Investigation of urinary volatile organic metabolites as potential cancer biomarkers by solid-phase microextraction in combination with gas chromatography-mass spectrometry

BACKGROUND: Non-invasive diagnostic strategies aimed at identifying biomarkers of cancer are of great interest for early cancer detection. Urine is potentially a rich source of volatile organic metabolites (VOMs) that can be used as potential cancer biomarkers. Our aim was to develop a generally reliable, rapid, sensitive, and robust analytical method for screening large numbers of urine samples, resulting in a broad spectrum of native VOMs, as a tool to evaluate the potential of these metabolites in the early diagnosis of cancer. METHODS: To investigate urinary volatile metabolites as potential cancer biomarkers, urine samples from 33 cancer patients (oncological group: 14 leukaemia, 12 colorectal and 7 lymphoma) and 21 healthy (control group, cancer-free) individuals were qualitatively and quantitatively analysed. Dynamic solid-phase microextraction in headspace mode (dHS-SPME) using a carboxenpolydimethylsiloxane (CAR/PDMS) sorbent in combination with GC-qMS-based metabolomics was applied to isolate and identify the volatile metabolites. This method provides a potential non-invasive method for early cancer diagnosis as a first approach. To fulfil this objective, three important dHS-SPME experimental parameters that influence extraction efficiency (fibre coating, extraction time and temperature of sampling) were optimised using a univariate optimisation design. The highest extraction efficiency was obtained when sampling was performed at 501C for 60min using samples with high ionic strengths (17% sodium chloride, wv 1) and under agitation. RESULTS: A total of 82 volatile metabolites belonging to distinct chemical classes were identified in the control and oncological groups. Benzene derivatives, terpenoids and phenols were the most common classes for the oncological group, whereas ketones and sulphur compounds were the main classes that were isolated from the urine headspace of healthy subjects. The results demonstrate that compound concentrations were dramatically different between cancer patients and healthy volunteers. The positive rates of 16 patients among the 82 identified were found to be statistically different (Po0.05). A significant increase in the peak area of 2-methyl3-phenyl-2-propenal, p-cymene, anisole, 4-methyl-phenol and 1,2-dihydro-1,1,6-trimethyl-naphthalene in cancer patients was observed. On average, statistically significant lower abundances of dimethyl disulphide were found in cancer patients. CONCLUSIONS: Gas chromatographic peak areas were submitted to multivariate analysis (principal component analysis and supervised linear discriminant analysis) to visualise clusters within cases and to detect the volatile metabolites that are able to differentiate cancer patients from healthy individuals. Very good discrimination within cancer groups and between cancer and control groups was achieved.

Dynamic headspace solid-phase microextraction combined with one-dimensional gas chromatography–mass spectrometry as a powerful tool to differentiate banana cultivars based on their volatile metabolite profile

In this study the effect of the cultivar on the volatile profile of five different banana varieties was evaluated and determined by dynamic headspace solid-phase microextraction (dHS-SPME) combined with one-dimensional gas chromatography–mass spectrometry (1D-GC–qMS). This approach allowed the definition of a volatile metabolite profile to each banana variety and can be used as pertinent criteria of differentiation. The investigated banana varieties (Dwarf Cavendish, Prata, Maçã, Ouro and Platano) have certified botanical origin and belong to the Musaceae family, the most common genomic group cultivated in Madeira Island (Portugal). The influence of dHS-SPME experimental factors, namely, fibre coating, extraction time and extraction temperature, on the equilibrium headspace analysis was investigated and optimised using univariate optimisation design. A total of 68 volatile organic metabolites (VOMs) were tentatively identified and used to profile the volatile composition in different banana cultivars, thus emphasising the sensitivity and applicability of SPME for establishment of the volatile metabolomic pattern of plant secondary metabolites. Ethyl esters were found to comprise the largest chemical class accounting 80.9%, 86.5%, 51.2%, 90.1% and 6.1% of total peak area for Dwarf Cavendish, Prata, Ouro, Maçã and Platano volatile fraction, respectively. Gas chromatographic peak areas were submitted to multivariate statistical analysis (principal component and stepwise linear discriminant analysis) in order to visualise clusters within samples and to detect the volatile metabolites able to differentiate banana cultivars. The application of the multivariate analysis on the VOMs data set resulted in predictive abilities of 90% as evaluated by the cross-validation procedure.

