Análise comparativa dos métodos MQL, MQL/Água e convencional na retificação cilíndrica do aço ABNT 52100, com rebolo de óxido de alumínio

Pós-graduação em Engenharia Mecânica - FEB

Avaliação do estresse oxidativo e atividade da δ-aminolevulínico desidratase em tecidos de tilápias do Nilo (Oreochromis niloticus) exposta a chumbo e benzo[a]pireno

Pós-graduação em Biologia Animal - IBILCE

25 kHz amorphous core transformer for induction heating applications

The analysis of the feasibility and economics of amorphous core power transformers for induction heating applications in the field 10-50 kHz is developped. The results obtained on a 25 kHz-150 kVA concentric winding trial unit are presented. © 1990.

Preparation of a clay-modified carbon paste electrode based on 2-thiazoline-2-thiol-hexadecylammonium sorption for the sensitive determination of mercury

A montmorillonite from Wyoming-USA was used to prepare an organo-clay complex, named 2-thiazoline-2-thiol-hexadecyltrimethylammonium-clay (TZT-HDTA-clay), for the purpose of the selective adsorption of the heavy metals ions and possible use as a chemically modified carbon paste electrode (CMCPE). Adsorption isotherms of Hg 2+, Pb 2+, Cd 2+, Cu 2+, and Zn 2+ from aqueous solutions as a function of the pH were studied at 298 K. Conditions for quantitative retention and elution were established for each metal by batch and column methods. The organo-clay complex was very selective to Hg(II) in aqueous solution in which other metals and ions were also present. The accumulation voltammetry of Hg(II) was studied at a carbon paste electrode chemically modified with this material. The mercury response was evaluated with respect to the pH, electrode composition, preconcentration time, mercury concentration, cleaning solution, possible interferences and other variables. A carbon paste electrode modified by TZT-HDTA-clay showed two peaks: one cathodic peak at about 0.0 V and an anodic peak at 0.25 V, scanning the potential from -0.2 to 0.8 V (0.05 M KNO 3 vs. Ag/AgCl). The anodic peak at 0.25 V presents excellent selectivity for Hg(II) ions in the presence of foreign ions. The detection limit was estimated as 0.1 μg L -1. The precision of determination was satisfactory for the respective concentration level. 2005 © The Japan Society for Analytical Chemistry.

Identificação e caracterização de metagenomas e isolados bacterianos visando a biorremediação de solos de áreas de mineração

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

ECODESIGN: designers brasileiros de adornos que trabalham com sustentabilidade

The ornaments have always been appreciated by human. And today is obviously the need to include the concepts of ecology in all areas. In this scenario ecodesign becomes a great ally for professionals who work in the making of ornaments, including jewelers. Aiming to decrease and the preservation of noble metals and the use of alternative materials, the ecodesign of adornment makes even more valued and attractive, it promotes sustainable consumption. Based on these concepts, this paper aims to investigate the Brazilian professionals who use sustainable ideas for making your accessories and social work related to this activity.

Efeitos da exposição gestacional a cádmio e dimetoato sobre o comportamento de ansiedade na prole de ratos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Comportamento materno e câncer de bexiga urinária: implicações da modulação de eixos hormonais e receptores de esteroides na fisiopatologia de lesões neoplásicas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Dissolução redutiva de minério de ferro por Acidithiobacillus ferrooxidans para a recuperação de metais de interesse econômico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Phytostabilisation : use of wetland plants to treat mine tailings

