Emission of polycyclic aromatic hydrocarbons from gasohol and ethanol vehicles

The exhaust emission of the polycyclic aromatic hydrocarbons (PAHs) considered toxic to human health were investigated on two spark ignition light duty vehicles, one being gasohol (Gasohol, in Brazil, is the generic denomination for mixtures of pure gasoline plus 20-25% of anhydrous ethyl alcohol fuel (AEAF).)-fuelled and the other a flexible-fuel vehicle fuelled with hydrated ethanol. The influence of fuel type and quality, aged lubricant oil type and use of fuel additives on the formation of these compounds was tested using standardized tests identical to US FTP-75 cycle. PAH sampling and chemical analysis followed the basic recommendations of method TO-13 (United States. Environmental Protection Agency, 1999. Compendium Method TO-13A - Determination of polycyclic Aromatic hydrocarbons (PAH) in Ambient Air Using Gas Chromatography/Mass Spectrometry (CG/MS). Center for environmental research information, Cincinnati, p. 78), with the necessary modification for this particular application. Results showed that the total PAH emission factor varied from 41.9 mu g km(-1) to 612 mu g km(-1) in the gasohol vehicle, and from 11.7 mu g km(-1) to 27.4 mu g km(-1) in the ethanol-fuelled vehicle, a significant difference in favor of the ethanol vehicle. Generally, emission of light molecular weight PAHs was predominant, while high molecular weights PAHs were not detected. In terms of benzo(a)pyrene toxicity equivalence, emission factors varied from 0.00984 mu g TEQ km(-1) to 4.61 mu g TEQ km(-1) for the gasohol vehicle and from 0.0117 mu g TEQ km(-1) to 0.0218 mu g TEQ km(-1) in the ethanol vehicle. For the gasohol vehicle, results showed that the use of fuel additive causes a significant increase in the emission of naphthalene and phenanthrene at a confidence level of 90% or higher; the use of rubber solvent on gasohol showed a reduction in the emission of naphthalene and phenanthrene at the same confidence level; the use of synthetic oil instead of mineral oil also contributed significantly to a decrease in the emission of naphthalene and fluorene. In relation to the ethanol vehicle, the same factors were tested and showed no statistically significant influence on PAH emission. (c) 2008 Elsevier Ltd. All rights reserved.

Fatty acid composition of intramuscular fat from Nellore steers fed dry or high moisture corn and calcium salts of fatty acids

The purpose of this work was to evaluate the fatty acid composition of the Longissimus muscle from carcasses of Nellore steers fed diets with calcium salts of fatty acids (CSFA) and high moisture corn. Forty eight steers were fed during 70 days four diets containing dry corn (DC), high moisture corn (HM). dry corn plus CSFA (DC-CSFA) or high moisture corn plus CSFA (HM-CSFA). Fatty acid composition of the Longissimus muscle was determined by gas chromatography. Corn type had no effect on the ether extract percentage and in the content of the majority of the fatty acids, although steers fed HMC showed higher levels of polyunsaturated fatty acids and polyunsaturated/saturated ratio. Feeding CSFA increased ether extract percentage but had no effect on total of saturated, unsaturated and saturated: unsaturated ratio. Both high moisture corn and calcium salts of fatty acids increased CIA (cis9, trans11) and total CIA concentrations in intramuscular fat (C) 2008 Elsevier B.V. All rights reserved.

Supercritical fluid extracts from the Brazilian cherry (Eugenia uniflora L.): Relationship between the extracted compounds and the characteristic flavour intensity of the fruit

Supercritical carbon dioxide (SC-CO(2)) extractions of Brazilian cherry (Eugenia uniflora L.) were carried out under varied conditions of pressure and temperature, according to a central composite 2(2) experimental design, in order to produce flavour-rich extracts. The composition of the extracts was evaluated by gas chromatography coupled with mass spectrometry (GC/MS). The abundance of the extracted compounds was then related to sensory analysis results, assisted by principal component and factorial discriminant analysis (PCA and FDA, respectively). The identified sesquiterpenes and ketones were found to strongly contribute to the characteristic flavour of the Brazilian cherry. The extracts also contained a variety of other volatile compounds, and part of the fruit wax contained long-chain hydrocarbons that according to multivariate analysis, contributed to the yield of the extracts, but not the flavour. Volatile phenolic compounds, to which antioxidant properties are attributed, were also present in the extracts in high proportion, regardless of the extraction conditions. (C) 2010 Elsevier Ltd. All rights reserved.