Headspace solid-phase microextraction-gas chromatography-quadrupole mass spectrometric methodology for the establishment of the volatile composition of Passiflora fruit species

Dynamic headspace solid-phase microextraction (HS-SPME) followed by thermal desorption gas chromatography-quadrupole mass spectrometry analysis (GC-qMS), was used to investigate the aroma profile of different species of passion fruit samples. The performance of five commercially available SPME fibres: 65 μm polydimethylsiloxane/divinylbenzene, PDMS/DVB; 100 μm polydimethylsiloxane, PDMS; 85 μm polyacrylate, PA; 50/30 μm divinylbenzene/carboxen on polydimethylsiloxane, DVB/CAR/PDMS (StableFlex); and 75 μm carboxen/polydimethylsiloxane, CAR/PDMS; was evaluated and compared. Several extraction times and temperature conditions were also tested to achieve optimum recovery. The SPME fibre coated with 65 μm PDMS/DVB afforded the highest extraction efficiency, when the samples were extracted at 50 °C for 40 min with a constant stirring velocity of 750 rpm, after saturating the sample with NaCl (17%, w/v — 0.2 g). A comparison among different passion fruit species has been established in terms of qualitative and semi-quantitative differences in volatile composition. By using the optimal extraction conditions and GC-qMS it was possible to tentatively identify seventy one different compounds in Passiflora species: 51 volatiles in Passiflora edulis Sims (purple passion fruit), 24 in P. edulis Sims f. flavicarpa (yellow passion fruit) and 21 compounds in Passiflora mollissima (banana passion fruit). It was found that the ethyl esters comprise the largest class of the passion fruit volatiles, including 82.8% in P. edulis variety, 77.4% in P. edulis Sims f. flavicarpa variety and 39.9% in P. mollissima. The semi-quantitative results were then submitted to principal component analysis (PCA) in order to establish relationships between the compounds and the different passion fruit species under investigation.

Optimisation of solid-phase microextraction combined with gas chromatography–mass spectrometry based methodology to establish the global volatile signature in pulp and skin of Vitis vinifera L. grape varieties

The volatiles (VOCs) and semi-volatile organic compounds (SVOCs) responsible for aroma are mainly present in skin of grape varieties. Thus, the present investigation is directed towards the optimisation of a solvent free methodology based on headspace-solid-phase microextraction (HS-SPME) combined with gas chromatography–quadrupole mass spectrometry (GC–qMS) in order to establish the global volatile composition in pulp and skin of Bual and Bastardo Vitis vinifera L. varieties. A deep study on the extraction-influencing parameters was performed, and the best results, expressed as GC peak area, number of identified compounds and reproducibility, were obtained using 4 g of sample homogenised in 5 mL of ultra-pure Milli-Q water in a 20 mL glass vial with addition of 2 g of sodium chloride (NaCl). A divinylbenzene/carboxen/polydimethylsiloxane fibre was selected for extraction at 60 °C for 45 min under continuous stirring at 800 rpm. More than 100 VOCs and SVOCs, including 27 monoterpenoids, 27 sesquiterpenoids, 21 carbonyl compounds, 17 alcohols (from which 2 aromatics), 10 C13 norisoprenoids and 5 acids were identified. The results showed that, for both grape varieties, the levels and number of volatiles in skin were considerably higher than those observed in pulp. According to the data obtained by principal component analysis (PCA), the establishment of the global volatile signature of grape and the relationship between different part of grapes—pulp and skin, may be an useful tool to winemaker decision to define the vinification procedures that improves the organoleptic characteristics of the corresponding wines and consequently contributed to an economic valorization and consumer acceptance.

