Síntese e atividade anti-HCV, anti-candida e antibacteriana de nitrochalconas

Pós-graduação em Química - IBILCE

Pré-tratamento do bagaço de cana-de-açúcar, hidrólise e sua caracterização química e estrutural, visando a produção de etanol de segunda geração

Pós-graduação em Biotecnologia - IQ

Obtenção e caracterização de nanocelulose a partir de fibras de Chorisia speciosa St. Hil

Natural fibers have been highlighted as a renewable material that can replace materials from oil and its derivatives. In this context, Brazil becomes the perfect setting because of the diversity of fibers found in its territory, such as sugarcane, sisal, rice, cotton, coconut, pineapple, among others. The paineiras (Chorisia speciosa St. Hil) are typically Brazilian trees, which produce paina as fruit. These fruits are still little studied as a source of lignocellulose by research groups. This project aimed obtaining and characterization of cellulose nanofibers from the fibers from the paina fibers. Obtaining nanocellulose is practically made through simplified chemical processes. First, was performed out pre-treatments to removal of waxes, lignin and hemicellulose. The first stage of pre-treatment was carried out by alkaline aqueous solution of sodium hydroxide (NaOH) at 5wt%, where the fibers were under constant agitation for 1h at 70°C. Through alkali treatment it was possible to remove most of the lignin, hemicellulose, waxes and extractives. After the alkaline treatment was done bleaching with an aqueous solution of sodium hydroxide (NaOH) to 4wt% and hydrogen peroxide (H2O2) to 24wt% 1:1 during 2h with constant stirring to 50 °C. Through bleaching was possibe to remove residual lignin, and got cellulose with 72% of crystallinity. Nanocellulose of paina fibers was extracted using different conditions of acid hydrolysis with sulfuric acid (H2SO4) to 50wt%. After acid hydrolysis, the suspensions were centrifuged during 30 min and dialyzed in water to remove excess acid until neutral pH (6-7). Then the suspensions were passed by ultrasonification in an ultrasound 20 kHz during 1h in an ice bath. Untreated, alkalinized and bleached fibers as well as cellulose nanoparticles were characterized by the techniques of thermogravimetry ... (Complete abastract click electronic access below)

RB30-246 Testing Ice Cream for Butterfat

Butterfat is usually the most expensive ingredient of ice cream; hence, great care is necessary in controllng its use. The manufacturer of ice cream, whether doing a large or a small volume of business, must manufacture a product that will comply with the established fat standard. Some means of determining the percentage of butterfat in the product must be available in order to establish this control. This 1930 research bulletin discusses the different testing equipment used to test butterfat in ice cream.

Phytoplankton Dynamics in Three Rocky Mountain Lakes, Colorado, U.S.A.

In 1984 and 1985 seasonal changes in phytoplankton were studied in a system of three lakes in Loch Vale, Rocky Mountain National Park, Colorado. Three periods were evident: (1) A spring bloom, during snowmelt, of the planktonic diatom Asterionella Formosa, (2) a mid- summer period of minimal algal abundance, and (3) a fall bloom of the blue-green alga Oscillatoria limnetica. Seasonal phytoplankton dynamics in these lakes are controlled partially by the rapid flushing rate during snowmelt and the transport of phytoplankton from the highest lake to the lower lakes by the stream, Icy Brook. During snowmelt, the A. formosa population in the most downstream lake has a net rate of increase of 0.34 d-1, which is calculated from the flushing rate and from the A. formosa abundance in the inflow from the upstream lake and in the downstream lake. Measurement of photosynthetic rates at different depths during the three periods confirmed the rapid growth of A. formosa during the spring. The decline in A. formosa after snowmelt may be related to grazing by developing zooplankton populations. The possible importance of the seasonal variations in nitrate concentrations were evaluated in situ enrichment experiments. For A. formosa and O. limnetica populations, growth stimulation resulted from 8- or 16-micromolar amendments of calcium nitrate and sulfuric acid, but the reason for this stimulation could not be determined from these experiments.

