A GC-FID Method to Determine Styrene in Polystyrene Glasses

The styrene levels of polystyrene (PS) glasses from the most consumed brands of disposable glasses intended for water and coffee in Brazil were determined. A GC-FID method was developed and validated, showing good precision and accuracy. The method was successfully used to determine styrene in 11 PS glass brands. The styrene levels ranged from 1.68 to 43.69 mg/100 g glass, depending on the kind of polymer, thickness, and glass brand. It could be used to control the content of styrene in the polymer. The migration of styrene from the glasses into water and 20 % ethanol was not detected.

Determinação simultânea de Glicerol livre e total, MONO-, DI e triglicerídeos em biodiesel etílico de girassol, mamona e da mistura de sebo e soja empregando GC-FID

O biodiesel produzido para ser comercializado no Brasil deve estar de acordo aos padrões de qualidade estabelecidos pela resolução de 4 de fevereiro de 2010 da Agência Nacional do Petróleo, Gás Natural e do Biocombustível (ANP, 04/2010). Neste trabalho, foi estudada a aplicação dos métodos ASTM D 6584 e EN 14105 para o biodiesel de mamona e biodiesel oriundo de rota etílica. Ambos os métodos empregam GC (Cromatografia Gasosa, do inglês Gas Chromatography) com FID (Detecção por Ionização em Chama, do inglês Flame Ionization Detection) e reação de sililação com N-metil-N-(trimetilsilil)trifluoracetamida (MSTFA). Os compostos foram identificados para quantificação pelos tempos de retenção, para os diglicerídeos e triglicerídeos foram utilizadas bandas de tempo de retenção. Os parâmetros de validação considerados foram: curva analítica, linearidade, sensibilidade, robustez, precisão e exatidão. Os métodos ASTM D 6584 e EN 14105 apresentaram sensibilidade semelhante para todos os compostos. Foram escolhidas as condições cromatográficas estabelecidas pelo método ASTM D 6584 por ser mais rápido que o EN14105 e ter sensibilidade semelhante. O método apresentou boa linearidade com todas as curvas analíticas com r maiores que 0,999. A reação de sililação com MSTFA foi otimizada para o biodiesel etílico de mamona em virtude da sua composição química. Um volume de 500 μL de MSTFA foi escolhido para realização dos ensaios de exatidão e precisão. Os valores de exatidão ficaram entre 67 e 145,9% com valores de precisão menores que 11%. Foi avaliada a ocorrência de efeito matriz para biodiesel etílico de mamona, sendo que esse efeito foi considerado baixo para glicerol, monooleína e dioleína e médio para trioleína. Mesmo havendo efeito de matriz o preparo das curvas analíticas em solvente conforme sugerido pelos métodos de referência foi mantido. O método foi robusto frente às variações da composição química da matriz. Na aplicação do método, esse se mostrou adequado para amostras de biodiesel etílico de mamona, de girassol e da mistura de sebo e soja.

Catalytic ethanolysis of soybean oil with immobilized lipase from Candida antarctica and (1)H NMR and GC quantification of the ethyl esters (biodiesel) produced

The catalytic ethanolysis of soybean oil with commercial immobilized lipase type B from Candida antarctica to yield ethyl esters (biodiesel) has been investigated. Transesterification was monitored with respect to the following parameters: quantity of biocatalyst, reaction time, amount of water added and turnover of lipase. The highest yields of biodiesel (87% by (1)H NMR; 82.9% by GC) were obtained after a reaction time of 24 h at 32 degrees C in the presence of lipase equivalent to 5.0% (w/w) of the amount of soybean oil present. The production of ethyl esters by enzymatic ethanolysis was not influenced by the addition of water up to 4.0% (v/v) of the alcohol indicating that it is possible to use hydrated ethanol in the production of biodiesel catalyzed by lipase. The immobilized enzyme showed high stability under moderate reaction conditions and retained its activity after five production cycles. The (1)H NMR methodology elaborated for the quantification of biodiesel in unpurified reaction mixtures showed good correlations between the signal areas of peaks associated with the alpha-methylene groups of the ethyl esters and those of the triacyl-glycerides in residual soybean oil. Monoacylglycerides, diacylglycerides and triglycerides could also be detected and quantified in the crude biodiesel using (1)H NMR spectroscopic and GC-FID chromatographic methods. The biodiesel production by enzymatic catalysis was promising. In this case, was produced a low concentration of glycerol (0.74%) and easily removed by water extraction. (C) 2010 Elsevier B.V. All rights reserved.