Mine tailings can be rich in sulphide minerals and may form acid mine drainage (AMD) through reaction with atmospheric oxygen and water. AMD contains elevated levels of metals and arsenic (As) that could be harmful to animals and plants. An oxygen-consuming layer of organic material and plants on top of water-covered tailings would probably reduce oxygen penetration into the tailings and thus reduce the formation of AMD. However, wetland plants have the ability to release oxygen through the roots and could thereby increase the solubility of metals and As. These elements are released into the drainage water, taken up and accumulated in the plant roots, or translocated to the shoots. The aim was to examine the effects of plant establishment on water-covered mine tailings by answering following questions: A) Is plant establishment on water-covered mine tailings possible? B) What are the metal and As uptake and translocation properties of these plants? C) How do plants affect metal and As release from mine tailings, and which are the mechanisms involved? Carex rostrata Stokes, Eriophorum angustifolium Honck., E. scheuchzeri Hoppe, Phragmites australis (Cav.) Steud., Salix phylicifolia L. and S. borealis Fr. were used as test plants. Influences of plants on the release of As, Cd, Cu, Pb, Zn and in some cases Fe in the drainage water, and plant element uptake were studied in greenhouse experiments and in the field. The results obtained demonstrate that plant establishment are possible on water-covered unweathered mine tailings, and a suitable amendment was found to be sewage sludge. On acidic, weathered tailings, a pH increasing substance such as ashes should be added to improve plant establishment. The metal and As concentrations of the plant tissue were found to be generally higher in roots than in shoots. The uptake was dependent on the metal and As concentrations of the tailings and the release of organic acids from plant roots may have influenced the uptake. The metal release from tailings into the drainage water caused by E. angustifolium was found to depend greatly on the age and chemical properties of the tailings. However, no effects of E. angustifolium on As release was found. Water from old sulphide-, metal- and As-rich tailings with low buffering capacity were positively affected by E. angustifolium by causing higher pH and lower metal concentrations. In tailings with relatively low sulphide, metal and As contents combined with a low buffering capacity, plants had the opposite impact, i.e. a reduction in pH and elevated metal levels of the drainage water. The total release of metal and As from the tailings, i.e. drainage water together with the contents in shoots and roots, was found to be similar for C. rostrata, E. angustifolium and P. australis, except for Fe and As, where the release was highest for P. australis. The differences in metal and As release from mine tailings were mainly found to be due to the release of O2 from the roots, which changes the redox potential. Release of organic acids from the roots slightly decreased the pH, although did not have any particular influence on the release of metal and As. In conclusion, as shown here, phytostabilisation may be a successful technique for remediation of mine tailings with high element and sulphide levels, and low buffering capacity.

Nuovi catalizzatori per l'idrogenazione, l'idrogenolisi/ring-opening di composti aromatici policiclici

The removal of aromatic hydrocarbons from diesel has received considerable attention after environmental regulations that require petroleum refiners to raise cetane number and to limit aromatics in diesel fuel in order to improve combustion efficiency and reduce particulate and NOx emissions. An alternative is blending with Fischer–Tropsch (FT) gas-to-liquid diesel fuel; however, this option may not be economically viable solution in case of extensive blend. Another alternative is to incorporate in the diesel pool a greater fraction of the so-called light cycle oil (LCO). Due to its high aromatics content and its low cetane number (typically between 20 and 30), the incorporation of LCO may have a negative impact on the quality of diesel. Current technologies for LCO improvement are based on hydrogenation to adjust both sulphur and cetane number but while an important fraction of the aromatics present in LCO can be saturated in a deep hydrogenation process, the cetane number may still be lower than the target values specified in diesel legislations, so further upgrading is needed. An interesting technology for improving the cetane number of diesels and maintaining meanwhile high diesel yields is achieved by combining a complete hydrogenation process with a selective ring opening (SRO) reaction of the naphthenic rings. The SRO can be defined as naphthene ring-opening to form compounds with high cetane number, but without any carbon losses. Controlling the interconversion of six- and five- membered rings via an acid-catalyzed ring-contraction step is also of great importance, since selective conversion of six-membered to five-membered naphthene rings greatly influences ring-opening rates and selectivity. High intrinsic activity may be enhanced by deposition of noble metals on acidic, high surface area supports, because it is possible to arrange close proximity of the metal and acid sites. Moreover, in large-pore supports, the diffusion resistance of liquid reactants into the pores is minimized. In addition to metal centres, the acid sites of support also plays role in aromatics hydrogenation. However, the functions of different kinds of acid sites (Brønsted vs. Lewis acidity), and their optimal concentrations and strengths, remain unclear. In the present study we investigated the upgrading of an aromatic-rich feedstock over different type of metal supported on mesoporous silica-alumina. The selective hydrogenolysis and ring opening of tetrahydronaphthalene (THN or tetralin) was carried out as representative of LCO fractions after deep hydrogenation process. In this regards the aim of this study is to evaluate both the effect of metals and that of the supports characterized by different acid distribution and strength, on conversion and selectivity. For this purpose a series of catalysts were prepared by impregnation. The catalysts were characterized and conversion tests of THN were performed in a lab-scale plant operating in the pressure range from 7.0-5.0 MPa and in the temperature range from 300 to 360°C.

