Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

Síntese de zeólitas e argilas ácidas pilarizadas a partir de matérias primas naturais

Structural changes in waste for zeolites synthesis are subject of many studies carried out in the synthesis of molecular sieves. These materials are named molecular sieves because they have well defined pore sizes and they have the capacity of select molecules by its size. In this work, it was studied the synthesis processes of two types of molecular sieves: pillared acid clays using as starting material one natural montmorillonite clay and the synthesis of zeolites from a silico-aluminous residue. This residue is a byproduct of the extraction of lithium -spodumene. The preparation of pillared acid clays was performed in two steps: 1° acid treatment of clay samples (time and temperature studies) and 2°pilarization of them with Al13 (Keggin ion). The temperature and acid concentration affect the removal of cations in the structure and porosity of the material obtained. The analysis of X-ray diffraction (XRD) and infrared spectroscopy (IR), showed that increasing the severity of the acid treatment compromises the structural material. Also the pore size distribution is approximately uniform. Despite presenting a structural disorganization, the samples were pillared. As evidenced by XRD increasing the basal spacing, specific area and uniform porosity by adsorption of N2. Regarding the microporous molecular sieves were synthesized zeolites A and NaP1 from a silico-aluminous residue, a byproduct of extracting lithium. The temperature and time of agitation during the synthesis were the most important factors for obtaining zeolite A. The aging of the gel and the highest crystallization time promoted the formation of zeolite NaP1 using a Si / Al ratio = 3.2

Porous solids from layered clays by combined pillaring and templating approaches

The pore structure formation in bentonite, pillared with a mixed sol of silicon and titanium hydroxides and treated subsequently with quaternary ammonium surfactants, is investigated. The surfactant micelles act as a template, similar to their role in MCM41 synthesis. Because both the surfactant micelles and the sol particles are positively charged, it is greatly favorable for them to form meso-phase assembles in the galleries between the clay layers that bear negative charges. Besides, the sol particles do not bond the clay layers strongly as other kinds of pillar precursors do, so that the treatment with surfactants can result in radical structure changes in sol-pillared clays. This allows us to tailor the pore structure of these porous clays by choice of surfactant. The surfactant treatment also results in profound increases in porosity and improvement in thermal stability. Therefore, the product porous clays have great potential to be Used to deal with large molecules or at high operating temperatures. We also found that titanium in these samples is highly dispersed in the silica matrix rather than existing in the form of small particles of pure titania. Such highly dispersed Ti active centers may offer excellent activities for catalytic oxidation reactions such as alkanes into alcohols and ketones.

Comparison between computational alanine scanning and per-residue binding free energy decomposition for protein-protein association using MM-GBSA: application to the TCR-p-MHC complex.

Recognition by the T-cell receptor (TCR) of immunogenic peptides (p) presented by Class I major histocompatibility complexes (MHC) is the key event in the immune response against virus-infected cells or tumor cells. A study of the 2C TCR/SIYR/H-2K(b) system using a computational alanine scanning and a much faster binding free energy decomposition based on the Molecular Mechanics-Generalized Born Surface Area (MM-GBSA) method is presented. The results show that the TCR-p-MHC binding free energy decomposition using this approach and including entropic terms provides a detailed and reliable description of the interactions between the molecules at an atomistic level. Comparison of the decomposition results with experimentally determined activity differences for alanine mutants yields a correlation of 0.67 when the entropy is neglected and 0.72 when the entropy is taken into account. Similarly, comparison of experimental activities with variations in binding free energies determined by computational alanine scanning yields correlations of 0.72 and 0.74 when the entropy is neglected or taken into account, respectively. Some key interactions for the TCR-p-MHC binding are analyzed and some possible side chains replacements are proposed in the context of TCR protein engineering. In addition, a comparison of the two theoretical approaches for estimating the role of each side chain in the complexation is given, and a new ad hoc approach to decompose the vibrational entropy term into atomic contributions, the linear decomposition of the vibrational entropy (LDVE), is introduced. The latter allows the rapid calculation of the entropic contribution of interesting side chains to the binding. This new method is based on the idea that the most important contributions to the vibrational entropy of a molecule originate from residues that contribute most to the vibrational amplitude of the normal modes. The LDVE approach is shown to provide results very similar to those of the exact but highly computationally demanding method.