COMPOSITION OF SUPERCRITICAL CARBON DIOXIDE EXTRACTS OF PITANGA (EUGENIA UNIFLORA L.) LEAVES

The leaves of the Pitanga bush (Eugenia uniflora L.) are considered to be effective against many diseases. Extracts from Pitanga leaves have been found to show pronounced anti-inflammatory action and to have antimicrobial and antifungal activities, among other properties. In this work, extracts from Pitanga leaves were obtained by hydrodistillation and by extraction with supercritical carbon dioxide (SC-CO(2)) at three conditions of temperature and pressure. In the SC-CO(2) extractions also were collected the components that are lost with the CO(2) in the exit of the system using Porapak-Q polymer trap. All extracts were analyzed by gas chromatography-mass spectrometry (GC-MS). Thirty-nine compounds were found in the extracts and twenty-six were identified. The main components identified in the extracts in decreasing quantitative order were: curzerene, germacrene B, C(15)H(20)O(2) and beta-elemene for hydrodistillation; C(15)H(20)O(2) and curzerene for SC-CO(2) extracts and 3-hexen-1-ol, curzerene, C(15)H(20)O(2), beta-elemene and germacrene B for SC-CO(2) extracts captured in Porapak-Q. PRACTICAL APPLICATIONS The natural extracts are a potential source of compounds possessing biological activities. They can be used in foods, pharmaceutics and cosmetics. Pitanga is an exotic fruit from Brazil and extracts from its leaves have been used against many diseases in Brazilian folk medicine. Supercritical extraction is an interesting process for the production of natural extracts because it is a clean process and the knowledge of composition of extracts is crucial for the identification of the probable active components.

Brazilian red propolis: unreported substances, antioxidant and antimicrobial activities

BACKGROUND: Chloroform, ethyl acetate and methanol extracts of a sample of red propolis from the state of Alagoas (northeast Brazil) were analyzed by gas chromatography-mass spectrometry and high-performance liquid chromatography-diode array detection-electrospray ionization-mass spectrometry. Antimicrobial and antioxidant activities were also obtained. RESULTS: The propolis sample contained low content of narigenin-8-C-hexoside, this being the first report of a C-glycoside in propolis. The main constituent found was characterized as 3,4,2`,3`-tetrahydroxychalcone. Other important constituents were the chalcone isoliquiritigenin, the isoflavans (3S)-vestitol, (3S)-7-O-methylvestitol, the pterocarpan medicarpin, the phenylpropenes trans-anethol, methyl eugenol, elimicin, methoxyeugenol and cis-asarone, and the triterpenic alcohols lupeol and alpha- and beta- amyrins. The methanol extract exhibited high antioxidant activities by 2,2-diphenyl-1-picrylhydrazyl and beta-carotene/linoleic acid assay methods, and antimicrobial activity toward Gram-positive and Gram-negative bacteria. CONCLUSION: Structures are suggested for new substances never before seen in any kind of propolis. This is the first report of 3,4,2`,3`-tetrahydroxychalcone and a flavone C-glycoside in a propolis sample. (C) 2011 Society of Chemical Industry

Coupling Virus-Induced Gene Silencing to Exogenous Green Fluorescence Protein Expression Provides a Highly Efficient System for Functional Genomics in Arabidopsis and across All Stages of Tomato Fruit Development

Since the advent of the postgenomic era, efforts have focused on the development of rapid strategies for annotating plant genes of unknown function. Given its simplicity and rapidity, virus-induced gene silencing (VIGS) has become one of the preeminent approaches for functional analyses. However, several problems remain intrinsic to the use of such a strategy in the study of both metabolic and developmental processes. The most prominent of these is the commonly observed phenomenon of ""sectoring"" the tissue regions that are not effectively targeted by VIGS. To better discriminate these sectors, an effective marker system displaying minimal secondary effects is a prerequisite. Utilizing a VIGS system based on the tobacco rattle virus vector, we here studied the effect of silencing the endogenous phytoene desaturase gene (pds) and the expression and subsequent silencing of the exogenous green fluorescence protein (gfp) on the metabolism of Arabidopsis (Arabidopsis thaliana) leaves and tomato (Solanum lycopersicum) fruits. In leaves, we observed dramatic effects on primary carbon and pigment metabolism associated with the photobleached phenotype following the silencing of the endogenous pds gene. However, relatively few pleiotropic effects on carbon metabolism were observed in tomato fruits when pds expression was inhibited. VIGS coupled to gfp constitutive expression revealed no significant metabolic alterations after triggering of silencing in Arabidopsis leaves and a mild effect in mature green tomato fruits. By contrast, a wider impact on metabolism was observed in ripe fruits. Silencing experiments with an endogenous target gene of interest clearly demonstrated the feasibility of cosilencing in this system; however, carefully constructed control experiments are a prerequisite to prevent erroneous interpretation.