Obtenção e caracterização de nanocelulose a partir de fibras de Chorisia speciosa St. Hil

Natural fibers have been highlighted as a renewable material that can replace materials from oil and its derivatives. In this context, Brazil becomes the perfect setting because of the diversity of fibers found in its territory, such as sugarcane, sisal, rice, cotton, coconut, pineapple, among others. The paineiras (Chorisia speciosa St. Hil) are typically Brazilian trees, which produce paina as fruit. These fruits are still little studied as a source of lignocellulose by research groups. This project aimed obtaining and characterization of cellulose nanofibers from the fibers from the paina fibers. Obtaining nanocellulose is practically made through simplified chemical processes. First, was performed out pre-treatments to removal of waxes, lignin and hemicellulose. The first stage of pre-treatment was carried out by alkaline aqueous solution of sodium hydroxide (NaOH) at 5wt%, where the fibers were under constant agitation for 1h at 70°C. Through alkali treatment it was possible to remove most of the lignin, hemicellulose, waxes and extractives. After the alkaline treatment was done bleaching with an aqueous solution of sodium hydroxide (NaOH) to 4wt% and hydrogen peroxide (H2O2) to 24wt% 1:1 during 2h with constant stirring to 50 °C. Through bleaching was possibe to remove residual lignin, and got cellulose with 72% of crystallinity. Nanocellulose of paina fibers was extracted using different conditions of acid hydrolysis with sulfuric acid (H2SO4) to 50wt%. After acid hydrolysis, the suspensions were centrifuged during 30 min and dialyzed in water to remove excess acid until neutral pH (6-7). Then the suspensions were passed by ultrasonification in an ultrasound 20 kHz during 1h in an ice bath. Untreated, alkalinized and bleached fibers as well as cellulose nanoparticles were characterized by the techniques of thermogravimetry ... (Complete abastract click electronic access below)

Saccharification of Brazilian sisal pulp: evaluating the impact of mercerization on non-hydrolyzed pulp and hydrolysis products

Cultivation of sisal, a plant with a short growth cycle, is highly productive in Brazil. This work is part of extensive research in which sisal is valued. In these studies, sisal fibers are used in the preparation of bio-based composites and in the derivatization of the pulp, including posterior preparation of films. This study aimed to examine the use of sisal pulp in the production of bioethanol, which can potentially be a high efficiency process because of the cellulose content of this fiber. A previous paper addressed the hydrolysis of sisal pulp using sulfuric acid as a catalyst. In the present study, the influence of the mercerization process on the acid hydrolysis of sisal pulp was evaluated. Mercerization was achieved in a 20% wt NaOH solution, and the cellulosic pulp was suspended and vigorously mixed for 1, 2 and 3 h, at 50 A degrees C. The previously characterized mercerized pulps were hydrolyzed (100 A degrees C, 30% H2SO4, v/v), and the results are compared with those obtained for unmercerized pulp (described in a companion paper). The starting sample was characterized by viscometry, alpha-cellulose content, crystallinity index and scanning electron microscopy. During the reactions, aliquots were withdrawn, and the liquor was analyzed by HPLC. The residual pulps (non-hydrolyzed) were also characterized by the techniques described for the initial sample. The results revealed that pretreatment decreases the polyoses content as well as causes a decrease of up to 23% in the crystallinity and up to 21% in the average molar mass of cellulose after 3 h of mercerization. The mercerization process proved to be very important to achieve the final target. Under the same reaction conditions (30% and 100 A degrees C, 6 h), the hydrolysis of mercerized pulp generated yields of up to 50% more glucose. The results of this paper will be compared with the results of subsequent studies obtained using other acids, and enzymes, as catalysts.

Influence of Modifications to the Pechini Method on the Electroactivity and Stability of Pt-RuOx/C Catalysts

Since electrode electroactivity and stability depend directly on the nature, morphology, and structure of the material, we have investigated how modifications to the Pechini method during the synthesis of Pt-RuOx/C electrocatalysts affected catalyst activity. The structure and stability of the resulting materials were investigated after their submission to a large number of potential scans and to constant potential for a prolonged time period in sulfuric acid 0.5 mol L-1 and methanol 0.1 mol L-1 solution. DMFC tests were accomplished using membrane electrode assemblies (MEAs) prepared by hot-pressing a pretreated Nafion 117 membrane together with the prepared Pt-RuOx anodes and a Pt cathode (from E-TEK), in order to compare the catalytic activity of the materials prepared by different methods. The stability studies demonstrated that the catalyst whose resin/carbon support mixture was agitated in a balls mill before undergoing heat-treatment was more stable than the other prepared catalysts. The catalysts synthesized with the single resin consisting of Pt and Ru and subjected to ultrasound before heat-treatment furnished the highest power density in the single fuel cell. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.011208jes]

