming in Tropical No-Till Soils

Aluminum toxicity is one of the major soil factors limiting root growth in acidic soils. Because of the increase in organic matter content in the upper few centimeters of soils under no-till systems (NTS), most Al in soil solution may be complexed to dissolved organic C (DOC), thus decreasing its bioavailability. The aim of this study was to evaluate the effects of surface liming on Al speciation in soil solution in Brazilian sites under NTS. Field experiments were performed in two regions with contrasting climates and levels of soil acidity: Rondonopolis, Mato Grosso State, on a Rhodic Haplustox, and Ponta Grossa, Parana State, on a Typic Hapludox. The treatments consisted of a control and three lime rates, surface applied to raise the base saturation to 50, 70, and 90%. Soil solution was obtained at soil water equilibrium (1:1 w/w soil/water ratio). The effects of surface liming on soil chemical attributes and on the composition of the soil solution were dependent on weather conditions, time under NTS, and soil weathering. Most Al in soil solution was complexed to DOC, representing about 70 to 80% of the total Al at pH <5.0, and about 30 to 4096 at pH >5.0. Under pH 5.5, the results were closely correlated with the solubility line for amorphous Al. Organic complexes may control Al(3+) release into soil solution at pH <5.5. Results suggest that in areas under NTS for a long period of time, Al toxicity might decrease due to its complexation to high-molecular-weight organic compounds.

Sodicity and salinity in a Brazilian Oxisol cultivated with sugarcane irrigated with wastewater

Changes in soil sodicity-salinity parameters are one of the most characteristic alterations after treated sewage effluent (TSE) irrigation in agro-systems. Considering the importance of these parameters for agricultural management, as well as the economical value of sugarcane for Brazil, the present study aimed at evaluating effects on soil sodicity and salinity under tropical conditions over 16 months of TSE irrigation in a sugarcane plantation at Lins, Sao Paulo State, Brazil. Soil samplings were carried out in February 2005 (before planting), December 2005 (after 8 months of TSE irrigation) and September 2006 (after 16 months of TSE irrigation) following a complete block design with four treatments and four replicates. Treatments consisted of. (i) control, without TSE irrigation; (ii) T100, T150 and T200, with TSE irrigation supplying 100% (0% surplus, total of 2524 mm), 150% (50% surplus, total of 3832 mm) and 200% (100% surplus, total of 5092 mm) of crop water demand, respectively. Compared to initial soil conditions, at the end of the experiment increases of exchangeable sodium (from 2.4 to 5.9 mmol(c) kg(-1)), exchangeable sodium percentage (ESP) (from 8 to 18%), soluble Na (from 1.4 to 4.7 mmol L(-1)) and sodium adsorption ratio (SAR) of soil solution (from 3.6 to 12.6 (mmol were found in the soil profile (0-100 cm) as an average for the irrigated plots due to high SAR of TSE. Associated with the increments were mostly significant increases in clay dispersion rates at depths 0-10, 10-20 and 20-40 cm. Electrical conductivity (EC) of soil solution increased during the TSE irrigation period whereas at the end of the experiment, after short term discontinuation of irrigation and harvest, EC in the topsoil (0-10 and 10-20 cm) decreased compared to the previous samplings. Moreover, despite increasing sodicity over time mainly insignificant differences within the different irrigated treatments were found in December 2005 and September 2006. This suggests that independent of varying irrigation amounts the increasing soil sodicity over time were rather caused by the continuous use of TSE than by its quantity applied. Moreover, also plant productivity showed no significant differences within the TSE irrigated plots. The study indicates that monitoring as well as remediation of soil after TSE irrigation is required for a sustainable TSE use in order to maintain agricultural quality parameters. (C) 2008 Elsevier B.V. All rights reserved.

Runoff and leachate losses of phosphorus in a sandy spodosol amended with biosolids

Florida Spodosols axe sandy, inherently low in Fe- and Al-based minerals, and sorb phosphorus (P) poorly. We evaluated runoff and leachate P losses from a typical Florida Spodosol amended with biosolids and triple superphosphate (TSP). Phosphorus losses were evaluated with traditional indoor rainfall simulations but used a double-deck box arrangement that allowed leaching and runoff to be determined simultaneously. Biosolids (Lakeland, OCUD, Milorganite, and Disney) represented contrasting values of total P, percent water-extractable p (PWEP), and percentage of solids. All P sources were surface applied at 224 kg P ha(-1), representing a soil P rate typical of N-based biosolids application. All biosolids-P sources lost less P than TSp, and leachate-P losses generally dominated. For Lakeland-amended I soil, bioavailable P (BAP) was mainly lost by runoff (81% of total BAP losses). This behavior was due to surface scaling and 1 drying after application of the slurry (31 g kg(-1) solids), material. For all other P sources, BAP losses in leachate were much,greater than in runoff, representing 94% of total BAP losses for TSP, 80% for Milorganite, 72% for Disney, and 69% for OCUD treatments. Phosphorus leaching can be extreme and represents a great concern in many coarse-textured Florida Spodosols, and other coastal plain soils with low P-sorption,capacities. The PWEP values of P sources were significantly correlared with total P and BAP losses in runoff and leachate. The PWEP of a source can serve as a good indicator of potential P loss when amended to sandy soils with low P-retention capacities.