Rapid determination of furanocoumarins in creams and pomades using SPE and GC

A solid-phase extraction and chromatography-flame ionization detection (GC-FID) method has been developed for the routine analysis of psoralen, bergapten, isopimpinellin and pimpinellin in creams and pomades employed in Brazil for the treatment of vitiligo. The calibration curve for psoralen was linear in the range 10-100 mu g ml(-1), for bergapten 5-90 mu g ml(-1), for pimpinellin 10-90 mu g ml(-1) and for isopimpinellin 5-100 mu g ml(-1). The best recoveries of the furanocoumarins in the creams analysed were 94-97%, whereas in the pomades, recoveries were 94-96%. The R.S.D. of the quantitative analysis of the furanocoumarins in the products analyses were within 5%. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Caryophyllene-Rich Essential Oil of Didymocarpus tomentosa: Chemical Composition and Cytotoxic Activity

The essential oil from the leaves of Didymocarpus tomentosa was extracted by hydrodistillation and analyzed by GC/FID and GC/MS. Twenty five constituents amounting to 81.6% of the oil were identified. The leaf oil contained 78.7% sesquiterpenes and 2.9% monoterpenes. The leaf essential oil of D. tomentosa is a unique caryophyllene-rich natural source containing beta-caryophyllene, caryophyllene oxide, alpha-humulene and humulene oxide. The cytotoxic activity of the oil was determined by the BSLT using shrimp larva and the MTT assay using HeLa tumor cell line. The oil showed significant cytotoxic activity with LC50 and IC50 values of 12.26 and 11.4 mu g/mL, respectively. This is the first report on the chemical composition and cytotoxic activity of the essential oil of D. tomentosa.

Lipídios como indicadores de processos biogeoquímicos em sedimentos da margem continental do Estado do Rio de Janeiro

Este estudo constitui parte do Projeto Habitats Heterogeneidade Ambiental da Bacia de Campos coordenado pelo CENPES/Petrobras, um projeto multidisciplinar de caracterização ambiental que considera as diferentes feições e habitats da margem continental do sudeste brasileiro. O objetivo desta tese foi investigar os processos relacionados com a origem, o transporte e o acúmulo de matéria orgânica (MO) em sedimentos da margem continental da Bacia de Campos (RJ). Para isso, foram determinados a composição elementar da matéria orgânica (carbono e nitrogênio) por combustão a seco e os lipídios (esteróis, álcoois e ácidos graxos) por CG-MS e CG-DIC. Foram analisadas 215 amostras de sedimento superficial (0-2 cm de profundidade), coletadas em duas amostragens (períodos seco e chuvoso de 2008/2009), distribuídas sobre 12 isóbatas (de 25 a 3000 m) ao longo de 9 transectos de norte a sul da bacia. Além disto, foram ainda consideradas as isóbatas de 400 a 1900 m em dois cânions submarinos no norte da bacia (Almirante Câmara e Grussaí). Com base nos resultados obtidos, a MO sedimentar na plataforma e talude da bacia revelou-se essencialmente autóctone, derivada de produtores primários e secundários. Com isto, a MO contém uma fração reativa significativa e, portanto, é potencialmente biodisponível para os organismos bentônicos. No entanto, foram observados gradientes espaciais significativos na qualidade e na quantidade da MO sedimentar. Na plataforma continental (25 m a 150 m de profundidade) as concentrações de lipídios foram intermediárias e houve predomínio de MO sedimentar lábil. Exceções foram as áreas influenciadas por ressurgência costeira e/ou intrusão sub-superficial (próximo à Cabo Frio, Cabo de São Tomé e no limite norte da bacia), onde as concentrações foram altas. No talude superior e médio (400 a 1300 m) as concentrações de MO foram notadamente mais elevadas, mas com maior influência de processos bacterianos de alteração de sua composição original. E no talude inferior (1900 a 3000 m) as concentrações de MO estiveram muito baixas e apenas os lipídios mais resistentes à degradação bacteriana foram encontrados em concentrações mensuráveis. Isto sugeriu a exportação de materiais da plataforma ao longo do gradiente batimétrico, possivelmente decorrente da ação de meandros e vórtices da Corrente do Brasil e das correntes de fundo atuantes na região. Além disto, por ser lábil e biodisponível, a MO no sedimento apresenta uma fração biodisponível que pode ter uma influência na ecologia das comunidades bentônicas, particularmente aquelas localizadas no talude superior. Os cânions Grussaí e Almirante Câmara se revelaram regiões de acúmulo de MO e importantes no transporte da MO com valor nutritivo para comunidades bentônicas do talude médio e inferior.

