Tryptophan oxidation by singlet molecular oxygen [O-2 ((1)Delta(g))]: Mechanistic studies using O-18-labeled hydroperoxides, mass spectrometry, and light emission measurements

Proteins have been considered important targets for reactive oxygen species. Indeed, tryptophan (W) has been shown to be a highly susceptible amino acid to many oxidizing agents, including singlet molecular oxygen [O-2 ((1)Delta(g))]. In this study, two cis- and trans-tryptophan hydroperoxide (WOOH) isomers were completely characterized by HPLC/mass spectrometry and NMR analyses as the major W-oxidation photoproducts. These photoproducts underwent thermal decay into the corresponding alcohols. Additionally, WOOHs were shown to decompose under heating or basification, leading to the formation of N-formylkynurenine (FMK). Using O-18-labeled hydroperoxides ((WOOH)-O-18-O-18), it was possible to confirm the formation of two oxygen-labeled FMK molecules derived from (WOOH)-O-18-O-18 decomposition. This result demonstrates that both oxygen atoms in FMK are derived from the hydroperoxide group. In addition, these reactions are chemiluminescent (CL), indicating a dioxetane cleavage pathway. This mechanism was confirmed since the CL spectrum of the WOOH decomposition matched the FMK fluorescence spectrum, unequivocally identifying FMK as the emitting species.

Cholesterol Hydroperoxides Generate Singlet Molecular Oxygen [O(2) ((1)Delta(g))]: Near-IR Emission, (18)O-Labeled Hydroperoxides, and Mass Spectrometry

In mammalian membranes, cholesterol is concentrated in lipid rafts. The generation of cholesterol hydroperoxides (ChOOHs) and their decomposition products induces various types of cell damage. The decomposition of some organic hydroperoxides into peroxyl radicals is known to be a potential source of singlet molecular oxygen [O(2) ((1)Delta(g))] in biological systems. We report herein on evidence of the generation of O(2) ((1)Delta(g)) from ChOOH isomers in solution or in liposomes containing ChOOHs, which involves a cyclic mechanism from a linear tetraoxide intermediate originally proposed by Russell. Characteristic light emission at 1270 nm, corresponding to O(2) ((1)Delta(g)) monomolecular decay, was observed for each ChOOH isomer or in liposomes containing ChOOHs. Moreover, the presence of O(2) ((1)Delta(g)) was unequivocally demonstrated using the direct spectral characterization of near-infrared light emission. Using (18)O-labeled cholesterol hydroperoxide (Ch(18)O(18)OH), we observed the formation of (18)O-labeled O(2) ((1)Delta(g)) [(18)O(2) ((1)Delta(g))] by the chemical trapping of (18)O(2) ((1)Delta(g)) with 9,10-diphenylanthracene (DPA) and detected the corresponding (18)O-labeled DPA endoperoxide (DPA(18)O(18)O) and the (18)O-labeled products of the Russell mechanism using high-performance liquid chromatography coupled to tandem mass spectrometry. Photoemission properties and chemical trapping clearly demonstrate that the decomposition of Ch(18)O(18)OH generates (18)O(2) ((1)Delta(g)), which is consistent with the Russell mechanism and points to the involvement of O(2) ((1)Delta(g)) in cholesterol hydroperoxide-mediated cytotoxicity.

Vision in click beetles (Coleoptera: Elateridae): pigments and spectral correspondence between visual sensitivity and species bioluminescence emission

Among lampyrids, intraspecific sexual communication is facilitated by spectral correspondence between visual sensitivity and bioluminescence emission from the single lantern in the tail. Could a similar strategy be utilized by the elaterids (click beetles), which have one ventral abdominal and two dorsal prothoracic lanterns? Spectral sensitivity [S(lambda)] and bioluminescence were investigated in four Brazilian click beetle species Fulgeochlizus bruchii, Pyrearinus termitilluminans, Pyrophorus punctatissimus and P. divergens, representing three genera. In addition, in situ microspectrophotometric absorption spectra were obtained for visual and screening pigments in P. punctatissimus and P. divergens species. In all species, the electroretinographic S(lambda) functions showed broad peaks in the green with a shoulder in the near-ultraviolet, suggesting the presence of short- and long-wavelength receptors in the compound eyes. The long-wavelength receptor in Pyrophorus species is mediated by a P540 rhodopsin in conjunction with a species-specific screening pigment. A correspondence was found between green to yellow bioluminescence emissions and its broad S(lambda) maximum in each of the four species. It is hypothesized that in elaterids, bioluminescence of the abdominal lantern is an optical signal for intraspecifc sexual communication, while the signals from the prothoracic lanterns serve to warn predators and may also provide illumination in flight.