An approach to chemotaxonomy to the fatty acid content of some Malvaceae species

Malvales is an order of flowering plants with a controversial circumscription. The relationships between taxa, particularly Malvaceae, Bombacaceae, Sterculiaceae, and Tiliaceae, are not well delineated. Several studies have reported the fatty acid compositions of Malvaceae plants but not for taxonomic purposes. In the present study, the fatty acid composition of oilseeds from seven species belonging to the Malvaceae family was determined by capillary gas chromatography/mass spectrometry (GC/MS), and the quantitative distribution of fatty acids was analyzed by a cluster analysis With Euclidean Distance and UPGMA. The oil content in the seeds was very low (8.3-11.8%). The profile of fatty acids showed that there were two distinct groups: species rich in palmitic acid (Herissantia tiubae, Sidastrum paniculatum and Sida rhombifolia) and species rich in linoleic acid (other Sida species). The fatty acid profiles found for Sida species are consistent with other reported data. Although our data support a distinction between Sida and Sidastrum, more species should be analyzed to evaluate the real taxonomic value of differences in fatty acid content for distinguishing Malvaceae. (C) 2010 Elsevier Ltd. All rights reserved.

Morphometrical, biochemical and molecular tools for assessing biodiversity. An example in Plebeia remota (Holmberg, 1903) (Apidae, Meliponini)

We see today many efforts to quantify biodiversity in different biomes. It is very important then to develop and to apply other methodologies that allow us to assess biodiversity. Here we present an example of application of three tools with this goal. We analyzed two populations of Plebeia remota from two distinct biomes that already showed several differences in morphology and behavior. Based on these differences, it has been suggested that the populations of Cunha and Prudentopolis do not represent a single species. In order to verify the existence or absence of gene flow between these two groups, we characterized the patterns of mtDNA through RFLP, the patterns of wing venation through geometric morphometry, and the cuticular hydrocarbons through gas chromatography-mass spectrometry. We used bees collected in these two locations and also from colonies which have being kept for around 9 years at Sao Paulo University. We found six different haplotypes in these specimens, of which three of them occurred exclusively in the population of Cunha and three only in the Prudentopolis population. The fact that the populations do not share haplotypes suggests no maternal gene flow between them. The two populations were differentiated by the pattern of the wing veins. They also had different mixtures of cuticle hydrocarbons. Furthermore it was shown that the colonies kept at the university did not hybridize. These two groups may constitute different species. We also show here the importance of using other methodologies than traditional taxonomy to assess and understand biodiversity, especially in bees.

Comparison of fatty acid composition in nine organs of the sympatric Antarctic teleost fish species Notothenia coriiceps and Notothenia rossii (Perciformes: Nototheniidae)

Fatty acid (FA) composition of nine organs from two closely related Antarctic fish species, Notothenia codiceps and Notothenia rossii, was determined through gas chromatography with flame ionization detection. A data set for each species was obtained using major FA profiles from specimens caught in the sea waters of Admiralty Bay during the summer season. The FA profiles for both species are overall similar, but organ peculiarities have been found, which could reflect metabolic specificities and feeding habits between species. With the exception of liver, the most abundant FA in organs was the n-3 polyunsaturated FA. The total n-6 polyunsaturated FAs were minor components in all evaluated organs. Palmitic acid was identified as the major saturated FA, whereas oleic acid was the most represented of the monounsaturated FA in almost all assessed organs of both species. The n-3/n-6 ratios of all organs were higher than 3.5. Differences in individual FA and FA metabolic profiles of some organs observed between N. coriiceps and N. rossii suggest specific requirements in the mobilization, transport, incorporation, and/or catabolism of lipids that were reinforced by differences on some FA ratios expressing the activity coefficient of enzymes implicated on the FA pathway flux. (C) 2009 Elsevier Inc. All rights reserved.

