Degradation analysis of the SnO2 and ZnO-based varistors using electrostatic force microscopy

The degradation phenomena of ZnO and SnO2-based varistors were investigated for two different degradation methods: DC voltage at increased temperature and degradation with 8/20 μs pulsed currents (lightning type). Electrostatic force microscopy (EFM) was used to analyze the surface charge accumulated at grain-boundary regions before and after degradation. Before the degradation process, 85% of the barriers are active in the SnO2 system, while the ZnO system presents only 30% effective barriers. Both systems showed changes in the electrical behavior when degraded with pulses. In the case of the ZnO system, the behavior after pulse degradation was essentially ohmic due to the destruction of barriers (about 99% of the interfaces are conductive). After the degradation with 8/20 μs pulsed currents, the SnO2 system still presents nonohmic behavior with a significant decrease in the quantity of effective barriers (from 85% to 5%). However, when the degradation is accomplished with continuous current, the SnO2 system exhibits minimum variation, while the ZnO system degrades from 30% to 5%. This result indicates the existence of metastable defects of low concentration and/or low diffusion in the SnO2 system. High energy is necessary to degrade the barriers due to defect annihilation in the SnO2 system. © 2013 The American Ceramic Society.

The analysis of gene transcripts associated with conidiation in the insect pathogenic fungus, Metarhizium anisopliae /

Conidia of the insect pathogenic fungus, Metarhizium anisopliae play an important role in pathogenicity because they are the infective propagules that adhere to the surface of the insect, then germinate and give rise to hyphal penetration of the insect cuticle. Conidia are produced in the final stages of insect infection as the mycelia emerge from the insect cadaver. The genes associated with conidiation have not yet been studied in this fiingus. hi this study we used the PCR-based technique, suppression subtractive hybridization (SSH) to selectively amplify conidial-associated genes in M. anisopliae. We then identified the presence of these differentially expressed genes using the National Center for Biotechnology Information database. One of the transcripts encoded an extracellular subtilisin-like protease, Prl, which plays a fundamental role in cuticular protein degradation. Analysis of the patterns of gene expression of the transcripts using RT-PCR indicated that conidial-associated cDNAs are expressed during the development of the mature conidium. RT-PCR analysis was also performed to examine in vivo expression of Prl during infection of waxworm larvae {Galleria mellonelld). Results showed expression of Prl as mycelia emerge and produce conidia on the surface of the cadaver. It is well documented that Prl is produced during the initial stages of transcuticular penetration by M. anisopliae. We suggest that upregulation of Prl is part of the mechanism by which reverse (from inside to the outside of the host) transcuticular penetration of the insect cuticle allows subsequent conidiation on the cadaver.

Physicochemical characterization of two deproteinized bovine xenografts

Calcium phosphate salts, or more specifically hydroxyapatite, are products of great interest in the fields of medical and dental science due to their biocompatibility and osteoconduction property. Deproteinized xenografts are primarily constituted of natural apatites, sintered or not. Variations in the industrial process may affect physicochemical properties and, therefore, the biological outcome. The purpose of this work was to characterize the physical and chemical properties of deproteinized xenogenic biomaterials, Bio-Oss (Geistlich Biomaterials, Wolhuser, Switzerland) and Gen-Ox (Baumer S.A., Brazil), widely used as bone grafts. Scanning electron microscopy, infrared region spectroscopy, X-ray diffraction, thermogravimetry and degradation analysis were conducted. The results show that both materials presented porous granules, composed of crystalline hydroxyapatite without apparent presence of other phases. Bio-Oss presented greater dissolution in Tris-HCl than Gen-Ox in the degradation test, possibly due to the low crystallinity and the presence of organic residues. In conclusion, both commercial materials are hydroxyapatite compounds, Bio-Oss being less crystalline than Gen-Ox and, therefore, more prone to degradation.