Carbon balance and crop residue management in dynamic equilibrium under a no-till system in Campos Gerais

The adoption of no-tillage systems (NT) and the maintenance of crop residues on the soil surface result in the long-term increase of carbon (C) in the system, promoting C sequestration and reducing C-CO2 emissions to the atmosphere. The purpose of this study was to evaluate the C sequestration rate and the minimum amount of crop residues required to maintain the dynamic C equilibrium (dC/dt = 0) of two soils (Typic Hapludox) with different textural classes. The experiment was arranged in a 2 x 2 x 2 randomized block factorial design. The following factors were analyzed: (a) two soil types: Typic Hapludox (Oxisol) with medium texture (LVTM) and Oxisol with clay texture (LVTA), (b) two sampling layers (0-5 and 5-20 cm), and (c) two sampling periods (P1 - October 2007; P2 - September 2008). Samples were collected from fields under a long-term (20 years) NT system with the following crop rotations: wheat/soybean/black oat + vetch/maize (LVTM) and wheat/maize/black oat + vetch/soybean (LVTA). The annual C sequestration rates were 0.83 and 0.76 Mg ha-1 for LVTM and LVTA, respectively. The estimates of the minimum amount of crop residues required to maintain a dynamic equilibrium (dC/dt = 0) were 7.13 and 6.53 Mg ha-1 year-1 for LVTM and LVTA, respectively. The C conversion rate in both studied soils was lower than that reported in other studies in the region, resulting in a greater amount of crop residues left on the soil surface.

EFFECT OF SOIL TILLAGE AND PLANT RESIDUE ON SURFACE ROUGHNESS OF AN OXISOL UNDER SIMULATED RAIN

Surface roughness of the soil is formed by mechanical tillage and is also influenced by the kind and amount of plant residue, among other factors. Its persistence over time mainly depends on the fundamental characteristics of rain and soil type. However, few studies have been developed to evaluate these factors in Latossolos (Oxisols). In this study, we evaluated the effect of soil tillage and of amounts of plant residue on surface roughness of an Oxisol under simulated rain. Treatments consisted of the combination of the tillage systems of no-tillage (NT), conventional tillage (CT), and minimum tillage (MT) with rates of plant residue of 0, 1, and 2 Mg ha-1 of oats (Avena strigosa Schreb) and 0, 3, and 6 Mg ha-1 of maize (Zea mays L.). Seven simulated rains were applied on each experimental plot, with intensity of 60±2 mm h-1 and duration of 1 h at weekly intervals. The values of the random roughness index ranged from 2.94 to 17.71 mm in oats, and from 5.91 to 20.37 mm in maize, showing that CT and MT are effective in increasing soil surface roughness. It was seen that soil tillage operations carried out with the chisel plow and the leveling disk harrow are more effective in increasing soil roughness than those carried out with the heavy disk harrow and leveling disk harrow. The roughness index of the soil surface decreases exponentially with the increase in the rainfall volume applied under conditions of no tillage without soil cover, conventional tillage, and minimum tillage. The oat and maize crop residue present on the soil surface is effective in maintaining the roughness of the soil surface under no-tillage.

Soil and crop residue CO2-C emission under tillage systems in sugarcane-producing areas of southern Brazil

Appropriate management of agricultural crop residues could result in increases on soil organic carbon (SOC) and help to mitigate gas effect. To distinguish the contributions of SOC and sugarcane (Saccharum spp.) residues to the short-term CO2-C loss, we studied the infl uence of several tillage systems: heavy offset disk harrow (HO), chisel plow (CP), rotary tiller (RT), and sugarcane mill tiller (SM) in 2008, and CP, RT, SM, moldboard (MP), and subsoiler (SUB) in 2009, with and without sugarcane residues relative to no-till (NT) in the sugarcane producing region of Brazil. Soil CO2-C emissions were measured daily for two weeks after tillage using portable soil respiration systems. Daily CO2-C emissions declined after tillage regardless of tillage system. In 2008, total CO2-C from SOC and/or residue decomposition was greater for RT and lowest for CP. In 2009, emission was greatest for MP and CP with residues, and smallest for NT. SOC and residue contributed 47% and 41%, respectively, to total CO2-C emissions. Regarding the estimated emissions from sugarcane residue and SOC decomposition within the measurement period, CO2-C factor was similar to sugarcane residue and soil organic carbon decomposition, depending on the tillage system applied. Our approach may define new emission factors that are associated to tillage operations on bare or sugarcane-residue-covered soils to estimate the total carbon loss.