In vitro evaluation of Cu and Fe bioavailability in cashew nuts by off-line coupled SEC-UV and SIMAAS

In this work Cu and Fe bioavailability in cashew nuts was evaluated using in vitro method. Extractions with simulated gastric and intestinal fluids and dialysis procedures were applied for this purpose. The proteins separation and quantification were performed by size exclusion chromatography (SEC) coupled on-line to ultra-violet (UV) and off-line to simultaneous multielement atomic absorption spectrometry (SIMAAS). The SEC-UV and SIMAAS profiles of the protein fractions obtained by alkaline extraction (NaOH) and precipitation with HCl indicated the presence of high and low molecular weight species in the range between >75 kDa and 9.3 kDa. Almost 83% of Cu and 78% of Fe were extracted during cashew nut digestion and 90% of both elements were dialyzed. With these results it is possible to assume that 75% of Cu and 70% of Fe present in cashew nut could be bioavailable. The SEC-UV and SIMAAS chromatographic profiles obtained after in vitro gastrointestinal digestion reveal that Cu and Fe not dialyzed can be associated to a compound of 9.2 kDa. (C) 2010 Elsevier B.V. All rights reserved.

A method for Ca, Fe, Ga, Na, Si and Zn determination in alumina by inductively coupled plasma optical emission spectrometry after aluminum precipitation

In this present work a method for the determination of Ca, Fe, Ga, Na, Si and Zn in alumina (Al(2)O(3)) by inductively coupled plasma optical emission spectrometry (ICP OES) with axial viewing is presented. Preliminary studies revealed intense aluminum spectral interference over the majority of elements and reaction between aluminum and quartz to form aluminosilicate, reducing drastically the lifetime of the torch. To overcome these problems alumina samples (250 mg) were dissolved with 5 mL HCl + 1.5 mLH(2)SO(4) + 1.5 mL H(2)O in a microwave oven. After complete dissolution the volume was completed to 20 mL and aluminum was precipitated as Al(OH)(3) with NH(3) (by bubbling NH(3) into the solution up to a pH similar to 8, for 10 min). The use of internal standards (Fe/Be, Ga/Dy, Zn/In and Na/Sc) was essential to obtain precise and accurate results. The reliability of the proposed method was checked by analysis of alumina certified reference material (Alumina Reduction Grade-699, NIST). The found concentrations (0.037%w(-1) CaO, 0.013% w w(-1) Fe(2)O(3), 0.012%w w(-1)Ga(2)O(3), 0.49% w w(-1) Na(2)O, 0.014% w w(-1) SiO(2) and 0.013% w w(-1) ZnO) presented no statistical differences compared to the certified values at a 95% confidence level. (C) 2011 Elsevier B.V. All rights reserved.

Overexpression of Nrp/b (nuclear restrict protein in brain) suppresses the malignant phenotype in the C6/ST1 glioma cell line

Upon searching for glucocorticoid-regulated cDNA sequences associated with the transformed to normal phenotypic reversion of C6/ST1 rat glioma cells, we identified Nrp/b (nuclear restrict protein in brain) as a novel rat gene. Here we report on the identification and functional characterization of the complete sequence encoding the rat NRP/B protein. The cloned cDNA presented a 1767 nucleotides open-reading frame encoding a 589 aminoacids residues sequence containing a BTB/POZ (broad complex Tramtrack bric-a-brac/Pox virus and zinc finger) domain in its N-terminal region and kelch motifs in its C-terminal region. Sequence analysis indicates that the rat Nrp/b displays a high level of identity with the equivalent gene orthologs from other organisms. Among rat tissues, Nrp/b expression is more pronounced in brain tissue. We show that overexpression of the Nrp/b cDNA in C6/ST1 cells suppresses anchorage independence in vitro and tumorigenicity in vivo, altering their malignant nature towards a more benign phenotype. Therefore, Nrp/b may be postulated as a novel tumor suppressorgene, with possible relevance for glioblastoma therapy. (C) 2009 Elsevier Ltd. All rights reserved.

