Optimization and validation of organochlorine compounds in adipose tissue by SPE-gas chromatography

Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid-phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18-E), benzenesulfonic acid modified silica cation exchanger (SA), poly (styrene-divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C18-E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries>70% with standard deviations (SD)<15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′-DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd.

Haptoglobin, acid phosphatase and demographic factors: obesity risk

The aim of this work is to study the risk of obesity posed by two genetic factors: haptoglobin phenotype and acid phosphatase phenotype, one enzymatic activity: acid phosphatase activity (ACP1), age and gender. Haptoglobin (Hp) is a protein of the immune system, and three phenotypes of Hp are found in humans: Hp1-1, Hp2-1, and Hp2-2. This protein is associated with a susceptibility to common pathological conditions, such as obesity. ACP1 is an intracellular enzyme The phenotypes of ACP1 (AA, AB, AC, BB, BC, CC) are also considered. We took a sample of 127 subjects with complete data from 714 registers. Since we intend to identify risk factors for obesity, an ordinal regression model is adjusted, using the Body Mass Index, BMI, to define weight categories. Haptoglobin phenotype, enzymatic activity of ACP1, acid phosphatase phenotype, age and gender are considered as regressor variables. We found three factors associated with an increased risk of obesity: phenotype Hp2-1 of haptoglobin (estimated odds ratio OR 11.54), phenotype AA of acid phosphatase (OR 33.788) and age (OR 1.39). The interaction between phenotype Hp2-1 and phenotype AC is associated with a decreased risk of obesity (OR 0.032); The interaction between phenotype AA and ACP1 activity is associated with a decreased risk of obesity (OR 0.954).

Application of wetland systems in the treatment of acid rock mine drainage

The presented work was conducted within the Dissertation / Internship, branch of Environmental Protection Technology, associated to the Master thesis in Chemical Engineering by the Instituto Superior de Engenharia do Porto and it was developed in the Aquatest a.s, headquartered in Prague, in Czech Republic. The ore mining exploitation in the Czech Republic began in the thirteenth century, and has been extended until the twentieth century, being now evident the consequences of the intensive extraction which includes contamination of soil and sub-soil by high concentrations of heavy metals. The mountain region of Zlaté Hory was chosen for the implementation of the remediation project, which consisted in the construction of three cells (tanks), the first to raise the pH, the second for the sedimentation of the formed precipitates and a third to increase the process efficiency in order to reduce high concentrations of metals, with special emphasis on iron, manganese and sulfates. This project was initiated in 2005, being pioneer in this country and is still ongoing due to the complex chemical and biological phenomenon’s inherent to the system. At the site where the project was implemented, there is a natural lagoon, thereby enabling a comparative study of the two systems (natural and artificial) regarding the efficiency of both in the reduction/ removal of the referred pollutants. The study aimed to assist and cooperate in the ongoing investigation at the company Aquatest, in terms of field work conducted in Zlaté Hory and in terms of research methodologies used in it. Thereby, it was carried out a survey and analysis of available data from 2005 to 2008, being complemented by the treatment of new data from 2009 to 2010. Moreover, a theoretical study of the chemical and biological processes that occurs in both systems was performed. Regarding the field work, an active participation in the collection and in situ sample analyzing of water and soil from the natural pond has been attained, with the supervision of Engineer, Irena Šupiková. Laboratory analysis of water and soil were carried out by laboratory technicians. It was found that the natural lagoon is more efficient in reducing iron and manganese, being obtained removal percentages of 100%. The artificial lagoon had a removal percentage of 90% and 33% for iron and manganese respectively. Despite the minor efficiency of the constructed wetland, it must be pointed out that this system was designed for the treatment and consequent reduction of iron. In this context, it can conclude that the main goal has been achieved. In the case of sulphates, the removal optimization is yet a goal to be achieved not only in the Czech Republic but also in other places where this type of contamination persists. In fact, in the natural lagoon and in the constructed wetland, removal efficiencies of 45% and 7% were obtained respectively. It has been speculated that the water at the entrance of both systems has different sources. The analysis of the collected data shows at the entrance of the natural pond, a concentration of 4.6 mg/L of total iron, 14.6 mg/L of manganese and 951 mg/L of sulphates. In the artificial pond, the concentrations are 27.7 mg/L, 8.1 mg/L and 382 mg/L respectively for iron, manganese and sulphates. During 2010 the investigation has been expanded. The study of soil samples has started in order to observe and evaluate the contribution of bacteria in the removal of heavy metals being in its early phase. Summarizing, this technology has revealed to be an interesting solution, since in addition to substantially reduce the mentioned contaminants, mostly iron, it combines the low cost of implementation with an reduced maintenance, and it can also be installed in recreation parks, providing habitats for plants and birds.