(Table 1) Calcium carbonate and <2 µm fractions of bulk sample and insoluble residue at DSDP Hole 92-597

Particles of red brown to yellow brown semiopaque oxides (RSO) dominate the insoluble residue fraction of the sediments at Site 597. Unlike the X-ray amorphous particles in the Bauer Deep sediments, these particles are composed of mainly goethite; the amount of X-ray amorphous ferric hydroxide and poorly crystalline ferromanganese oxyhydroxides is generally small relative to the amount of goethite. A qualitative goethite crystallinity index was established. The variations observed in the crystallinity of goethite with increasing depth and changes in lithology suggest that aging and long-term exposure to seawater in a high water/sediment regime influence and increase the rate of recrystallization of the Fe-oxyhydroxides of the RSO particles. The percentage of organic carbon is low in these sediments; it varies primarily between 0.2 and 0.4 wt.%. Phillipsite is present throughout the sediment column and is more concentrated in the youngest clay layer and in the oldest basal sediments.

Simulation of sugarcane residue decomposition and aboveground growth

Due to the worldwide increase in demand for biofuels, the area cultivated with sugarcane is expected to increase. For environmental and economic reasons, an increasing proportion of the areas are being harvested without burning, leaving the residues on the soil surface. This periodical input of residues affects soil physical, chemical and biological properties, as well as plant growth and nutrition. Modeling can be a useful tool in the study of the complex interactions between the climate, residue quality, and the biological factors controlling plant growth and residue decomposition. The approach taken in this work was to parameterize the CENTURY model for the sugarcane crop, to simulate the temporal dynamics of aboveground phytomass and litter decomposition, and to validate the model through field experiment data. When studying aboveground growth, burned and unburned harvest systems were compared, as well as the effect of mineral fertilizer and organic residue applications. The simulations were performed with data from experiments with different durations, from 12 months to 60 years, in Goiana, TimbaA(0)ba and Pradpolis, Brazil; Harwood, Mackay and Tully, Australia; and Mount Edgecombe, South Africa. The differentiation of two pools in the litter, with different decomposition rates, was found to be a relevant factor in the simulations made. Originally, the model had a basically unlimited layer of mulch directly available for decomposition, 5,000 g m(-2). Through a parameter optimization process, the thickness of the mulch layer closer to the soil, more vulnerable to decomposition, was set as 110 g m(-2). By changing the layer of mulch at any given time available for decomposition, the sugarcane residues decomposition simulations where close to measured values (R (2) = 0.93), contributing to making the CENTURY model a tool for the study of sugarcane litter decomposition patterns. The CENTURY model accurately simulated aboveground carbon stalk values (R (2) = 0.76), considering burned and unburned harvest systems, plots with and without nitrogen fertilizer and organic amendment applications, in different climates and soil conditions.

Structural tuning of Montmorillonite clays by pillaring: Designing of shape selective solid acid catalysts and PANI - Montmorillonite nanocomposites

Green chemistry boots eco-friendly,natural clays as catalysts in the chemical as well as in the pharmaceutical industry.Industry demands thermal stability,mechanical strength etc for the catalyst and there the modification methods becomes important.Pillaring tunes clays as efficient catalytic templates for shape selective organic synthesis.Here pillared clays are used as promising alternatives for the environmentally hazardous homogeneous catalysts in some industrially important Friedel-Crafts alkylation reactions of arenes with lower alchohols and higher olefins.The layer structure is enhanced upon pillaring and allows the nanocomposite formation with polyaniline to develop today’s nanoscale diameter devices.Present work gives an entry of pillared clays to the world of conducting composite nanofibers.