Analysis of EnterpriseVoIP Traffic from aWire line IMS System

With the rapid development of telecommunication industry, the IP multimedia Subsystem (IMS) could very well be the panacea for most telecom operators. It is originally defined as the core network for 3G mobile systems by the 3rd Generation Partnership Project (3GPP), the more recent development is merging between fixed line network and wireless networkd This report researchs the characteristic of the IMS data and proposes an IMS characterization analysis. We captured the IMS traffic data with 10 tousands users for about 41 hours. By analyzing the characteristics of the IMS, we know that the most important application in the IMS is VoIP call. Then we use the tool designed by Tsinghua University & Ericsson Company to recognize the data, and the results we got can be used to build the traffic models. From the results of the traffic models, I will get some reasons and conclusion. The traffic model gives out the types of session and types of VoIP call. I bring into a concept—busy hour. This concept is very important because it can help us to know which period is the peak of the VoIP call. The busy hour is from 10:00 to 11:00 in the morning. I also bring into another concept—connection ratio. This concept is significant because it can evaluate whether the VoIP call is good when it use IMS network. By comparing the traffic model with other one’s models, we found the different results from them, both the accuracy and the busy hour. From the contract, we got the advantages of our traffic models.

Energy Analysis within Industrial Hydraulics and Correspondent Solar PV System Design

Energy efficiency and renewable energy use are two main priorities leading to industrial sustainability nowadays according to European Steel Technology Platform (ESTP). Modernization efforts can be done by industries to improve energy consumptions of the production lines. These days, steel making industrial applications are energy and emission intensive. It was estimated that over the past years, energy consumption and corresponding CO2 generation has increased steadily reaching approximately 338.15 parts per million in august 2010 [1]. These kinds of facts and statistics have introduced a lot of room for improvement in energy efficiency for industrial applications through modernization and use of renewable energy sources such as solar Photovoltaic Systems (PV).The purpose of this thesis work is to make a preliminary design and simulation of the solar photovoltaic system which would attempt to cover the energy demand of the initial part of the pickling line hydraulic system at the SSAB steel plant. For this purpose, the energy consumptions of this hydraulic system would be studied and evaluated and a general analysis of the hydraulic and control components performance would be done which would yield a proper set of guidelines contributing towards future energy savings. The results of the energy efficiency analysis showed that the initial part of the pickling line hydraulic system worked with a low efficiency of 3.3%. Results of general analysis showed that hydraulic accumulators of 650 liter size should be used by the initial part pickling line system in combination with a one pump delivery of 100 l/min. Based on this, one PV system can deliver energy to an AC motor-pump set covering 17.6% of total energy and another PV system can supply a DC hydraulic pump substituting 26.7% of the demand. The first system used 290 m2 area of the roof and was sized as 40 kWp, the second used 109 m2 and was sized as 15.2 kWp. It was concluded that the reason for the low efficiency was the oversized design of the system. Incremental modernization efforts could help to improve the hydraulic system energy efficiency and make the design of the solar photovoltaic system realistically possible. Two types of PV systems where analyzed in the thesis work. A method was found calculating the load simulation sequence based on the energy efficiency studies to help in the PV system simulations. Hydraulic accumulators integrated into the pickling line worked as energy storage when being charged by the PV system as well.

qtl.outbred: Interfacing outbred line cross data with the R/qtl mapping software

Background qtl.outbred is an extendible interface in the statistical environment, R, for combining quantitative trait loci (QTL) mapping tools. It is built as an umbrella package that enables outbred genotype probabilities to be calculated and/or imported into the software package R/qtl. Findings Using qtl.outbred, the genotype probabilities from outbred line cross data can be calculated by interfacing with a new and efficient algorithm developed for analyzing arbitrarily large datasets (included in the package) or imported from other sources such as the web-based tool, GridQTL. Conclusion qtl.outbred will improve the speed for calculating probabilities and the ability to analyse large future datasets. This package enables the user to analyse outbred line cross data accurately, but with similar effort than inbred line cross data.

Uncertainties In Future Projections Of Extreme Rainfall: The Role Of Climate Model, Emission Scenario And Randomness

