Evolution of ethyl carbamate during Madeira wine ageing by GC-MS: a new methodology

Recently, ethyl carbamate (EC) was reclassified by the International Agency for Research on Cancer (IARC) as "probably carcinogenic to humans" and occurs mainly in fermented beverages. Nowadays many countries have set limit values for EC in alcoholic beverages. In this sense and taking into account the low concentrations found in alcoholic beverages, the scientific community has shown interest for the development of new analytical methods, whereby its simplification plays an important role in the EC control and prevention. Firstly, a simple, rapid and sensitive methodology was developed for the EC quantification in fortified wines by microextraction by packed sorbent (MEPS) with gas chromatography coupled with a mass spectrometer detector (GC-MS). This method showed good linearity (R2 = 0.999) and sensitivity (LOD = 1.5 μg/L). The accuracy of the method was assessed by means of repeatability and reproducibility (RSD < 7%). Moreover, a good recovery has been demonstrated (97 – 106%) as well as its applicability (16 fortified wines). Thus, the developed methodology has proven to be an excellent approach for routine quantification of EC in fortified wines. The EC evolution was also evaluated during a year and half of Madeira wine ageing submitted to two traditional ageing methods, estufagem and canteiro, in order to evaluate the formation kinetic. The results revealed that estufagem process increased the formation kinetic and promoted a linear increase of the EC concentration (R2 ≥ 0.977), proportionally to the ageing time (4 months). However, when the wines are firstly submitted to estufagem and then undergo canteiro ageing, the EC values remain almost constant during the following 14 months. The results suggest that estufagem does not seem to be the critical factor in the EC formation, but instead the amount of precursors in the medium.

Olfactory perception threshold assessment of volatile acidity in Madeira wines

Madeira wine is a fortified wine with impact in the Madeira Island’s economy. Similarly to other wines, its acidity should be well controlled in order to ensure Madeira wine quality, mostly the volatile acidity. Due to Madeira wine complex flavour, it is crucial to get a better knowledge about the volatile acidity impact in its features, namely determine the perception limit of acetic acid and ethyl acetate, as both are the main contributors for volatile acidity. Firstly, the olfactory perception threshold of volatile acidity was assessed by a trained and an untrained panel, using 5 and 10 years-old Sercial and Malvasia wines. Moreover, the current work also presents the evolution of organic acids, acetic acid and ethyl acetate during 540 days of ageing of Madeira wines (Malvasia, Bual, Verdelho and Sercial), comparing the same wines aged by both traditional ageing processes: canteiro and estufagem. Other wine samples, aged in wood casks (canteiro) for at least 5 years, were also evaluated. HS-SPME followed by GC-MS analysis was used to determine ethyl acetate concentration and IEC-HPLC-DAD was used for the organic acids determination, including acetic acid. The results indicated that acetic acid and ethyl acetate olfactory perception threshold depends essentially on wine’s age. Concerning acetic acid, the untrained panel was in average 5.45 g/L (5 years-old) and 6.22 g/L (10 years-old). Training the expert panel to recognize acetic acid odour, the values decreased for 1.44 g/L (5 years-old) and 1.87 g/L (10 years-old), but still remained higher than the established volatile acidity legal limits. Ethyl acetate threshold was similar for both panels (in average 327.97 mg/L). Both compounds tend to increase exponentially with age, being more evident in sweet wines. Organic acids in young Madeira wines depend mostly on the nature of grape varieties, but this difference is minimized with wine ageing.

HPLC-DAD methodology for the quantification of organic acids, furans and polyphenols by direct injection of wine samples

This article proposes a simple and sensitive HPLC method with photo-diode array detection for the analysis of organic acids, monomeric polyphenols and furanic compounds in wine samples by direct injection. The chromatographic separation of 8 organic acids, 2 furans and 22 phenolic compounds was carried out with a buffered solution (pH 2.70) and acetonitrile as mobile phases and a difunctionally bonded C18 stationary phase, Atlantis dC18 (250 4.6 mm, 5mm) column. The elution was performed in 12 min for the organic acids and in 60 min for the phenolic compounds, including phenolic acids, stilbenes and flavonoids. Target compounds were detected at 210 nm (organic acids, flavan-3-ols and benzoic acids), 254 nm (ellagic acid), 280 nm (furans and cinnamic acid), 315 nm (hydroxycinnamic acids and trans-resveratrol) and 360 nm (flavonoids). The RSD for the repeatability test (n55) of peak area and retention times were below 3.1 and 0.3%, respectively, for phenolics and below 1.0 and 0.2% for organic acids. The RSDs expressing the reproducibility of the method were higher than for the repeatability results but all below 9.0%. Method accuracy was evaluated by the recovery results, with averaged values between 80 and 104% for polyphenols and 97–105% for organic acids. The calibration curves, obtained by triplicate injection of standard solutions, showed good linearity with regression coefficients higher than 0.9982 for polyphenols and 0.9997 for organic acids. The LOD was in the range of 0.07–0.49 mg/L for polyphenols (cinnamic and gallic acids, respectively) and 0.001–0.046 g/L for organic acids (oxalic and lactic acids, respectively). The method was successfully used to measure and assess the polyphenolic fingerprint and organic acids profile of red, white, rose ´ and fortified wines.