Cluster-derived Gold/Iron catalysts for environmental applications

During the last years we assisted to an exponential growth of scientific discoveries for catalysis by gold and many applications have been found for Au-based catalysts. In the literature there are several studies concerning the use of gold-based catalysts for environmental applications and good results are reported for the catalytic combustion of different volatile organic compounds (VOCs). Recently it has also been established that gold-based catalysts are potentially capable of being effectively employed in fuel cells in order to remove CO traces by preferential CO oxidation in H2-rich streams. Bi-metallic catalysts have attracted increasing attention because of their markedly different properties from either of the costituent metals, and above all their enhanced catalytic activity, selectivity and stability. In the literature there are several studies demostrating the beneficial effect due to the addition of an iron component to gold supported catalysts in terms of enhanced activity, selectivity, resistence to deactivation and prolonged lifetime of the catalyst. In this work we tried to develop a methodology for the preparation of iron stabilized gold nanoparticles with controlled size and composition, particularly in terms of obtaining an intimate contact between different phases, since it is well known that the catalytic behaviour of multi-component supported catalysts is strongly influenced by the size of the metal particles and by their reciprocal interaction. Ligand stabilized metal clusters, with nanometric dimensions, are possible precursors for the preparation of catalytically active nanoparticles with controlled dimensions and compositions. Among these, metal carbonyl clusters are quite attractive, since they can be prepared with several different sizes and compositions and, moreover, they are decomposed under very mild conditions. A novel preparation method was developed during this thesis for the preparation of iron and gold/iron supported catalysts using bi-metallic carbonyl clusters as precursors of highly dispersed nanoparticles over TiO2 and CeO2, which are widely considered two of the most suitable supports for gold nanoparticles. Au/FeOx catalysts were prepared by employing the bi-metallic carbonyl cluster salts [NEt4]4[Au4Fe4(CO)16] (Fe/Au=1) and [NEt4][AuFe4(CO)16] (Fe/Au=4), and for comparison FeOx samples were prepared by employing the homometallic [NEt4][HFe3(CO)11] cluster. These clusters were prepared by Prof. Longoni research group (Department of Physical and Inorganic Chemistry- University of Bologna). Particular attention was dedicated to the optimization of a suitable thermal treatment in order to achieve, apart from a good Au and Fe metal dispersion, also the formation of appropriate species with good catalytic properties. A deep IR study was carried out in order to understand the physical interaction between clusters and different supports and detect the occurrence of chemical reactions between them at any stage of the preparation. The characterization by BET, XRD, TEM, H2-TPR, ICP-AES and XPS was performed in order to investigate the catalysts properties, whit particular attention to the interaction between Au and Fe and its influence on the catalytic activity. This novel preparation method resulted in small gold metallic nanoparticles surrounded by highly dispersed iron oxide species, essentially in an amorphous phase, on both TiO2 and CeO2. The results presented in this thesis confirmed that FeOx species can stabilize small Au particles, since keeping costant the gold content but introducing a higher iron amount a higher metal dispersion was achieved. Partial encapsulation of gold atoms by iron species was observed since the Au/Fe surface ratio was found much lower than bulk ratio and a strong interaction between gold and oxide species, both of iron oxide and supports, was achieved. The prepared catalysts were tested in the total oxidation of VOCs, using toluene and methanol as probe molecules for aromatics and alchols, respectively, and in the PROX reaction. Different performances were observed on titania and ceria catalysts, on both toluene and methanol combustion. Toluene combustion on titania catalyst was found to be enhanced increasing iron loading while a moderate effect on FeOx-Ti activity was achieved by Au addition. In this case toluene combustion was improved due to a higher oxygen mobility depending on enhanced oxygen activation by FeOx and Au/FeOx dispersed on titania. On the contrary ceria activity was strongly decreased in the presence of FeOx, while the introduction of gold was found to moderate the detrimental effect of iron species. In fact, excellent ceria performances are due to its ability to adsorb toluene and O2. Since toluene activation is the determining factor for its oxidation, the partial coverage of ceria sites, responsible of toluene adsorption, by FeOx species finely dispersed on the surface resulted in worse efficiency in toluene combustion. Better results were obtained for both ceria and titania catalysts on methanol total oxidation. In this case, the performances achieved on differently supported catalysts indicate that the oxygen mobility is the determining factor in this reaction. The introduction of gold on both TiO2 and CeO2 catalysts, lead to a higher oxygen mobility due to the weakening of both Fe-O and Ce-O bonds and consequently to enhanced methanol combustion. The catalytic activity was found to strongly depend on oxygen mobility and followed the same trend observed for catalysts reducibility. Regarding CO PROX reaction, it was observed that Au/FeOx titania catalysts are less active than ceria ones, due to the lower reducibility of titania compared to ceria. In fact the availability of lattice oxygen involved in PROX reaction is much higher in the latter catalysts. However, the CO PROX performances observed for ceria catalysts are not really high compared to data reported in literature, probably due to the very low Au/Fe surface ratio achieved with this preparation method. CO preferential oxidation was found to strongly depend on Au particle size but also on surface oxygen reducibility, depending on the different oxide species which can be formed using different thermal treatment conditions or varying the iron loading over the support.