Determination of phthalate acid esters plasticizers in plastic by ultrasonic solvent extraction combined with solid-phase microextraction using calix[4]arene fiber

Ultrasonic solvent extraction combined with solid-phase microextraction (SPME) with calix[4]arene/hydroxy-terminated silicone (C[4]/OHTSO) oil coated fiber was used to extract phthalate acid esters (PAEs) plasticizers in plastic, such as blood bags, transfusion tubing, food packaging bag, and mineral water bottle for analysis by gas chromatography (GC). Both extraction parameters (i.e. extraction time, extraction temperature, ionic strength) and conditions of the thermal desorption in a GC injector were optimized by analysis of eight phthalates. The fiber shows wonderful sensitivity and selectivity to the tested compounds. Owing to its high thermal stability (380 degreesC), the carryover effect that often encountered when using conventional fibers can be reduced by appropriately enhancing the injector temperature. The method showed linear response over two to four orders of magnitude with correlation coefficients (r) better than 0.996, and limits of detection (LOD) ranged between 0.006 and 0.084 mug l(-1). The relative standard deviation values obtained were less than or equal to 10%. bis-2-Ethylhexyl phthalate (DEHP) was the sole analyte detected in these plastics and recoveries were in the ranges 95.5-101.4% in all the samples. (C) 2004 Elsevier B.V. All rights reserved.

沈阳地区典型绿化树种生物源挥发性有机物的排放速率

采用二次热解析仪与GC-FID联用技术对沈阳地区8种典型绿化树种生物源挥发性有机物(BVOCs)的排放速率进行了观测和研究。结果表明:银中杨和垂柳的BVOCs排放量显著高于其它6种树木,排放速率分别为97.63和18.24μg.(g.h)-1。阔叶树中银中杨、垂柳、丁香、水腊主要排放异戊二烯,排放速率分别为97.33、17.71、3.78、0.13μg·(g·h)-1,榆树、皂角、银杏主要排放柠檬烯,排放速率分别为0.60、1.64、2.00μg·(g·h)-1;而针叶树油松以排放α-蒎烯为主,排放速率为2.25μg·(g·h)-1。

Quantification of oxygenated volatile organic compounds in seawater by membrane inlet-proton transfer reaction/mass spectrometry

The role of the ocean in the cycling of oxygenated volatile organic compounds (OVOCs) remains largely unanswered due to a paucity of datasets. We describe the method development of a membrane inlet-proton transfer reaction/mass spectrometer (MI-PTR/MS) as an efficient method of analysing methanol, acetaldehyde and acetone in seawater. Validation of the technique with water standards shows that the optimised responses are linear and reproducible. Limits of detection are 27 nM for methanol, 0.7 nM for acetaldehyde and 0.3 nM for acetone. Acetone and acetaldehyde concentrations generated by MI-PTR/MS are compared to a second, independent method based on purge and trap-gas chromatography/flame ionisation detection (P&T-GC/FID) and show excellent agreement. Chromatographic separation of isomeric species acetone and propanal permits correction to mass 59 signal generated by the PTR/MS and overcomes a known uncertainty in reporting acetone concentrations via mass spectrometry. A third bioassay technique using radiolabelled acetone further supported the result generated by this method. We present the development and optimisation of the MI-PTR/MS technique as a reliable and convenient tool for analysing seawater samples for these trace gases. We compare this method with other analytical techniques and discuss its potential use in improving the current understanding of the cycling of oceanic OVOCs.