Prospecção de genes de interesse biotecnológico : uma abordagem metagenômica

The total number of prokaryotic cells on Earth has been estimated at 4 to 6x1030 and only about 1% of microorganisms present in the environment can be cultivated by standard techniques of cultivation and plating. Therefore, it is a huge biological and genetic pool that can be exploited, for the identification and characterization of genes with biotechnological potential. Within this perspective, the metagenomics approach was applied in this work. Functional screening methods were performed aiming to identify new genes related to DNA repair and / or oxidative stress resistance, hydrocarbon degradation and hydrolytic activities (lipase, amylase and protease). Metagenomic libraries were built utilizing DNA extracted from soil samples collected in João Câmara RN. The libraries were analyzed functionally using specific substrate containing solid medium (hydrolytic activity), supplemented with H2O2 (DNA repair and / or resistance to oxidative stress) and liquid medium supplemented with light Arabian oil (activity, degradation of hydrocarbons). After confirmation of activity and exclusion of false-positive results, 49 clones were obtained, being 2 positive for amylase activity, 22 resistant to oxidative stress generated by H2O2 and 25 clones active for hydrocarbons degradation. Analysis of the sequences showed hypothetical proteins, dienelactona hydrolase, DNA polymerase, acetyltransferase, phosphotransferase, methyltransferase, endonucleases, among other proteins. The sequence data obtained matched with the functions tested, highlighting the success of metagenomics approaches combined with functional screening methods, leading to very promising results

Análise da degradação ambiental das áreas de preservação permanente localizadas no estuário do rio Ceará-mirim/RN

The purpose of this paper is to identify and analyze the main environmental impacts taking place in the permanent preservation areas located in the Ceará-Mirim River estuary/RN and its surrounding areas. For that, the study was divided in two chapters, structured in the shape of a scientific paper. The first is a theoretical proposition on the occupation of the APPs in light of the discussion of the geographic space and the sustainability of the development, where a bibliographical review was made emphasizing the production of the geographic space, the sustainability of the development and the permanent preservation areas. In the second chapter, from a systemic approach, geoprocessing techniques and the adaptation of the Pressure-State- Response Indicators System were used, the latter being developed by the Organization for Economic Co-operation and Development OECD. Therefore, from the methodological approaches used, it's been observed that the use of permanent preservation areas for purposes other than those determined in the legislation and, mainly guided by capitalist interests, leads to the environmental degradation of these areas, fact which has been confirmed in the empiric study conducted in the second chapter, where it was possible to identify a series of environmental impacts such as: deforestation of mangrove and riparian vegetation for carciniculture implantation, the devastation of dune areas caused by the urban expansion in the coastal stretch and siltation of fluvial channel

A comparative study of the photophysics and photochemistry of 4-chlorophenol adsorbed on silicalite and beta-cyclodextrin

The photochemistry and photophysics of 4-chlorophenol (4-CP) were studied onto two model solid supports, silicalite and beta-cyclodextrin (beta-Cl)), using time resolved diffuse reflectance techniques and product degradation analysis. The results have shown that the photochemistry and photophysics of 4-CP are different from solution and depend on the solid. Ground state diffuse reflectance and time resolved luminescence demonstrated the inclusion of the probe in both substrates. 4-CP exhibits room temperature luminescence in both hosts, being structured and much more intense in beta-CD. The emission was assigned to phosphorescence of the inclusion complex. Transient absorption demonstrated the formation of the unsubstituted phenoxyl radical and of 4-chlorophenoxyl radical in beta-CD. In silicalite only the later was detected. The studies of the photodegradation products indicate that phenol is the main photoproduct in beta-CD. In silicalite the chromatographic analysis indicates the presence of products that involve the ring cleavage. (C) 2002 Elsevier Science B.V. All rights reserved.

Photochemistry of 4-chlorophenol on cellulose and silica

The photochemistry of 4-chlorophenol (4-CP) was studied on silica and cellulose, using time-resolved diffuse reflectance techniques and product degradation analysis. The results have shown that the photochemistry of 4-CP depends on the support, on the concentration, and also on the sample preparation method. Transient absorption and photoproduct results can be understood by assuming the formation of the carbene 4-oxocyclohexa-2,5-dienylidene in both supports. On cellulose, at concentrations lower than 10 mumol g(-1), the carbene leads to the unsubstituted phenoxyl radical, and phenol is the main degradation product. At higher concentrations a new transient resulting from phenoxyl radicals coupling was also observed, and dihydroxybiphenyls are also formed. The reaction of the carbene with ground-state 4-CP was also detected through the formation of 5-chloro-2,4'-dihydroxybiphenyl. 4-Chlorophenoxyl radical and degradations products resulting from its coupling were also detected. Oxygen has little effect on the photochemistry of 4-CP on cellulose. On silica the transient benzoquinone O-oxide was formed in the presence of oxygen. Benzoquinone and hydroquinone are the main degradation products. In well-dried samples the formation of hydroquinone is reduced. At higher concentrations the same products as detected on cellulose were observed. 4-CP undergoes slow photochemical decomposition under solar radiation in both supports. The same main degradation products were observed in these conditions.