Components of Surface Charge in Tropical Soils With Contrasting Mineralogies

Study of surface electric charges of soil colloids helps in understanding the physicochemical phenomena that influence the capacity of retaining nutrients and their availability to plants. The structural charge (sigma(0), (min)), the variable charge (sigma(q, min)), and the organic matter (OM) charge (sigma(total) (OM)) of 12 tropical soils with contrasting mineralogies were evaluated based on the difference of selectivity for Cs(+) and Li(+) between the functional ionizable surfaces groups and the mineral 2:1 siloxane surface. Soils were divided into three groups: G1, soils with a predominance of kaolinite and gibbsite in the clay fraction; G2, soils with hydroxy-interlayered 2:1 minerals; and G3, soils with smectite but without hydroxy-interlayered 2:1 minerals. The Cs absorption method was efficient for detecting the charge components in tropical soils. The mineral structural charge contributed 11% and 16%, 28% and 31%, and 52% and 59% of total soil charge of A and B horizons of soils from groups G 1, G2, and G3, respectively. On the other hand, OM contributed 53% and 37%, 48% and 41%, and 21% and 20% of total charge for the same samples, respectively, In highly weathered soils of group G I and, to a lesser extent, in soils in group G2, surface charges depended mainly on their variable components, resulting from the OM (sigma(toal) (OM)), as well as from imperfections found in 1:1 minerals (sigma(q, min)). The importance of OM in determining the magnitude of electric charges in humid tropical soils is highlighted.

Chemical Composition and Antioxidant/Antidiabetic Potential of Brazilian Native Fruits and Commercial Frozen Pulps

Foods provide essential and bioactive compounds with health-promoting properties such as antioxidant, anti-inflammatory, and hypocholesterolemic activities, which have been related to vitamins A, C, and E and phenolic compounds such as flavonoids. Therefore, the aim of this work was to identify potential sources of bioactive compounds through the determination of flavonoids and ellagic acid contents and the in vitro antioxidant capacity and alpha-glucosidase and alpha-amylase inhibitory activities of Brazilian native fruits and commercial frozen pulps. Camu-camu, cambuci, uxi, and tucuma and commercial frozen pulps of cambuci, cagaita, coquinho azedo, and araca presented the highest antioxidant capacities. Cambuci and cagaita exhibited the highest alpha-glucosidase and alpha-amylase inhibitory activities. Quercetin and kaempferol derivatives were the main flavonoids present in most of the samples. Ellagic acid was detected only in umbu, camu-camu, cagaita, araca, and cambuci. According to the results, native Brazilian fruits can be considered as excellent sources of bioactive compounds.

Antioxidant capacity of Brazilian fruit, vegetables and commercially-frozen fruit pulps

Several epidemiological and research studies suggest that a high intake of foods rich in natural antioxidants increases the antioxidant capacity of the plasma and reduces the risk of some kinds of cancers, heart diseases, and stroke. These health benefits are attributed to a variety of constituents, including vitamins, minerals, fiber, and numerous phytochemicals, such as flavonoids. Thus, in addition to measuring the composition of the usual macronutrients and micronutrients, it seems important to also measure the antioxidant capacity of foods. For this purpose, 28 foods including fruits, vegetables and commercially-frozen fruit pulps were analyzed for antioxidant capacity. The antioxidant capacity of the foods varied from 0.73 to 19.8 mu mol BHT equiv/g. The highest values were observed for wild mulberries (19.8 mu mol BHT equiv/g), acai fruit pulp (18.2 mu mol BHT equiv/g) and watercress (9.6 mu mol BHT equiv/g). The antioxidant capacities are only indicative of the potential of the bioactive compounds; however, these data are important to explore and understand the role of fruit, vegetables and other foods in health promotion. (C) 2009 Elsevier Inc. All rights reserved.

Enterotoxigenic and genetic profiles of Bacillus cereus strains of food origin in Brazil

In Brazil. the incidence of Bacillus cereus outbreaks is unknown, and there is little information about B. cereus occurrence in food. In addition, data on toxin production and genetic characterization of the B. cereus isolates cannot be found. This pathogen causes two distinct types of toxin-mediated foodborne illnesses known as diarrheal and emetic syndromes. Diarrheal syndrome has been linked to three different enterotoxins: two protein complexes, hemolysin BL (HBL) and nonhemolytic enterotoxin (NHE); and an enterotoxic protein, cytotoxin K (cytK). Emetic syndrome is related to cereulide, a toxin encoded by the ces gene. In this study, NHE and HBL production capacities of 155 strains of B. cereus isolated from Brazilian food products were evaluated with an immunoassay. Strains were also tested for the presence of the genes of the HBL and NHE complexes, cytK, cytK-1, cytK-2, and ces, using PCR. HBL was detected in 105 (67.7%) strains and NHE in 154 (99.4%) strains. All the strains harbored at least one gene of the NHE complex, while 96.1% of them were positive for at least one of those of the HBL complex. Genes cytK1 and ces were not detected. All strains showed toxigenic capacity and could represent a risk for consumers if good practices are not followed. This is the first report on toxigenic and genetic profiles of B. cereus strains isolated in Brazil.

Attainment and Characterization of Ternary Complexes of Simvastatin-Cyclodextrin-Hydrossoluble Polymers

The purpose of this study was to attain and characterize ternary complexes of simvastatin, beta-cyclodextrin (beta CD) and different polymers, and then select those that lead to a greater increase in drug solubility. The complexes were prepared with the co-evaporation method and the polymers used were polyethylene glycol 1500, polyethylene glycol 4000, povidone, copovidone, crospovidone, maltodextrin and hydroxypropyl methyl cellulose. The characterization of complexes was carried out through aqueous solubility, DSC and TG. There was an increase in solubility for all the complexes prepared with beta CD and the different polymers, but only when crospovidone and maltodextrin were used was there a significant difference observed between the solubility of the physical mixture and that of the complex. The DSC curves indicate that the non-complexed drug is even in the sample of the complex with higher solubility, thus none of the polymers was able to achieve a total complexation of the drug.