Quantification of polyphenols with potential antioxidant properties in wines using reverse phase HPLC

A RP-HPLC method with photodiode array detection (DAD) was developed to separate, identify and quantify simultaneously the most representative phenolic compounds present in Madeira and Canary Islands wines. The optimized chromatographic method was carefully validated in terms of linearity, precision, accuracy and sensitivity. A high repeatability and a good stability of phenolics retention times (a3%) were obtained, as well as relative peak area. Also high recoveries were achieved, over 80.3%. Polyphenols calibration curves showed a good linearity (r2 A0.994) within test ranges. Detection limits ranged between 0.03 and 11.5 lg/mL for the different polyphenols. A good repeatability was obtained, with intra-day variations less than 7.9%. The described method was successfully applied to quantify several polyphenols in 26 samples of different kinds of wine (red, ros and white wines) from Madeira and Canary Islands. Gallic acid was by far the most predominant acid. It represents more than 65% of all phenolics, followed by p-coumaric and caffeic acids. The major flavonoid found in Madeira wines was trans-resveratrol. In some wines, (–)-epicatechin was also found in highest amount. Canary wines were shown to be rich in gallic, caffeic and p-coumaric acids and quercetin.

Simultaneous analysis of free amino acids and biogenic amines in honey and wine samples using in loop orthophthalaldeyde derivatization procedure

This work presents a RP-HPLC method for the simultaneous quantification of free amino acids and biogenic amines in liquid food matrices and the results of the application to honey and wine samples obtained from different production processes and geographic origins. The developed methodology is based on a pre-column derivatization with o-phthaldialdehyde carried out in the sample injection loop. The compounds were separated in a Nova-Pack RP-C18 column (150 mm × 3.9 mm, 4 μm) at 35 °C. The mobile phase used was a mixture of phase A: 10 mM sodium phosphate buffer (pH 7.3), methanol and tetrahydrofuran (91:8:1); and phase B: methanol and phosphate buffer (80:20), with a flow rate of 1.0 ml/min. Fluorescence detection was used at an excitation wavelength of 335 nm and an emission wavelength of 440 nm. The separation and quantification of 19 amino acids and 6 amines was carried out in a single run as their OPA/MCE derivatives elute within 80 min, ensuring a reproducible quantification. The method showed to be adequate for the purpose, with an average RSD of 2% for the different amino acids; detection limits varying between 0.71 mg/l (Asn) and 8.26 mg/l (Lys) and recovery rates between 63.0% (Cad) and 98.0% (Asp). The amino acids present at the highest concentration in honey and wine samples were phenylalanine and arginine, respectively. Only residual levels of biogenic amines were detected in the analysed samples.

Nas marés da vida: histórias e Saberes das mulheres marisqueiras

The harsh reality of women in the municipality of Indiaroba enlarges to much more from everyday household . Every day, they need courage and determination to adentrarem in mangrove cross functional seafood, which sold, ensure their survival. The life of catadoras seafood, fishing in mangrove and have your family's work, is the object of this study, through which search will be highlighted the history of women who perform a subsistence activity in your daily life. Will reflect on their work in the environment into which are entered, the vision that have labour, environment, family, sexuality, and their social relations. The research p Espírito Santo, in which these women, forgetting seafood calls, play activities diversified in its role of being a woman, reason personal awareness, generating an academic curiosity to know their life stories. Through ethnographic method, which spans observations, interviews, workshops and testimonials, we have tried to learn more about the daily life of forgetting seafood. This gives visibility to the human condition in one of its expressions which can help you understand and appreciate the cultural diversity of knowledge and knowledge constructed this activity pecheurfalco