Long-term reliability of power GaN HEMTS

The world is quickly changing, and the field of power electronics assumes a pivotal role in addressing the challenges posed by climate change, global warming, and energy management. The introduction of wide-bandgap semiconductors, particularly gallium nitride (GaN), in contrast to the traditional silicon technology, is leading to lightweight, compact and evermore efficient circuitry. However, GaN technology is not mature yet and still presents reliability issues which constrain its widespread adoption. Therefore, GaN reliability is a hotspot for the research community. Extensive efforts have been directed toward understanding the physical mechanisms underlying the performance and reliability of GaN power devices. The goal of this thesis is to propose a novel in-circuit degradation analysis in order to evaluate the long-term reliability of GaN-based power devices accurately. The in-circuit setup is based on measure-stress-measure methodology where a high-speed synchronous buck converter ensures the stress while the measure is performed by means of full I-V characterizations. The switch from stress mode to characterization mode and vice versa is automatic thanks to electromechanical and solid-state relays controlled by external unit control. Because these relays are located in critical paths of the converter layout, the design has required a comprehensive study of electrical and thermal problems originated by the use of GaN technology. In addition, during the validation phase of the converter, electromagnetic-lumped-element circuit simulations are carried out to monitor the signal integrity and junction temperature of the devices under test. However, the core of this work is the in-circuit reliability analysis conducted with 80 V GaN HEMTs under several operating conditions of the converter in order to figure out the main stressors which contribute to the device's degradation.

Development of a flow through photo-reactor to study degradation of organic compounds by Sequential Injection Analysis (SIA)

This work describes a photo-reactor to perform in line degradation of organic compounds by photo-Fenton reaction using Sequential Injection Analysis (SIA) system. A copper phthalocyanine-3,4',4²,4²¢-tetrasulfonic acid tetrasodium salt dye solution was used as a model compound for the phthalocyanine family, whose pigments have a large use in automotive coatings industry. Based on preliminary tests, 97% of color removal was obtained from a solution containing 20 µmol L-1 of this dye.

Biomimetic oxidative treatment of spruce wood studied by pyrolysis-molecular beam mass spectrometry coupled with multivariate analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis: implications for fungal degradation of wood

In this work, pyrolysis-molecular beam mass spectrometry analysis coupled with principal components analysis and (13)C-labeled tetramethylammonium hydroxide thermochemolysis were used to study lignin oxidation, depolymerization, and demethylation of spruce wood treated by biomimetic oxidative systems. Neat Fenton and chelator-mediated Fenton reaction (CMFR) systems as well as cellulosic enzyme treatments were used to mimic the nonenzymatic process involved in wood brown-rot biodegradation. The results suggest that compared with enzymatic processes, Fenton-based treatment more readily opens the structure of the lignocellulosic matrix, freeing cellulose fibrils from the matrix. The results demonstrate that, under the current treatment conditions, Fenton and CMFR treatment cause limited demethoxylation of lignin in the insoluble wood residue. However, analysis of a water-extractable fraction revealed considerable soluble lignin residue structures that had undergone side chain oxidation as well as demethoxylation upon CMFR treatment. This research has implications for our understanding of nonenzymatic degradation of wood and the diffusion of CMFR agents in the wood cell wall during fungal degradation processes.

Analysis of the gate capacitance measurement technique and its application for the evaluation of hot-carrier degradation in submicrometer MOSFETs

The use of gate-to-drain capacitance (C-gd) measurement as a tool to characterize hot-carrier-induced charge centers in submicron n- and p-MOSFET's has been reviewed and demonstrated. By analyzing the change in C-gd measured at room and cryogenic temperature before and after high gate-to-drain transverse field (high field) and maximum substrate current (I-bmax) stress, it is concluded that the degradation was found to be mostly due to trapping of majority carriers and generation of interface states. These interface states were found to be acceptor states at top half of band gap for n-MOSFETs and donor states at bottom half of band gap for p-MOSFETs. In general, hot electrons are more likely to be trapped in gate oxide as compared to hot holes while the presence of hot holes generates more interface states. Also, we have demonstrated a new method for extracting the spatial distribution of oxide trapped charge, Q(ot), through gate-to-substrate capacitance (C-gb) measurement. This method is simple to implement and does not require additional information from simulation or detailed knowledge of the device's structure. (C) 2001 Elsevier Science Ltd. All rights reserved.