Association between pharyngeal residue and posterior oral spillage with penetration and aspiration in Stroke

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Residue-specific investigation of the relationship between oxidation and activity of a dual specificity phosphatase by mass spectrometry

Redox regulation of signalling pathways is critical in proliferation and apoptosis; redox imbalance can lead to pathologies such as inflammation and cancer. Vaccinia H1-related protein (VHR; DUSP3) is a dual-specificity phosphatase important in controlling MAP kinase activity during cell cycle. the active-site motif contains a cysteine that acts as a nucleophile during catalysis. We used VHR to investigate the effect of oxidation in vitro on phosphatase activity, with the aim of determining how the profile of site-specific modification related to catalytic activity. Recombinant human VHR was expressed in E. coli and purified using a GST-tag. Protein was subjected to oxidation with various concentrations of SIN-1 or tetranitromethane (TNM) as nitrating agents, or HOCl. the activity was assayed using either 3-O-methylfluorescein phosphate with fluorescence detection or PIP3 by phosphate release with malachite green. the sites of oxidation were mapped using HPLC coupled to tandem mass spectrometry on an ABSciex 5600TripleTOF following in-gel digestion. More than 25 different concentration-dependent oxidative modifications to the protein were detected, including oxidations of methionine, cysteine, histidine, lysine, proline and tyrosine, and the % oxidized peptide (versus unmodified peptide) was determined from the extracted ion chromatograms. Unsurprisingly, methionine residues were very susceptible to oxidation, but there was a significant different in the extent of their oxidation. Similarly, tyrosine residues varied greatly in their modifications: Y85 and Y138 were readily nitrated, whereas Y38, Y78 and Y101 showed little modification. Y138 must be phosphorylated for MAPK phosphatase activity, so this susceptibility impacts on signalling pathways. Di- and tri- oxidations of cysteine residues were observed, but did not correlate directly with loss of activity. Overall, the catalytic activity did not correlate with redox state of any individual residue, but the total oxidative load correlated with treatment concentration and activity. This study provides the first comprehensive analysis of oxidation modifications of VHR, and demonstrates both heterogenous oxidant effects and differential residue susceptibility in a signalling phosphatase.

Method development for the analysis of smokeless powders and organic gunshot residue by ultra performance liquid chromatography with tandem mass spectrometry

The goal of this project was to develop a rapid separation and detection method for analyzing organic compounds in smokeless powders and then test its applicability on gunshot residue (GSR) samples. In this project, a total of 20 common smokeless powder additives and their decomposition products were separated by ultra performance liquid chromatography (UPLC) and confirmed by tandem mass spectrometry (MS/MS) using multiple reaction monitoring mode (MRM). Some of the targeted compounds included diphenylamines, centralites, nitrotoluenes, nitroglycerin, and various phthalates. The compounds were ionized in the MS source using simultaneous positive and negative electrospray ionization (ESI) with negative atmospheric pressure chemical ionization (APCI) in order to detect all compounds in a single analysis. The developed UPLC/MS/MS method was applied to commercially available smokeless powders and gunshot residue samples recovered from the hands of shooters, spent cartridges, and smokeless powder retrieved from unfired cartridges. Distinct compositions were identified for smokeless powders from different manufacturers and from separate manufacturing lots. The procedure also produced specific chemical profiles when tested on gunshot residues from different manufacturers. Overall, this thesis represents the development of a rapid and reproducible procedure capable of simultaneously detecting the widest possible range of components present in organic gunshot residue.^

Determination of pindolol enantiomers in human plasma and urine by simple liquid-liquid extraction and high-performance liquid chromatography

A simple method for the measurement of pindolol enantiomers by HPLC is presented. Alkalinized serum or urine is extracted with ethyl acetate and the residue remaining after evaporation of the organic layer is then derivatised with (S)-(-)-alpha-methylbenzyl isocyanate. The diastereoisomers of derivatised pindolol and metoprolol (internal standard) are separated by high-performance liquid chromatography (HPLC) using a C-18 silica column and detected using fluorescence (excitation lambda: 215 nm, emission lambda: 320 nm). The assay displays reproducible linearity for pindolol enantiomers with a correlation coefficient of r(2) greater than or equal to 0.998 over the concentration range 8-100 ng ml(-1) for plasma and 0.1-2.5 mu g ml(-1) for urine. The coefficient of variation for accuracy and precision of the quality control samples for both plasma and urine are consistently