The Effects of Several Paper Characteristics and Application Methods on the Sublimation Rate of Cyclododecane

Cyclododecane (CDD) is a waxy, solid cyclic hydrocarbon (C12H24) that sublimes at room temperature and possesses strong hydrophobicity. In paper conservation CDD is used principally as a temporary fixative of water-soluble media during aqueous treatments. Hydrophobicity, ease of reversibility, low toxicity, and absence of residues are reasons often cited for its use over alternative materials although the latter two claims continue to be debated in the literature. The sublimation rate has important implications for treatment planning as well as health and safety considerations given the dearth of reliable information on its toxicity and exposure limits. This study examined how the rate of sublimation is affected by fiber type, sizing, and surface finish as well as delivery in the molten phase and as a saturated solution in low boiling petroleum ether. The effect of warming the paper prior to application was also evaluated. Sublimation was monitored using gravimetric analysis after which samples were tested for residues with gas chromatography-flame ionization detection (GC-FID) to confirm complete sublimation. Water absorbency tests were conducted to determine whether this property is fully reestablished. Results suggested that the sublimation rate of CDD is affected minimally by all of the paper characteristics and application methods examined in this study. The main factors influencing the rate appear to be the thickness and mass of the CDD over a given surface area as well as temperature and ventilation. The GC-FID results showed that most of the CDD sublimed within several days of its disappearance from the paper surface regardless of the application method. Minimal changes occurred in the water absorbency of the samples following complete sublimation.

A new analytical approach for the detection of palm oil in vegetable oil blends

The new Food Information Regulation (1169/2011), dictates that in a refined vegetable oil blend, the type of oil must be clearly identified in the package in contract with current practice where is labelled under the generic and often misleading term “vegetable oil”. With increase consumer awareness in food authenticity, as shown in the recent food scandal with horsemeat in beef products, the identification of the origin of species in food products becomes increasingly relevant. Palm oil is used extensively in food manufacturing and as global demand increases, producing countries suffer from the aftermath of intensive agriculture. Even if only a small portion of global production, sustainable palm oil comes in great demand from consumers and industry. It is therefore of interest to detect the presence of palm oil in food products as consumers have the right to know if it is present in the product or not, mainly from an ethical point of view. Apart from palm oil and its derivatives, rapeseed oil and sunflower oil are also included. With DNA-based methods, the gold standard for the detection of food authenticity and species recognition deemed not suitable in this analytical problem, the focus is inevitably drawn to the chromatographic and spectroscopic methods. Both chromatographic (such as GC-FID and LC-MS) and spectroscopic methods (FT-IR, Raman, NIR) are relevant. Previous attempts have not shown promising results due to oils’ natural variation in composition and complex chemical signals but the suggested two-step analytical procedure is a promising approach with very good initial results.

Chemical composition and pharmacological activities of essential oils of Lavandula spp.