Voltammetric analysis of mancozeb and its degradation product ethylenethiourea

The purpose of this work was to develop a reliable alternative method for the determination of the dithiocarbamate pesticide mancozeb (MCZ) in formulations. Furthermore, a method for the analysis of MCZ's major degradation product, ethylenethiourea (ETU), was also proposed. Cyclic voltammetry was used to characterize the electrochemical behavior of MCZ and ETU, and square-wave adsorptive stripping voltammetry (SWAdSV) was employed for MCZ quantification in commercial formulations. It was found that both MCZ and ETU are irreversibly reduced (− 0.6 V and − 0.5 V vs Ag/AgCl, respectively) at the surface of a glassy carbon electrode in a mainly diffusion-controlled process, presenting maximum peak current intensities at pH 7.0 (in phosphate buffered saline electrolyte). Several parameters of the SWAdSV technique were optimized and linear relationships between concentration and peak current intensity were established between 10–90 μmol L− 1 and 10–110 μmol L− 1 for MCZ and ETU, respectively. The limits of detection were 7.0 μmol L− 1 for MCZ and 7.8 μmol L− 1 for ETU. The optimized method for MCZ was successfully applied to the quantification of this pesticide in two commercial formulations. The developed procedures provided accurate and precise results and could be interesting alternatives to the established methods for quality control of the studied products, as well as for analysis of MCZ and ETU in environmental samples.

Stochastic modeling of the thermal and catalytic degradation of polyethylene using simultaneous DSC/TG analysis

Dissertação para obtenção do Grau de Mestre em Engenharia Química e Bioquímica

Genome-scale metabolic network reconstruction of Polaromonas sp. strain JS666: analysis of cDCE degradation rates and design of experiments for bioremediation improvement

Release of chloroethene compounds into the environment often results in groundwater contamination, which puts people at risk of exposure by drinking contaminated water. cDCE (cis-1,2-dichloroethene) accumulation on subsurface environments is a common environmental problem due to stagnation and partial degradation of other precursor chloroethene species. Polaromonas sp. strain JS666 apparently requires no exotic growth factors to be used as a bioaugmentation agent for aerobic cDCE degradation. Although being the only suitable microorganism found capable of such, further studies are needed for improving the intrinsic bioremediation rates and fully comprehend the metabolic processes involved. In order to do so, a metabolic model, iJS666, was reconstructed from genome annotation and available bibliographic data. FVA (Flux Variability Analysis) and FBA (Flux Balance Analysis) techniques were used to satisfactory validate the predictive capabilities of the iJS666 model. The iJS666 model was able to predict biomass growth for different previously tested conditions, allowed to design key experiments which should be done for further model improvement and, also, produced viable predictions for the use of biostimulant metabolites in the cDCE biodegradation.

Proteomic analysis of nitrate-dependent acetone degradation by Alicycliphilus denitrificans strain BC

Alicycliphilus denitrificans strain BC grows anaerobically on acetone with nitrate as electron acceptor. Comparative proteomics of cultures of A. denitrificans strain BC grown on either acetone or acetate with nitrate was performed to study the enzymes involved in the acetone degradation pathway. In the proposed acetone degradation pathway, an acetone carboxylase converts acetone to acetoacetate, an AMP-dependent synthetase/ligase converts acetoacetate to acetoacetyl-CoA, and an acetyl-CoA acetyltransferase cleaves acetoacetyl-CoA to two acetyl-CoA. We also found a putative aldehyde dehydrogenase associated with acetone degradation. This enzyme functioned as a -hydroxybutyrate dehydrogenase catalyzing the conversion of surplus acetoacetate to -hydroxybutyrate that may be converted to the energy and carbon storage compound, poly--hydroxybutyrate. Accordingly, we confirmed the formation of poly-?-hydroxybutyrate in acetone-grown cells of strain BC. Our findings provide insight in nitrate-dependent acetone degradation that is activated by carboxylation of acetone. This will aid studies of similar pathways found in other microorganisms degrading acetone with nitrate or sulfate as electron acceptor.