Ecosapentanoic acid (EPA) does not affect cell kinetics in peripheral lymphocites from patients with Crohn's disease (CD) according to IL6 174G/C polymorphism

Rationale: Omega 3 fatty acids have been shown to be of potential benefit in patients with CD. The aim of the present study was to evaluate whether EPA can modulate the inflammatory response according to different genotypes of IL6G174G/C polymorphism. Methods: Peripheral blood cells were collected from CD patients with different genotypes for IL6 174G/C (GG, n = 16, GC, n = 8, CC, n = 7), and lymphocytes were established in culture media. Replicates with the addition of EPA (25 mM) were analysed in a period of 24h, 48h and 72h. Expression of IL6 e a PGE2 was assessed by ELISA. Apoptosis and cellular proliferation was determined by flow cytometry.

Evidence of inadequate docosahexaenoic acid status in Brazilian pregnant and lactating women

Recently published data concerning dietary intake of fat and food sources of (n-3) long-chain polyunsaturated fatty acids (LCPUFA) in Brazil are reviewed together with data on biochemical indices of PUFA status during pregnancy and lactation and PUFA composition of breast milk in Brazilian adolescents and adults. Potential inadequacies of docosahexaenoic acid (DHA) status among Brazilian pregnant and lactating women have not yet been thoroughly evaluated. The data reviewed show that dietary intake of food sources of n-3 LCPUFA is low and possibly deficient in Brazil, and that biochemical indices of maternal DHA status and breast milk DHA content are low compared to the international literature. These data indicate inadequate DHA status among Brazilian women during pregnancy and lactation, but this evidence needs confirmation through comprehensive and specific population-based studies.

Trans fatty acid intake among the population of the city of São Paulo, Brazil

OBJECTIVE: To analyze the monounsaturated and polyunsaturated trans fatty acid intake among the general population. METHODS: A cross-sectional study was conducted in São Paulo, Southeastern Brazil, in 2003, on a representative sample of 2,298 male and female subjects, including 803 adolescents (12 to 19 years), 713 adults (20 to 59 years) and 782 elderly people (60 years or over). Food intake was measured using 24-hour recall. Mean trans fatty acid intake was described according to gender and age group. RESULTS: The mean trans fatty acid intake was 5.0 g/day (SE = 0.1), accounting for 2.4% (SE = 0.1) of total energy and 6.8% (SE = 0.1) of total lipids. The adolescents had the highest mean intake levels (7.4 g/day; 2.9% of energy) while the adults and the elderly had similar intake (2.2% of energy for both; 6.4% of lipids and 6.5% of lipids, respectively). The mean trans fatty acid intake among adult and elderly women (approximately 2.5% of energy and 7.0% of lipids) was higher than among men in the same age group. The food item with the highest contribution towards trans fatty acids was margarine, accounting for more than 30% of total intake, followed by filled cookies among adolescents and meat among adults and the elderly. CONCLUSIONS: The trans fatty acid intake is above the level recommended by the World Health Organization. Replacement of the trans fatty acids in manufactured food items may be an effective measure for reducing trans fatty acid intake in Brazil.