Lavandula spp. belong to the family Lamiatae and some species are often used in popular medicine and have been used for centuries in a large number of medical applications and in aromatherapy. Although similar ethnobotanical properties of Lavandula spp., its essential oils, general chemical composition and therapeutic applications differ from different species. Lavandula stoechas L. subsps. luisieri (Rozeira) Rozeira and L. viridis L’Hér are endemic to the Iberian Peninsula, widespread in the South of Portugal, namely in Southern Alentejo and Algarve. The aim of our study was evaluate the chemical composition and toxicological and pharmacological activities of leaves essential oils of spontaneous plants of L. stoechas L. subsps. luisieri (Alentejo) and L. viridis (Algarve). The essential oils of these wild plants, collected in spring, were obtained by hydrodistillation in a Clevenger-type apparatus and its chemical composition was evaluated by GC/FID. The acute toxicity of essential oils was evaluated "in vitro" using brine shrimp (LC50) and "in vivo" using Swiss mice (DL50). The analgesic and anti-inflammatory pharmacological properties of L. stoechas subsp. luisieri essential oil were evaluated in mouse or rats by the Amour-Smith and carrageen-induced paw edema tests, respectively. Results showed important differences in chemical composition of essential oils from two species analyzed either to diversity and proportion of its constituents. The essentials oils showed citotoxicity against Artemia salina and a DL50 higher than 2000 mg/kg for mice. The analgesic and anti-inflammatory activities of essential oils were exhibit for the doses of 100 and 200 mg/kg.

CHEMICAL COMPOSITION AND ANTIMICROBIAL ACTIVITY OF ESSENTIAL OILS OF LAVANDULA SPP.

Lavenders belong to the family Labiatae and represent some of the most popular medicinal plants of great economic importance. Their essential oils are important for the perfume, cosmetic, flavouring and pharmaceutical industries. However, despite its popularity, and the long tradition of use, biological properties of the various Lavandula species are not yet been well sustained by scientific or clinical studies and some available data being inconclusive and controversial [1]. Although Lavandula spp. have similar ethnobotanical properties, however, chemical composition and therapeutic uses differ from different species and main composition of essential oils showed differences with species and with the region were they grow [1,2,3]. L. stoechas L. subsps. luisieri (Rozeira) Rozeira. L. pedunculata (Mill.) Cav. and L. viridis L’Hér are endemic to the Iberian Peninsula, widespread in the South of Portugal, namely in Alentejo and Algarve. In our work, essential oils from the stems or leaves from wild grown plants of L. luisieri (Alentejo), L. pedunculata (Alentejo) and L. viridis (Algarve), were extracted by hydrodistillation and analyzed by GC-FID. Antimicrobial activity was evaluated by solid diffusion disk assay and minimal inhibitory concentration (MIC) against pathogenic Gram-positive and Gram-negative bacteria and food spoilage fungi.

Antioxidant,antimicrobial and toxicological properties of Schinus molle L. essential oils

Ethnopharmacological relevance: Schinus molle L. has been used in folk medicine as antibacterial, antiviral, topical antiseptic, antifungal, antioxidant, anti-inflammatory, anti-tumoural as well as antispasmodic and analgesic; however, there are few studies of pharmacological and toxicological properties of S. molle essential oils. Aim of the study: The aim of this study was to evaluate the antioxidant and antimicrobial activities of S. molle leaf and fruit essential oils, correlated with their chemical composition and evaluate their acute toxicity. Materials and methods: The chemical composition of S. molle leaf and fruit essential oils were evaluated by GC-FID and GC-MS. Antioxidant properties were determined using the 2,2-diphenyl-1-picryl-hydrazyl (DPPH) free radical and β-carotene/linoleic acid methods. Antimicrobial properties were evaluated by the agar disc diffusion method and minimal inhibitory concentration assay. Toxicity in Artemia salina and acute toxicity with behavioural screening in mice were evaluated. Results: The dominant compounds found in leaf and fruit essential oils (EOs) were monoterpene hydrocarbons, namely -phellandrene, β-phellandrene, β-myrcene, limonene and α-pinene. EOs showed low scavenging antioxidant activity by the DPPH free radical method and a higher activity by the β-carotene/linoleic acid method. Antimicrobial activity of EOs was observed for Gram+, Gram– pathogenic bacteria and food spoilage fungi. EOs showed cytotoxicity for Artemia salina and lower toxicity in Swiss mice. Conclusions: The result showed that EOs of leaves and fruits of S. molle demonstrated antioxidant and antimicrobial properties, suggesting their potential use in food or pharmaceutical industries.