Climate change has resulted in substantial variations in annual extreme rainfall quantiles in different durations and return periods. Predicting the future changes in extreme rainfall quantiles is essential for various water resources design, assessment, and decision making purposes. Current Predictions of future rainfall extremes, however, exhibit large uncertainties. According to extreme value theory, rainfall extremes are rather random variables, with changing distributions around different return periods; therefore there are uncertainties even under current climate conditions. Regarding future condition, our large-scale knowledge is obtained using global climate models, forced with certain emission scenarios. There are widely known deficiencies with climate models, particularly with respect to precipitation projections. There is also recognition of the limitations of emission scenarios in representing the future global change. Apart from these large-scale uncertainties, the downscaling methods also add uncertainty into estimates of future extreme rainfall when they convert the larger-scale projections into local scale. The aim of this research is to address these uncertainties in future projections of extreme rainfall of different durations and return periods. We plugged 3 emission scenarios with 2 global climate models and used LARS-WG, a well-known weather generator, to stochastically downscale daily climate models’ projections for the city of Saskatoon, Canada, by 2100. The downscaled projections were further disaggregated into hourly resolution using our new stochastic and non-parametric rainfall disaggregator. The extreme rainfall quantiles can be consequently identified for different durations (1-hour, 2-hour, 4-hour, 6-hour, 12-hour, 18-hour and 24-hour) and return periods (2-year, 10-year, 25-year, 50-year, 100-year) using Generalized Extreme Value (GEV) distribution. By providing multiple realizations of future rainfall, we attempt to measure the extent of total predictive uncertainty, which is contributed by climate models, emission scenarios, and downscaling/disaggregation procedures. The results show different proportions of these contributors in different durations and return periods.

Novas perspectivas da análise estratégica: estudo de caso do UOL: como o caso do Universo On Line (UOL) pode criar novas perspectivas para a análise estratégica?

Estudo dos desafios e novas perspectivas estratégicas que se apresentam com o estudo de caso do UOL - Universo On Line - provedor de acesso e portal líder no Brasil, baseado em fatos e estatísticas do mercado e entrevista com o UOL.

Como criar possibilidades de financiamento para a agricultura familiar adotando o Plano ABC Nacional?

Ao longo dos últimos anos, através do aprimoramento das políticas agrícolas, observaram-se aumentos consistentes dos recursos orçamentários destinados à Agricultura Familiar, através do Pronaf. O incremento dos recursos efetivamente aplicados e o número cada vez maior de contratos também são realidade e podem ser vistos em todas as regiões do País. De acordo com os dados divulgados pelo Banco Central do Brasil, através do Anuário Estatístico do Crédito Rural (2014), foram aplicados no Brasil em 2004 aproximadamente R$ 4,39 bilhões, já em 2012 foram pouco mais de R$ 16,35 bilhões, ou seja, incremento de 272% no intervalo analisado. Em relação ao número de contratos, o crescimento foi em torno de 35,5% no mesmo período. A importância da Agricultura Familiar no contexto atual é corroborada no âmbito internacional pela Resolução 66/222, de 28.03.2012, da Assembleia-Geral, que conferiu à Organização das Nações Unidas para Alimentação e Agricultura (FAO) o mandato de implementar o Ano Internacional da Agricultura Familiar (AIAF) neste ano de 2014, em parceria com os governos dos países membros bem como com outros organismos internacionais e organizações não-governamentais atuantes no tema da agricultura e da segurança alimentar. Concomitantemente, diante da crescente preocupação com as questões ambientais, o Plano Setorial de Mitigação e de Adaptação às Mudanças Climáticas para a Consolidação de uma Economia de Baixa Emissão de Carbono na Agricultura - Plano ABC - é uma importante parte do compromisso voluntário assumido pelo Brasil em 2009, na 15ª Conferência das Partes – COP15 ocorrida em Copenhague, na redução da emissão de gases de efeito estufa até 2020. Parte desse compromisso assumido precisa ser atendido pela agricultura familiar, o que aumenta a responsabilidade da mesma para questões que vão além do fornecimento de alimentos, matérias primas e geração de energia etc. O Programa ABC, instrumento pelo qual os agricultores brasileiros podem acessar crédito para implementar tecnologias de baixas emissões de carbono, já está integrado nas ações previstas na Política de Crédito Agropecuário Brasileiro. Porém, ainda se observam vários desafios no Programa ABC, como aumentar o repasse desses recursos, não obstante ao aumento das operações contratadas pelos produtores nos últimos anos. O objetivo do estudo é investigar como a agricultura familiar pode contribuir com o Plano ABC e nos compromissos voluntários assumidos pelo País para a redução de emissão dos gases de efeito estufa no setor agropecuário. Para atingir esse objetivo, realizou-se uma revisão da bibliografia e das linhas de crédito disponíveis pelos bancos públicos e privados relacionadas ao Programa ABC e ao Pronaf. Conclui-se que há sinergias entre algumas linhas de crédito do Pronaf e também do Fundo Constitucional de Financiamento do Nordeste - FNE - Sudene com as tecnologias previstas no Plano ABC. Nesse sentido, o Plano ABC prevê a aplicação de tecnologias de redução de emissões em cerca de 4,97 milhões de ha ocupados pela agricultura familiar, sendo recursos do Pronaf previstos para fomentar tal aplicação, através das linhas Pronaf Eco e Pronaf Floresta. Contudo, verificou-se que tais linhas do Pronaf contemplam o uso de recursos para diversas outras atividades não relacionadas diretamente àquelas previstas no Plano ABC ou capazes de reduzir emissões de gases de efeito estufa. Dessa forma, não há como assegurar que a aplicação de recursos nessas linhas seja direcionada para tecnologias e ações que reduzam emissões, nem tão pouco há como monitorar o volume de recursos do Pronaf aplicados de fato em atividades aderentes ao Plano ABC. Portanto, sugere-se a criação/incorporação de novas linhas de crédito ao Pronaf, como por exemplo, Pronaf ABC Eco e o Pronaf ABC Floresta. Além disso, apresentou-se estudo de caso para o município de Bragança Paulista (SP), onde verificou-se que a utilização dos recursos do Programa ABC poderia ser usada para recomposição de áreas de preservação permanente ou de reserva legal, importantes na preservação das nascentes e rios da região. Essa possibilidade é de elevada importância no contexto e nas discussões atuais sobre a escassez dos recursos hídricos que abastecem grandes cidades, a exemplo do que vem ocorrendo na região metropolitana do Estado de São Paulo. Como conclusão, identifica-se alguns gargalos e apresenta-se algumas sugestões de melhorias para aumentar a utilização e eficácia do Programa ABC, como promover com mais ênfase apoio das assistências técnicas junto aos produtores, priorizar as ações previstas no Plano ABC em algumas regiões do País e aumentar a atuação mais direcionada do Ministério do Desenvolvimento Agrário (MDA) para difusão e incorporação das tecnologias de uma agricultura de baixa emissão de carbono no segmento da agricultura familiar.