Spontane-Desorption-Massenspektrometrie zur Charakterisierung von gemischten, selbstorganisierten Schichten zur Metallabscheidung und zur Beobachtung von chemischen Reaktionen in dünnsten Filmen

Spontane-Desorption-Massenspektrometrie zur Charakterisierung von gemischten, selbstorganisierten Schichten zur Metallabscheidung und zur Beobachtung von chemischen Reaktionen in dünnsten Filmen Stephan Krämer Ein Ziel dieser Arbeit war es, selbstorganisierte Schichten aus steifen benzolhaltigen Thiolen herzustellen und zu charakterisieren. Diese selbstorganisierten Schichten sollten als optimale Substrate zur Abscheidung von Metallen durch CVD dienen.In einem ersten Schritt wurden Schichten aus Biphenylthiol (BT) und Biphenyldithiol (BDT) auf Edelmetalloberflächen hergestellt. Die Abhängigkeit der Eigenschaften der Schicht von dem verwendeten Substrat und von der Dauer der Selbstorganisation wurde mit der Spontane-Desorption-Massenspektrometrie untersucht. Die Untersuchung der Schichtdicke erfolgte mit Oberflächenplasmonen-Spektroskopie und die Frage der Struktur der Schichten wurde versucht, mit Hilfe der Fourier-Transform-Infrarot-Spektroskopie zu klären. Nach der Charakterisierung der reinen Schichten wurden binäre Mischungen aus BT und BDT hergestellt und auf Goldoberflächen abgeschieden. Die so hergestellten binären Schichten wurden als Substrate zur Abscheidung von Gold benutzt. Dazu wurde mit Hilfe der CVD-Technik Gold auf den Filmen abgeschieden. Im nächsten Schritt wurden die einfacheren Halogen-substituierten Phenylthiole sowohl als reine Schichten als auch als binäre Mischungen untersucht. Ein weiterer Schwerpunkt stellte die Untersuchungen zur Abscheidung von Metallen auf selbstorganisierten Schichten durch CVD dar. Neben der schon vorgestellten Abscheidung von Gold wurde die Abscheidung von Palladium und von Kupfer untersucht. Im letzten Teil dieser Arbeit wurden der Verlauf einer chemischen Reaktion in einem ultradünnen Polymerfilm beobachtet. Dazu wurden die Vernetzungsreaktion und die Hydrolyse des Copolymer P[tBMA1-co-DMIMA0,11] untersucht.