On the diurnal cycle of urban aerosols, black carbon and the occurrence of new particle formation events in springtime Sao Paulo, Brazil

Large conurbations are a significant source of the anthropogenic pollution and demographic differences between cities that result in a different pollution burden. The metropolitan area of Sao Paulo (MASP, population 20 million) accounts for one fifth of the Brazilian vehicular fleet. A feature of MASP is the amount of ethanol used by the vehicular fleet, known to exacerbate air quality. The study describes the diurnal behaviour of the submicron aerosol and relies on total particle number concentration, particle number size distribution, light scattering and light absorption measurements. Modelled planetary boundary layer (PBL) depth and air mass movement data were used to aid the interpretation. During morning rush-hour, stagnant air and a shallow PBL height favour the accumulation of aerosol pollution. During clear-sky conditions, there was a wind shift towards the edge of the city indicating a heat island effect with implications on particulate pollution levels at the site. The median total particle number concentration for the submicron aerosol typically varied in the range 1.6 x 10(4)-3.2 x 10(4) cm(-3) frequently exceeding 4 x 10(4) cm-3 during the day. During weekdays, nucleation-mode particles are responsible for most of the particles by numbers. The highest concentrations of total particle number concentrations and black carbon (BC) were observed on Fridays. Median diurnal values for light absorption and light scattering (at 637 nm wavelength) varied in the range 12-33 Mm(-1) and 21-64 Mm(-1), respectively. The former one is equal to 1.8-5.0 mu g m(-3) of BC. The growth of the PBL, from the morning rush-hour until noon, is consistent with the diurnal cycle of BC mass concentrations. Weekday hourly median single-scattering albedo (omega(0)) varied in the range 0.59-0.76. Overall, this suggests a top of atmosphere (TOA) warming effect. However, considering the low surface reflectance of urban areas, for the given range of omega(0), the TOA radiative forcing can be either positive or negative for the sources within the MASP. On the average, weekend omega(0) values were 0.074 higher than during weekdays. During 11% of the days, new particle formation (NPF) events occurred. The analysed events growth rates ranged between 9 and 25 nm h(-1). Sulphuric acid proxy concentrations calculated for the site were less than 5% of the concentration needed to explain the observed growth. Thus, other vapours are likely contributors to the observed growth.

Synthesis of high-surface-area gamma-Al2O3 from aluminum scrap and its use for the adsorption of metals: Pb(II), Cd(II) and Zn(II)

Several types of alumina were synthesized from sodium aluminate (NaAlO2) by precipitation with sulfuric acid (H2SO4) and subsequently calcination at 500 degrees C to obtain gamma-Al2O3. The precursor aluminate was derived from aluminum scrap. The various gamma-Al2O3 synthesized were characterized by Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), adsorption-desorption of N-2 (S-BET) and scanning electron microscopy (SEM). XRD revealed that distinct phases of Al2O3 were formed during thermal treatment. Moreover, it was observed that conditions of synthesis (pH, aging time and temperature) strongly affect the physicochemical properties of the alumina. A high-surface-area alumina (371 m(2) g(-1)) was synthesized under mild conditions, from inexpensive raw materials. These aluminas were tested for the adsorption of Cd(II), Zn(II) and Pb(II) from aqueous solution at toxic metal concentrations, and isotherms were determined. (C) 2012 Elsevier B.V. All rights reserved.