Allergic asthma exhaled breath metabolome: a challenge for comprehensive two-dimensional gas chromatography

Allergic asthma represents an important public health issue, most common in the paediatric population, characterized by airway inflammation that may lead to changes in volatiles secreted via the lungs. Thus, exhaled breath has potential to be a matrix with relevant metabolomic information to characterize this disease. Progress in biochemistry, health sciences and related areas depends on instrumental advances, and a high throughput and sensitive equipment such as comprehensive two-dimensional gas chromatography–time of flight mass spectrometry (GC × GC–ToFMS) was considered. GC × GC–ToFMS application in the analysis of the exhaled breath of 32 children with allergic asthma, from which 10 had also allergic rhinitis, and 27 control children allowed the identification of several hundreds of compounds belonging to different chemical families. Multivariate analysis, using Partial Least Squares-Discriminant Analysis in tandem with Monte Carlo Cross Validation was performed to assess the predictive power and to help the interpretation of recovered compounds possibly linked to oxidative stress, inflammation processes or other cellular processes that may characterize asthma. The results suggest that the model is robust, considering the high classification rate, sensitivity, and specificity. A pattern of six compounds belonging to the alkanes characterized the asthmatic population: nonane, 2,2,4,6,6-pentamethylheptane, decane, 3,6-dimethyldecane, dodecane, and tetradecane. To explore future clinical applications, and considering the future role of molecular-based methodologies, a compound set was established to rapid access of information from exhaled breath, reducing the time of data processing, and thus, becoming more expedite method for the clinical purposes.

Uma metodologia para a análise do desempenho sustentável dos postos de revenda de combustível na cidade de Natal/RN, com o uso de data envelopment analysis-DEA

The increasing use of fossil fuels in line with cities demographic explosion carries out to huge environmental impact in society. For mitigate these social impacts, regulatory requirements have positively influenced the environmental consciousness of society, as well as, the strategic behavior of businesses. Along with this environmental awareness, the regulatory organs have conquered and formulated new laws to control potentially polluting activities, mostly in the gas stations sector. Seeking for increasing market competitiveness, this sector needs to quickly respond to internal and external pressures, adapting to the new standards required in a strategic way to get the Green Badge . Gas stations have incorporated new strategies to attract and retain new customers whom present increasingly social demand. In the social dimension, these projects help the local economy by generating jobs and income distribution. In this survey, the present research aims to align the social, economic and environmental dimensions to set the sustainable performance indicators at Gas Stations sector in the city of Natal/RN. The Sustainable Balanced Scorecard (SBSC) framework was create with a set of indicators for mapping the production process of gas stations. This mapping aimed at identifying operational inefficiencies through multidimensional indicators. To carry out this research, was developed a system for evaluating the sustainability performance with application of Data Envelopment Analysis (DEA) through a quantitative method approach to detect system s efficiency level. In order to understand the systemic complexity, sub organizational processes were analyzed by the technique Network Data Envelopment Analysis (NDEA) figuring their micro activities to identify and diagnose the real causes of overall inefficiency. The sample size comprised 33 Gas stations and the conceptual model included 15 indicators distributed in the three dimensions of sustainability: social, environmental and economic. These three dimensions were measured by means of classical models DEA-CCR input oriented. To unify performance score of individual dimensions, was designed a unique grouping index based upon two means: arithmetic and weighted. After this, another analysis was performed to measure the four perspectives of SBSC: learning and growth, internal processes, customers, and financial, unifying, by averaging the performance scores. NDEA results showed that no company was assessed with excellence in sustainability performance. Some NDEA higher efficiency Gas Stations proved to be inefficient under certain perspectives of SBSC. In the sequence, a comparative sustainable performance and assessment analyzes among the gas station was done, enabling entrepreneurs evaluate their performance in the market competitors. Diagnoses were also obtained to support the decision making of entrepreneurs in improving the management of organizational resources and promote guidelines the regulators. Finally, the average index of sustainable performance was 69.42%, representing the efforts of the environmental suitability of the Gas station. This results point out a significant awareness of this segment, but it still needs further action to enhance sustainability in the long term