Development of muliplexed analytical methods based on bioluminescent whole-cell biosensors

The subject of this Ph.D. research thesis is the development and application of multiplexed analytical methods based on bioluminescent whole-cell biosensors. One of the main goals of analytical chemistry is multianalyte testing in which two or more analytes are measured simultaneously in a single assay. The advantages of multianalyte testing are work simplification, high throughput, and reduction in the overall cost per test. The availability of multiplexed portable analytical systems is of particular interest for on-field analysis of clinical, environmental or food samples as well as for the drug discovery process. To allow highly sensitive and selective analysis, these devices should combine biospecific molecular recognition with ultrasensitive detection systems. To address the current need for rapid, highly sensitive and inexpensive devices for obtaining more data from each sample,genetically engineered whole-cell biosensors as biospecific recognition element were combined with ultrasensitive bioluminescence detection techniques. Genetically engineered cell-based sensing systems were obtained by introducing into bacterial, yeast or mammalian cells a vector expressing a reporter protein whose expression is controlled by regulatory proteins and promoter sequences. The regulatory protein is able to recognize the presence of the analyte (e.g., compounds with hormone-like activity, heavy metals…) and to consequently activate the expression of the reporter protein that can be readily measured and directly related to the analyte bioavailable concentration in the sample. Bioluminescence represents the ideal detection principle for miniaturized analytical devices and multiplexed assays thanks to high detectability in small sample volumes allowing an accurate signal localization and quantification. In the first chapter of this dissertation is discussed the obtainment of improved bioluminescent proteins emitting at different wavelenghts, in term of increased thermostability, enhanced emission decay kinetic and spectral resolution. The second chapter is mainly focused on the use of these proteins in the development of whole-cell based assay with improved analytical performance. In particular since the main drawback of whole-cell biosensors is the high variability of their analyte specific response mainly caused by variations in cell viability due to aspecific effects of the sample’s matrix, an additional bioluminescent reporter has been introduced to correct the analytical response thus increasing the robustness of the bioassays. The feasibility of using a combination of two or more bioluminescent proteins for obtaining biosensors with internal signal correction or for the simultaneous detection of multiple analytes has been demonstrated by developing a dual reporter yeast based biosensor for androgenic activity measurement and a triple reporter mammalian cell-based biosensor for the simultaneous monitoring of two CYP450 enzymes activation, involved in cholesterol degradation, with the use of two spectrally resolved intracellular luciferases and a secreted luciferase as a control for cells viability. In the third chapter is presented the development of a portable multianalyte detection system. In order to develop a portable system that can be used also outside the laboratory environment even by non skilled personnel, cells have been immobilized into a new biocompatible and transparent polymeric matrix within a modified clear bottom black 384 -well microtiter plate to obtain a bioluminescent cell array. The cell array was placed in contact with a portable charge-coupled device (CCD) light sensor able to localize and quantify the luminescent signal produced by different bioluminescent whole-cell biosensors. This multiplexed biosensing platform containing whole-cell biosensors was successfully used to measure the overall toxicity of a given sample as well as to obtain dose response curves for heavy metals and to detect hormonal activity in clinical samples (PCT/IB2010/050625: “Portable device based on immobilized cells for the detection of analytes.” Michelini E, Roda A, Dolci LS, Mezzanotte L, Cevenini L , 2010). At the end of the dissertation some future development steps are also discussed in order to develop a point of care (POCT) device that combine portability, minimum sample pre-treatment and highly sensitive multiplexed assays in a short assay time. In this POCT perspective, field-flow fractionation (FFF) techniques, in particular gravitational variant (GrFFF) that exploit the earth gravitational field to structure the separation, have been investigated for cells fractionation, characterization and isolation. Thanks to the simplicity of its equipment, amenable to miniaturization, the GrFFF techniques appears to be particularly suited for its implementation in POCT devices and may be used as pre-analytical integrated module to be applied directly to drive target analytes of raw samples to the modules where biospecifc recognition reactions based on ultrasensitive bioluminescence detection occurs, providing an increase in overall analytical output.