Sequential extraction of phosphorus in an Oxisol amended with biosolids in a long-term field experiment in Brazil

The continued growth of large cities is producing increasing volumes of urban sewage sludge. Disposing of this waste without damaging the environment requires careful management. The application of large quantities of biosolids (treated sewage sludge) to agricultural lands for many years may result in the excessive accumulation of nutrients like phosphorus (P) and thereby raise risks of eutrophication in nearby water bodies. We evaluated the fractionation of P in samples of an Oxisol collected as part of a field experiment in which biosolids were added at three rates to a maize (Zea mays L) plantation over four consecutive years. The biosolids treatments were equivalent to one, two and four times the recommended N rate for maize crops. In a fourth treatment, mineral fertilizer was applied at the rate recommended for maize. Inorganic P forms were extracted with ammonium chloride to remove soluble and loosely bound P; P bound to aluminum oxide (P-Al) was extracted with ammonium fluoride; P bound to iron oxide (P-Fe) was extracted with sodium hydroxide; and P bound to calcium (P-Ca) was extracted with sulfuric acid. Organic P was calculated as the difference between total P and inorganic P. The predominant fraction of P was P-Fe, followed by P-Al and P-Ca. P fractions were positively correlated to the amounts of P applied, except for P-Ca. The low values of P-Ca were due to the advanced weathering processes to which the Oxisol have been subjected, under which forms of P-Ca are converted to P-Fe and P-Al. The fertilization with P via biosolids increased P availability for maize plants even when a large portion of P was converted to more stable forms. Phosphorus content in maize leaves and grains was positively correlated with P fractions in soils. From these results it can be concluded that the application of biosolids in highly weathered tropical clayey soils for many years, even above the recommended rate based on N requirements for maize, tend to be less potentially hazardous to the environment than in less weathered sandy soils because the non-readily P fractions are predominant after the addition of biosolids. (C) 2012 Elsevier B.V. All rights reserved.

SUPERAÇÃO DE DORMÊNCIA DAS SEMENTES E CONTROLE QUÍMICO DE Momordicacharantia L.

Objetivou-se com este estudo avaliar diferentes métodos para a superação da dormência das sementes e a eficiência de herbicidas no controle químico de plantas de Momordicacharantia L. no estádio reprodutivo. O primeiro experimento constituiu-seem esquema fatorial 2 x 8 (duas épocas de coleta das sementes (2006 e 2007) e oito métodos de quebra de dormência: escarificação mecânica; imersão em ácido sulfúrico concentrado e a 50%; imersão em nitrato de potássio a 2%por três e seis horas; calor seco a 60°C; água quente a 60°C e uma testemunha sem tratamento). No segundo ensaio avaliou-se o controle da Momordicacharantia L. por meio de seis herbicidas distintos: Imazapic, Metsulfuron-methyl, Metribuzin, 2,4-D, Amicarbazone, Paraquat e uma testemunha sem aplicação de herbicidas. Em ambos os ensaios, o delineamento experimental utilizado foi o inteiramente casualizados, com quatro repetições. Após a aplicação dos tratamentos,pode-se concluir que a imersão das sementes em ácido sulfúrico concentrado por 3 minutos proporcionou uma maior porcentagem e velocidade de germinação e que o herbicida Metribuzin alcançou, embora tardiamente, um controle total das plantas de melão de São-Caetano.

Using sulfur isotope fractionation to understand the atmospheric oxidation of SO 2

Sulfate aerosol plays an important but uncertain role in cloud formation and radiative forcing of the climate, and is also important for acid deposition and human health. The oxidation of SO2 to sulfate is a key reaction in determining the impact of sulfate in the environment through its effect on aerosol size distribution and composition. This thesis presents a laboratory investigation of sulfur isotope fractionation during SO2 oxidation by the most important gas-phase and heterogeneous pathways occurring in the atmosphere. The fractionation factors are then used to examine the role of sulfate formation in cloud processing of aerosol particles during the HCCT campaign in Thuringia, central Germany. The fractionation factor for the oxidation of SO2 by ·OH radicals was measured by reacting SO2 gas, with a known initial isotopic composition, with ·OH radicals generated from the photolysis of water at -25, 0, 19 and 40°C (Chapter 2). The product sulfate and the residual SO2 were collected as BaSO4 and the sulfur isotopic compositions measured with the Cameca NanoSIMS 50. The measured fractionation factor for 34S/32S during gas phase oxidation is αOH = (1.0089 ± 0.0007) − ((4 ± 5) × 10−5 )T (°C). Fractionation during oxidation by major aqueous pathways was measured by bubbling the SO2 gas through a solution of H2 O2