Intraocular pressure and its correlation with blood gas parameters in crested caracaras (Caracara plancus) anesthetized with isoflurane and sevoflurane

Avaliou-se a pressão intra-ocular (PIO) e estimaram-se as correlações entre PIO e pressão de dióxido de carbono (PaCO2) e pH arterial de cinco caracarás (Caracara plancus), anestesiados com isofluorano (ISO) ou sevofluorano (SEV). Valores basais da PIO foram aferidos em ambos os olhos (M0). Cateterizou-se previamente a artéria braquial para obtenção de parâmetros hemogasométricos e cardiorrespiratórios. Anestesia foi induzida com ISO a 5V% e mantida por 40 minutos com 2,5V%. PIO e amostras de sangue foram avaliadas em diferentes momentos até o final do procedimento. Após recuperação, uma segunda anestesia foi realizada com SEV a 6% e mantida com 3,5%. Os parâmetros foram aferidos nos mesmos momentos estabelecidos previamente. A PIO decresceu significativamente (P=0,012) de M0 em todos os momentos e não houve diferença estatística entre ISO e SEV. Correlações significativas entre PIO e PaCO2 e entre PIO e pH sangüíneo foram observadas apenas para a anestesia com SEV. O pH sangüíneo decresceu paralelamente a PIO, enquanto a PaCO2 aumentou, em carcarás anestesiados com isofluorano e sevofluorano.

Simulador computacional do comportamento em regime de poços de petróleo equipados com gas-lift contínuo

Amongst the results of the AutPoc Project - Automation of Wells, established between UFRN and Petrobras with the support of the CNPq, FINEP, CTPETRO, FUNPEC, was developed a simulator for equipped wells of oil with the method of rise for continuous gas-lift. The gas-lift is a method of rise sufficiently used in production offshore (sea production), and its basic concept is to inject gas in the deep one of the producing well of oil transform it less dense in order to facilitate its displacement since the reservoir until the surface. Based in the use of tables and equations that condense the biggest number of information on characteristics of the reservoir, the well and the valves of gas injection, it is allowed, through successive interpolations, to simulate representative curves of the physical behavior of the existing characteristic variable. With a simulator that approaches a computer of real the physical conditions of an oil well is possible to analyze peculiar behaviors with very bigger speeds, since the constants of time of the system in question well are raised e, moreover, to optimize costs with assays in field. The simulator presents great versatility, with prominance the analysis of the influence of parameters, as the static pressure, relation gas-liquid, pressure in the head of the well, BSW (Relation Basic Sediments and Water) in curves of request in deep of the well and the attainment of the curve of performance of the well where it can be simulated rules of control and otimization. In moving the rules of control, the simulator allows the use in two ways of simulation: the application of the control saw software simulated enclosed in the proper simulator, as well as the use of external controllers. This implies that the simulator can be used as tool of validation of control algorithms. Through the potentialities above cited, of course one another powerful application for the simulator appears: the didactic use of the tool. It will be possible to use it in formation courses and recycling of engineers

Pyrolysis and combustion of pulp mill lime sludge

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

Rapid determination of desorption efficiency, and analysis of solvent mixtures for occupational exposure studies

An analytical procedure has been developed for simultaneous determination of solvent mixture vapors to enable evaluation of occupational exposure. To determine the desorption efficiency the volatile components of the solvent mixtures were generated from a glass tube filled with glass wool. This device is easy to prepare and use. These vapors were then collected in activated charcoal tubes and analyzed by capillary gas chromatography. The method was tested with a mixture of 22 solvents, including aliphatic and aromatic hydrocarbons, alcohols, ethers, esters, and ketones, oil at low concentrations. All the components were defected. When a 99: 1 mixture of carbon disulfide-dimethylformamide was used for desorption the efficiency was > 75% for most of the solvents.