Determination of tartaric acid in wines by FIA with tubular tartrate-selective electrodes

A flow injection analysis (FIA) system comprising a tartrate- (TAT) selective electrode has been developed for determination of tartaric acid in wines. Several electrodes constructed for this purpose had a PVC membrane with a complex of quaternary ammonium and TAT as anion exchanger, a phenol derivative as additive, and a more or less polar mediator solvent. Characterization of the electrodes showed behavior was best for membranes with o-nitrophenyl octyl ether as solvent. On injection of 500 μL into a phosphate buffer carrier (pH = 3.1; ionic strength 10–2 mol/L) flowing at 3 mL/min, the slope was 58.06 ± 0.6 with a lower limit of linear range of 5.0 × 10–4 mol/L TAT and R2 = 0.9989. The interference of several species, e.g. chloride, bromide, iodide, nitrate, gallic acid, tannin, sucrose, glucose, fructose, acetate, and citrate, was evaluated in terms of potentiometric selectivity coefficients. The Hofmeister series was followed for inorganic species and the most interfering organic ion was citrate. When red and white wines were analyzed and the results compared with those from an independent method they were found to be accurate, with relative standard deviations below 5.0%.

Transformations induced in bulk amorphous silica by ultrafast laser direct writingTransformations induced in bulk amorphous silica by ultrafast laser direct writing

Agências Financiadoras: Fundação para a Ciência e a Tecnologia - PTDC/FIS/102127/2008 e PTDC/FIS/102127/2008 e SFRH/BPD/78871/2011; Spanish Ministerio de Ciencia e Innovacion - FUNCOAT-CSD2008-00023-CONSOLIDER; Instituto Superior Técnico;

Rapid determination of tartaric acid in wines

A flow-spectrophotometric method is proposed for the routine determination of tartaric acid in wines. The reaction between tartaric acid and vanadate in acetic media is carried out in flowing conditions and the subsequent colored complex is monitored at 475 nm. The stability of the complex and the corresponding formation constant are presented. The effect of wavelength and pH was evaluated by batch experiments. The selected conditions were transposed to a flowinjection analytical system. Optimization of several flow parameters such as reactor lengths, flow-rate and injection volume was carried out. Using optimized conditions, a linear behavior was observed up to 1000 µg mL-1 tartaric acid, with a molar extinction coefficient of 450 L mg-1 cm-1 and ± 1 % repeatability. Sample throughput was 25 samples per hour. The flow-spectrophotometric method was satisfactorily applied to the quantification of tartaric acid (TA) in wines from different sources. Its accuracy was confirmed by statistical comparison to the conventional Rebelein procedure and to a certified analytical method carried out in a routine laboratory.

FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks

Ascorbic acid is found in many food samples. Its clinical and technological importance demands an easyto- use, rapid, robust and inexpensive method of analysis. For this purpose, this work proposes a new flow procedure based on the oxidation of ascorbic acid by periodate. A new potentiometric periodate sensor was constructed to monitor this reaction. The selective membranes were of PVC with porphyrin-based sensing systems and a lipophilic cation as additive. The sensor displayed a near-Nernstian response for periodate over 1.0x10-2–6.0x10-6 M, with an anionic slope of 73.9 ± 0.9 mV decade-1. It was pH independent in acidic media and presented good selectivity features towards several inorganic anions. The flow set-up operated in double-channel, carrying a 5.0x10-4 M IO- 4 solution and a suitable buffer; these were mixed in a 50-cm reaction coil. The overall flow rate was 7 ml min-1 and the injection volume 70 µl. Under these conditions, a linear behaviour against concentration was observed for 17.7–194.0 µg ml-1, presenting slopes of 0.169 mV (mg/l)-1, a reproducibility of ±1.1 mV (n = 5), and a sampling rate of ~96 samples h-1. The proposed method was applied to the analysis of beverages and pharmaceuticals.

Distribution system operation supported by contextual energy resource management based on intelligent SCADA

Future distribution systems will have to deal with an intensive penetration of distributed energy resources ensuring reliable and secure operation according to the smart grid paradigm. SCADA (Supervisory Control and Data Acquisition) is an essential infrastructure for this evolution. This paper proposes a new conceptual design of an intelligent SCADA with a decentralized, flexible, and intelligent approach, adaptive to the context (context awareness). This SCADA model is used to support the energy resource management undertaken by a distribution network operator (DNO). Resource management considers all the involved costs, power flows, and electricity prices, allowing the use of network reconfiguration and load curtailment. Locational Marginal Prices (LMP) are evaluated and used in specific situations to apply Demand Response (DR) programs on a global or a local basis. The paper includes a case study using a 114 bus distribution network and load demand based on real data.