Il monitoraggio suolo-pianta per la valutazione dell'inquinamento da metalli pesanti nell'ambiente urbano

Il lavoro di tesi è incentrato sulla valutazione del degrado del suolo dovuto a fenomeni di inquinamento da metalli pesanti aerodispersi, ovvero apportati al suolo mediante deposizioni atmosferiche secche ed umide, in ambiente urbano. Lo scopo della ricerca è legato principalmente alla valutazione dell’efficienza del metodo di monitoraggio ideato che affianca al campionamento e all’analisi pedologica l’utilizzo di bioindicatori indigeni, quali il muschio, il cotico erboso, le foglie di piante arboree e il materiale pulverulento depositatosi su di esse. Una semplice analisi pedologica infatti non permette di discriminare la natura dei contaminanti in esso ritrovati. I metalli pesanti possono raggiungere il suolo attraverso diverse vie. In primo luogo questi elementi in traccia si trovano naturalmente nei suoi; ma numerose sono le fonti antropiche: attività industriali, traffico veicolare, incenerimento dei rifiuti, impianti di riscaldamento domestico, pratiche agricole, utilizzo di acque con bassi requisiti di qualità, ecc. Questo fa capire come una semplice analisi del contenuto totale o pseudo - totale di metalli pesanti nel suolo non riesca a rispondere alla domanda su quale si la fonte di provenienza di queste sostanze. Il metodo di monitoraggio integrato suolo- pianta è stato applicato a due diversi casi di studio. Il primo denominato “Progetto per il monitoraggio e valutazione delle concentrazioni in metalli pesanti e micro elementi sul sistema suolo - pianta in aree urbane adibite a verde pubblico dell’Emilia – Romagna” ha permesso di valutare l’insorgenza di una diminuzione della qualità dell’ecosistema parco urbano causata dalla ricaduta di metalli pesanti aerotrasportati, in tre differenti realtà urbane dell’Emilia Romagna: le città di Bologna, Ferrara e Cesena. Le città presentano caratteristiche pedologiche, ambientali ed economico-sociali molto diverse tra loro. Questo ha permesso di studiare l’efficienza del metodo su campioni di suolo e di vegetali molto diversi per quanto riguarda le aliquote di metalli pesanti riscontrate. Il secondo caso di studio il “Monitoraggio relativo al contenuto in metalli pesanti e microelementi nel sistema acqua-suolo-pianta delle aree circostanti l’impianto di termovalorizzazione e di incenerimento del Frullo (Granarolo dell’Emilia - BO)” è stato invece incentrato sulla valutazione della qualità ambientale delle aree circostanti l’inceneritore. Qui lo scenario si presentava più omogeneo dal punto di vista pedologico rispetto al caso di studio precedente, ma molto più complesso l’ecosistema di riferimento (urbano, extra-urbano ed agricolo). Seppure il metodo suolo-pianta abbia permesso di valutare gli apporti di metalli pesanti introdotti per via atmosferica, non è stato possibile imputarne l’origine alle sole emissioni prodotte dall’inceneritore.