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Multiresidue determination of pesticides in honey samples by gas chromatography-mass spectrometry and application in environmental contamination

A simple and fast multiresidue method has been developed to determine 48 pesticides within the major groups of pesticides (organohalogen, organophosphorous, pyrethroids and organonitrogen) in representative samples of locally produced honey, in Bauru (State of São Paulo, Brazil) during 2003-2004. The recovery results found ranged from 76% to 95% and the limits of detection were lower than 0.01 mg/kg for gas chromatography with electron impact mass spectrometric detection in the selected ion monitoring mode (GC-MS-SIM). The results indicated that most pesticides found in the samples belonged to the organohalogen and organophosphorous groups and lower levels of residues of some organonitrogen and pyretroids were also detected. Malathion residues were detected in all the samples, in a high concentration, owing to its applications to control dengue mosquitoes in the area studied. (c) 2005 Elsevier Ltd. All rights reserved.

Thermoeconomic analysis method for optimization of combined heat and power systems

This article presents an thermoeconomic analysis of cogeneration plants, applied as a rational technique to produce electric power and saturated steam. The aim of this new methodology is the minimum exergetic manufacturing cost (EMC), based on the Second Law of Thermodynamics. The decision variables selected for the optimization are the pressure and the temperature of the steam leaving the boiler in the case of using steam turbine, and the pressure ratio, turbine exhaust temperature and mass flow in the case of using gas turbines. The equations for calculating the capital costs of the components and products are formulated as a function of these decision variables. An application of the method using real data of a multinational chemical industry located in São Paulo state is presented. The conditions which establish the minimum cost are presented as finals conclusions.

Thermoeconomic analysis applied in cold water production system using biogas combustion

In this paper is proposed the use of biogas generated in the Wastewater Treatment Plant of a Dairy industry. The objective is to apply a thermoeconomic analysis to the supplementary cold water production of an absorption refrigeration system (NH3 + H2O) by the burning of such gas. The exergoeconomic analysis is carried out to allow a comparison between an absorption refrigeration system and of an equivalent compression refrigeration system that uses NH3 as work fluid. The proposed exergoeconomic model uses functional diagrams and allows one to obtain the exergetic incremental functions for each component individually and for the system as a whole. The model minimizes the exergetic manufacturing cost (EMC) which represents the cost of supplementary cold water production at 1degreesC (exergetic base) needed for this dairy's cold storage. As a conclusion, the absorption refrigeration system is better than compression refrigeration system, when the biogas cost is not considered. 2004 Elsevier Ltd. All rights reserved.

Combined cycle versus one thousand diesel power plants: pollutant emissions, ecological efficiency and economic analysis

The increase in the use of natural gas in Brazil has stimulated public and private sectors to analyse the possibility of using combined cycle systems for generation of electrical energy. Gas turbine combined cycle power plants are becoming increasingly common due to their high efficiency, short lead times, and ability to meet environmental standards. Power is produced in a generator linked directly to the gas turbine. The gas turbine exhaust gases are sent to a heat recovery steam generator to produce superheated steam that can be used in a steam turbine to produce additional power. In this paper a comparative study between a 1000 MW combined cycle power plant and 1000 kW diesel power plant is presented. In first step, the energetic situation in Brazil, the needs of the electric sector modification and the needs of demand management and integrated means planning are clarified. In another step the characteristics of large and small thermoelectric power plants that use natural gas and diesel fuel, respectively, are presented. The ecological efficiency levels of each type of power plant is considered in the discussion, presenting the emissions of particulate material, sulphur dioxide (SO2), carbon dioxide (CO2) and nitrogen oxides (NOx). (c) 2006 Elsevier Ltd. All rights reserved.