Global modeling of pollutant transport and deposition from anthropogenic emission hot spots on global scale

Urban centers significantly contribute to anthropogenic air pollution, although they cover only a minor fraction of the Earth's land surface. Since the worldwide degree of urbanization is steadily increasing, the anthropogenic contribution to air pollution from urban centers is expected to become more substantial in future air quality assessments. The main objective of this thesis was to obtain a more profound insight in the dispersion and the deposition of aerosol particles from 46 individual major population centers (MPCs) as well as the regional and global influence on the atmospheric distribution of several aerosol types. For the first time, this was assessed in one model framework, for which the global model EMAC was applied with different representations of aerosol particles. First, in an approach with passive tracers and a setup in which the results depend only on the source location and the size and the solubility of the tracers, several metrics and a regional climate classification were used to quantify the major outflow pathways, both vertically and horizontally, and to compare the balance between pollution export away from and pollution build-up around the source points. Then in a more comprehensive approach, the anthropogenic emissions of key trace species were changed at the MPC locations to determine the cumulative impact of the MPC emissions on the atmospheric aerosol burdens of black carbon, particulate organic matter, sulfate, and nitrate. Ten different mono-modal passive aerosol tracers were continuously released at the same constant rate at each emission point. The results clearly showed that on average about five times more mass is advected quasi-horizontally at low levels than exported into the upper troposphere. The strength of the low-level export is mainly determined by the location of the source, while the vertical transport is mainly governed by the lifting potential and the solubility of the tracers. Similar to insoluble gas phase tracers, the low-level export of aerosol tracers is strongest at middle and high latitudes, while the regions of strongest vertical export differ between aerosol (temperate winter dry) and gas phase (tropics) tracers. The emitted mass fraction that is kept around MPCs is largest in regions where aerosol tracers have short lifetimes; this mass is also critical for assessing the impact on humans. However, the number of people who live in a strongly polluted region around urban centers depends more on the population density than on the size of the area which is affected by strong air pollution. Another major result was that fine aerosol particles (diameters smaller than 2.5 micrometer) from MPCs undergo substantial long-range transport, with about half of the emitted mass being deposited beyond 1000 km away from the source. In contrast to this diluted remote deposition, there are areas around the MPCs which experience high deposition rates, especially in regions which are frequently affected by heavy precipitation or are situated in poorly ventilated locations. Moreover, most MPC aerosol emissions are removed over land surfaces. In particular, forests experience more deposition from MPC pollutants than other land ecosystems. In addition, it was found that the generic treatment of aerosols has no substantial influence on the major conclusions drawn in this thesis. Moreover, in the more comprehensive approach, it was found that emissions of black carbon, particulate organic matter, sulfur dioxide, and nitrogen oxides from MPCs influence the atmospheric burden of various aerosol types very differently, with impacts generally being larger for secondary species, sulfate and nitrate, than for primary species, black carbon and particulate organic matter. While the changes in the burdens of sulfate, black carbon, and particulate organic matter show an almost linear response for changes in the emission strength, the formation of nitrate was found to be contingent upon many more factors, e.g., the abundance of sulfuric acid, than only upon the strength of the nitrogen oxide emissions. The generic tracer experiments were further extended to conduct the first risk assessment to obtain the cumulative risk of contamination from multiple nuclear reactor accidents on the global scale. For this, many factors had to be taken into account: the probability of major accidents, the cumulative deposition field of the radionuclide cesium-137, and a threshold value that defines contamination. By collecting the necessary data and after accounting for uncertainties, it was found that the risk is highest in western Europe, the eastern US, and in Japan, where on average contamination by major accidents is expected about every 50 years.