Genotoxicity and composition of particulate matter from biomass burning in the eastern Brazilian Amazon region

In the present study Tradescantia pallida micronucleus (Trad-MCN) bioassay was used to assess the genotoxicity of particulate matter with a mass median aerodynamic diameter less than 10 pm (PM(10)) in Tangara da Serra (MT), a Brazilian Amazon region that suffers the impact of biomass burning. The levels of PM (coarse and fine size fractions) and black carbon (BC) collected were also measured. Furthermore, the alkanes and polycyclic aromatic hydrocarbons (PAHs) were identified and quantified in the samples taken during the burning period by gas chromatography with flame ionization detection (GC-FID). The PM and BC results for both fractions indicate a strong correlation (p < 0.001). The analysis of alkanes indicates an anthropic influence. Retene was the most abundant PAH found, an indicator of biomass burning, and 12 other PAHs considered to be potentially mutagenic and/or carcinogenic were identified in this sample. The Trad-MCN bioassay showed a significant increase in micronucleus frequency during the period of most intense burning, possibly related to the mutagenic PAHs that were found in such extracts. This study demonstrated that Trad-MCN was sensitive and efficient in evaluating the genotoxicity of organic compounds from biomass burning. It further emphasizes the importance of performing chemical analysis, because changes in chemical composition generally have a negative effect on many living organisms. This bioassay (ex situ), using T. pallida with chemical analysis, is thus recommended for characterizing the genotoxicity of air pollution. Crown Copyright (C) 2011 Published by Elsevier Inc. All rights reserved.

Nanostructured copper thin film used for catalysis

Catalytic properties of copper thin films deposited in small channels and cavities were tested using Raman microscopy and mass spectroscopy (MS) techniques, mainly. The catalytic surface conditions were addressed visually and chemically by optical microscopy and X-ray photoelectron spectroscopy (XPS), respectively. The experimental conditions of present work induced copper oxidation; eventually a number of carbon species and graphite remained on the catalytic surface. Quartz crystal microbalance and mass spectroscopy data support both adsorption and catalysis phenomena. MS showed CO2 formation during n-hexane heating process but not to 2-propanol, probably due to redox reactions. XPS of copper surface present in the cavity after catalysis tests detected Cu2O and a range of possible carbon species. The adsorption and catalytic performance of copper films deposited in cavities and microchannels were quite similar. A simple miniaturized device for microanalysis was proposed. (C) 2007 Elsevier B.V. All rights reserved.

Early Changes in Gene Expression Induced by Tobacco Smoke: Evidence for the Importance of Estrogen within Lung Tissue

Lung cancer is the leading cause of cancer deaths in the United States, surpassing breast cancer as the primary cause of cancer-related mortality in women. The goal of the present study was to identify early molecular changes in the lung induced by exposure to tobacco smoke and thus identify potential targets for chemoprevention. Female A/J mice were exposed to either tobacco smoke or HEPA-filtered air via a whole-body exposure chamber (6 h/d, 5 d/wk for 3, 8, and 20 weeks). Gene expression profiles of lung tissue from control and smoke-exposed animals were established using a 15K cDNA microarray. Cytochrome P450 1b1, a phase I enzyme involved in both the metabolism of xenobiotics and the 4-hydroxylation of 17 beta-estradiol (E(2)), was modulated to the greatest extent following smoke exposure. A panel of 10 genes were found to be differentially expressed in control and smoke-exposed lung tissues at 3, 8, and 20 weeks (P < 0.001). The interaction network of these differentially expressed genes revealed new pathways modulated by short-term smoke exposure, including estrogen metabolism. In addition, E(2) was detected within murine lung tissue by gas chromatography-coupled mass spectrometry and immunohistochemistry. Identification of the early molecular events that contribute to lung tumor formation is anticipated to lead to the development of promising targeted chemopreventive therapies. In conclusion, the presence of E2 within lung tissue when combined with the modulation of cytochrome P450 1b1 and other estrogen metabolism genes by tobacco smoke provides novel insight into a possible role for estrogens in lung cancer. Cancer Prev Res; 3(6); 707-17. (C) 2010 AACR.

Useful Strategies for Algal Volatile Analysis

The production of volatile organic compounds (VOC) by plants is well known. However, few scientific groups have studied VOC produced by green, brown and red algae. Headspace collection of volatiles and solid phase microextraction, as well as the traditional extraction by hydrodistillation combined with analytical chromatographic techniques (i.e., GC-MS), have significantly improved the investigation of VOC from plants and algae. The major volatile compounds found in seaweeds are hydrocarbons, terpenes, phenols, alcohols, aldehydes, ketones, esters, fatty acids and halogen or sulfur-containing compounds. This article presents an overview of VOC isolated from and identified in marine macro-algae. Focus is given to non-halogenated and non-sulfur volatile compounds, as well as strategies to analyze and identify algal VOC by GC-MS.