Electrochemical and spectroscopic studies of the oxidation mechanism of the herbicide propanil

Electrochemical oxidation of propanil in deuterated solutions was studied by cyclic, differential pulse, and square wave voltammetry using a glassy carbon microelectrode. The oxidation of propanil in deuterated acid solutions occurs at the nitrogen atom of the amide at a potential of +1.15 V vs Ag/ AgCl. It was also found that, under the experimental conditions used, protonation at the oxygen atom of propanil occurs, leading to the appearance of another species in solution which oxidizes at +0.60 V. The anodic peak found at +0.79 V vs Ag/AgCl in deuterated basic solutions is related to the presence of an anionic species in which a negative charge is on the nitrogen atom. The electrochemical data were confirmed by the identification of all the species formed in acidic and basic deuterated solutions by means of NMR spectroscopy. The results are supported by electrochemical and spectroscopic studies of acetanilide in deuterated solutions.

An integrated recycling approach for GFRP pultrusion wastes: recycling and reuse assessment into new composite materials using Fuzzy Boolean Nets

In this study, efforts were made in order to put forward an integrated recycling approach for the thermoset based glass fibre reinforced polymer (GPRP) rejects derived from the pultrusion manufacturing industry. Both the recycling process and the development of a new cost-effective end-use application for the recyclates were considered. For this purpose, i) among the several available recycling techniques for thermoset based composite materials, the most suitable one for the envisaged application was selected (mechanical recycling); and ii) an experimental work was carried out in order to assess the added-value of the obtained recyclates as aggregates and reinforcement replacements into concrete-polymer composite materials. Potential recycling solution was assessed by mechanical behaviour of resultant GFRP waste modified concrete-polymer composites with regard to unmodified materials. In the mix design process of the new GFRP waste based composite material, the recyclate content and size grade, and the effect of the incorporation of an adhesion promoter were considered as material factors and systematically tested between reasonable ranges. The optimization process of the modified formulations was supported by the Fuzzy Boolean Nets methodology, which allowed finding the best balance between material parameters that maximizes both flexural and compressive strengths of final composite. Comparing to related end-use applications of GFRP wastes in cementitious based concrete materials, the proposed solution overcome some of the problems found, namely the possible incompatibilities arisen from alkalis-silica reaction and the decrease in the mechanical properties due to high water-cement ratio required to achieve the desirable workability. Obtained results were very promising towards a global cost-effective waste management solution for GFRP industrial wastes and end-of-life products that will lead to a more sustainable composite materials industry.

Exploring nature profits: development of novel and potent lipophilic antioxidants based on galloylecinnamic hybrids

Phenolic acids are ubiquitous antioxidants accounting for approximately one third of the phenolic compounds in our diet. Their importance was supported by epidemiological studies that suggest an inverse relationship between dietary intake of phenolic antioxidants and the occurrence of diseases, such as cancer and neurodegenerative disorders. However, until now, most of natural antioxidants have limited therapeutic success a fact that could be related with their limited distribution throughout the body and with the inherent difficulties to attain the target sites. The development of phenolic antioxidants based on a hybrid concept and structurally based on natural hydroxybenzoic (gallic acid) and hydroxycinnamic (caffeic acid) scaffolds seems to be a suitable solution to surpass the mentioned drawbacks. Galloylecinnamic hybrids were synthesized and their antioxidant activity as well as partition coefficients and redox potentials evaluated. The structureepropertyeactivity relationship (SPAR) study revealed the existence of a correlation between the redox potentials and antioxidant activity. The galloylecinnamic acid hybrid stands out as the best antioxidant supplementing the effect of a blend of gallic acid plus caffeic acid endorsing the hypothesis that the whole is greater than the sum of the parts. In addition, some hybrid compounds possess an appropriate lipophilicity allowing their application as chain-breaking antioxidant in biomembranes or other type of lipidic systems. Their predicted ADME properties are also in accordance with the general requirements for drug-like compounds. Accordingly, these phenolic hybrids can be seen as potential antioxidants for tackling the oxidative status linked to the neurodegenerative, inflammatory or cancer processes.