Aerial line transect survey to estimate abundance of marsh deer (Blastocerus dichotomus) (Illiger, 1815)

A população de cervo-do-pantanal (Blastocerus dichotomus) está drasticamente reduzida no Brasil. O nosso objetivo foi o de estimar a abundância do cervo-do-pantanal na bacia do Rio Paraná e discutir a metodologia aplicada. Os resultados darão suporte para uma análise do impacto do enchimento da represa de Porto Primavera sobre essa população. Sessenta e nove animais foram registrados através de sobrevôo utilizando-se a metodologia de transecção linear com amostragem das distâncias. Os dados não corrigidos resultaram em uma densidade estimada de 0,0035ind/ha e uma população de 636 indivíduos. A correção de g para os animais que não foram vistos apresentou uma densidade de 0,0049 ind/ha e uma abundância de 896 (CV=0,27) indivíduos. A metodologia foi aplicada com sucesso na estimativa de cervo-do-pantanal. Esse resultado é importante para avaliarmos a população do cervo-do-pantanal na área e para futuramente analisarmos o impacto do enchimento da represa.

Spatial variability of soil CO2 emission in a sugarcane area characterized by secondary information

Soil CO2 emission (FCO2) is governed by the inherent properties of the soil, such as bulk density (BD). Mapping of FCO2 allows the evaluation and identification of areas with different accumulation potential of carbon. However, FCO2 mapping over larger areas is not feasible due to the period required for evaluation. This study aimed to assess the quality of FCO2 spatial estimates using values of BD as secondary information. FCO2 and BD were evaluated on a regular sampling grid of 60 m × 60 m comprising 141 points, which was established on a sugarcane area. Four scenarios were defined according to the proportion of the number of sampling points of FCO2 to those of BD. For these scenarios, 67 (F67), 87 (F87), 107 (F107) and 127 (F127) FCO2 sampling points were used in addition to 127 BD sampling points used as supplementary information. The use of additional information from the BD provided an increase in the accuracy of the estimates only in the F107, F67 and F87 scenarios, respectively. The F87 scenario, with the approximate ratio between the FCO2 and BD of 1.00:1.50, presented the best relative improvement in the quality of estimates, thereby indicating that the BD should be sampled at a density 1.5 time greater than that applied for the FCO2. This procedure avoided problems related to the high temporal variability associated with FCO2, which enabled the mapping of this variable to be elaborated in large areas.

Fractal dimension and anisotropy of soil CO2 emission in a mechanically harvested sugarcane production area

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)