The formation of OH radicals from Criegee intermediates: a LIF-FAGE study from laboratory to ambient

Das Hydroxyl Radikal ist, auf globalem Maßstab, das bedeutendste Oxidant in der Atmosphäre. Es initiiert den Abbauprozess vieler, teilweise schädlicher, Spurengase und insbesondere den von flüchtigen Kohlenwasserstoffen (VOC). Die OH Konzentration ist somit ein gutes Maß für die augenblickliche Selbstreinigungskapazität der Atmosphäre. Messungen zu nächtlicher Zeit mit LIF-FAGE-Instrumenten (engl.: laser-induced fluorescence - fluorescence assay by gas expansion) haben Konzentrationen des Hydroxylradikals (OH) ergeben, die signifikant höher waren, als sich mit der bekannten Chemie erklären ließ. Um herauszufinden, ob ein solches Signal wirklich atmosphärisches OH ist oder von einer störenden Spezies stammt, die im Messinstrument OH produziert, wurde das LIF-FAGE-Instrument des Max-Planck-Instituts für Chemie (MPIC) im Rahmen dieser Doktorarbeit modifiziert und getestet. Dazu wurde ein so genannter Inlet Pre-Injector (IPI) entwickelt, mit dem in regelmäßigen Abständen ein OH-Fänger in die Umgebungsluft abgegeben werden kann, bevor das OH vom Instrument erfasst wird. Mit dieser Technik ist es möglich, ein Hintergrund-OH (OHbg), d. h. ein im Instrument erzeugtes OH-Signal, vom gemessenen OH-Gesamtsignal (OHtot) zu trennen. Die Differenz zwischen OHtot und OHbg ist die atmosphärische OH-Konzentration (OHatm). Vergleichsmessungen mit der hier entwickelten Technik, dem IPI, in zwei verschiedenen Umgebungen mit Instrumenten basierend auf Massenspektrometrie mit chemischer Ionisation (CIMS, engl.: chemical ionization mass spectrometry) als alternativer Methode des OH-Nachweises, zeigten eine weitgehende Übereinstimmung. Eine umfassende Beschreibung des Systems zur Ermittlung der Ursache des OHbg hat ergeben, dass es weder von einem Artefakt des Instruments noch von hinlänglich bekannten und beschriebenen LIF-FAGE-Interferenzen stammt. Zur Bestimmung der Spezies, die das OHbg-Signal verursacht, wurden verschiedene Laborstudien durchgeführt. Die Arbeit im Rahmen dieser Doktorarbeit hat ergeben, dass das LIF-FAGE-Instrument leicht auf OH reagiert, das beim monomolekularen Zerfall stabilisierter Criegee-Intermediate (SCI) im Niederdruckbereich des Instruments gebildet wird. Criegee-Intermediate oder Carbonyloxide entstehen bei der Ozonolyse ungesättigter flüchtiger Kohlenwasserstoffverbindungen (VOC, engl.: volatile organic compounds) und können daher in der Umgebungsluft vorkommen. Anhand von Tests mit verschiedenen Verweilzeiten der SCI im Niederdruckbereich des Instruments in Verbindung mit einem detaillierten Modell mit der neuesten SCI-Chemie wurde die monomolekulare Zerfallsgeschwindigkeit von 20  10 s-1 für den syn-Acetaldehyd-Oxykonformer bestimmt. Der in Feldkampagnen gemessene OHbg-Wert wurde dahingehend untersucht, ob SCI die Quelle des beobachteten Hintergrund-OH im Feld sein könnten. Das Budget für die SCI-Konzentration, das für die Kampagnen HUMPPA-COPEC 2010 und HOPE 2012 berechnet wurde, ergab eine SCI-Konzentration zwischen ca. 103 und 106 Molekülen pro cm3. In der Kampagne HUMPPA-COPEC 2010 ergab die Schwefelsäurekonzentration, dass die OH-Oxidation von SO2 allein die gemessene H2SO4-Konzentration nicht erklären konnte. In dieser Arbeit konnte gezeigt werden, dass das Hintergrund-OH mit dieser ungeklärten Produktionsrate von H2SO4 korreliert und somit die Oxidation von SO2 durch SCI als mögliche Erklärung in Frage kommt. Ferner korreliert das Hintergrund-OH in der Kampagne HOPE 2012 mit dem Produkt aus Ozon und VOC und konnte mit SO2 als SCI Fänger entfernt werden. Qualitativ zeigen wir somit, dass das in der Umgebungsluft gemessene Hintergrund-OH wahrscheinlich durch den monomolekularen Zerfall von SCI verursacht wird, doch sind weitere Studien notwendig, um die quantitativen Beziehung für diese Spezies und dem Hintergrund-OH in unserem Instrument zu bestimmen.