Geomorfologia e neotectônica no Vale do Apodi-Mossoró RN

Numerous studies have indicated that the Potiguar Basin is affected by Cenozoic tectonics. The reactivation of Cretaceous fault systems affect the post-rift units, witch include Neogene and overlying Quaternary sediments. In this context, the objectives of this thesis are the followings: (1) to characterize the effects of post-rift tectonics in the morphology of Apodi Mossoró-river valley located in the central portion of the Potiguar, (2) to characterize the drainage of the Apodi Mossoró river valley and investigate the behavior of their channels across active faults, and (3) to propose a geologic-geomorphological evolutionary model for the study area. This study used a geological and geomorphological mapping of the central part of the basin, with emphasis on the Quaternary record, luminescence dating of sediments, and geoelectric profiles of the area. The results reveal by maps of structural lineaments and drainage channels of the rivers form valleys that are affected by faults and folds. In Apodi-Mossoró valley, anomalies of channel morphology are associated with the deformation of the post-rift basin. These anomalies show the reactivation of major fault systems in the Potiguar Basin in Cenozoic. On a regional scale, can be seen through the vertical electric profiles that the Cenozoic tectonics is responsible for the elevation of a macro dome NE-SE-trending 70-km long and 50km wide and up to 270 above sea level. In this sector, the vertical electric profiles data show that the contact between the Cretaceous and Neogene rise more than 100m. This Is an important feature of inversion data obtained in this work showed that the deposits that cover the macro dome (Serra do Mel) have ages of 119 ka to 43 ka. In the river valley and surrounding areas Apodi-Mossoró ages vary between 319 ka and 2.7 ka. From these data it was possible to establish the correct geochronological posiconamento paleodepósitos of distinguishing them from the fluvial deposits of the Neogene (Barreiras Formation)

The effect of oestrogen and alendronate therapies on postmenopausal bone loss around osseointegrated titanium implants

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

Helminth component community of the paradoxal frog Pseudis platensis Gallardo, 1961 (Anura: Hylidae) from south-eastern Pantanal, Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hemoparasites of the genus Trypanosoma (Kinetoplastida: Trypanosomatidae) and hemogregarines in Anurans of the São Paulo and Mato Grosso do Sul States - Brazil

Os animais silvestres estão expostos a inúmeros patógenos,dentre eles estão os hemoparasitas. Podem-se destacar espécies do gênero Trypanosoma e do grupo das hemogregarinas,que ocorrem com freqüência parasitando anuros (rãs, pererecas e sapos). Normalmente, a descrição destes hemoparasitas é feita através da morfologia dos estágios observados nosangue periférico do hospedeiro e as pesquisas sobre o ciclobiológico desses hemoparasitas são escassas. Os objetivos dopresente estudo foram avaliar a presença de hemogregarinas eTrypanosoma spp. em anuros capturados nos Estados de São Paulo e Mato Grosso do Sul e fazer a caracterização morfológica e morfométrica dos seus hemoparasitas. As espécies deanuros examinadas foram: Dendropsophus nanus, D. minutus, Leptodactylus chaquensis, L. podicipinus, L. labyrinthicus, L. fuscus, Bufo granulosus, B. schneideri, Phyllomedusahypocondrialis, Trachicephalus venulosus, Scinax fuscovarius e Hypsiboas albopunctatus. Dos 40 animais estudados, foramencontrados quatro (10%) positivos para hemogregarinas e oito(20%) positivos para Trypanosoma spp. Foram observadosgamontes de hemogregarinas com morfologia variável e, alémdas formas intraeritrocíticas, também foram observados gamontes fora das hemácias. As formas de Trypanosoma encontradas eram muito polimórficas, conforme é descrito na literatura, sendo na sua maioria, larga e oval.

Natural history of the coral snake Micrurus Pyrrhocryptus Cope 1862 (Elapidae) from semideciduous forests of western Brazil.

Coral snakes in the genus Micrurus are widely distributed in the Neotropics, with more than 50 species already described in this region. They are primarily ground or leaf litter dwellers, feed on snakes or other elongate vertebrates, and tend to reproduce during the rainy season. We present data on the biology of Micrurus pyrrhocryptus from two semideciduous forests of Mato Grosso do Sul state, western Brazil. Two snake species were consumed: the dipsadid Sibynomorphus lavillai and the typhlopid Typhlops brongersmianus. Sexual dimorphism is marked in M. pyrrhocryptus. with males attaining larger sizes and having longer tails. Activity was concentrated in the wet season, when reproduction occurs. The defensive behavior in this species is similar to that displayed by other Micron's, although less pronounced.

Diversidade de pulgões e de seus parasitóides e predadores na cultura da alfafa

O objetivo deste trabalho foi verificar a diversidade de pulgões, seus predadores e parasitóides, e a influência de fatores climáticos nas suas populações. Foram realizadas coletas semanais no período de abril/1995 a março/1996, no campo de alfafa da Universidade Federal de Lavras (UFLA), em Lavras, MG. As espécies de pulgões coletadas foram Therioaphis trifolii (Monel) f. maculata, Acyrthosiphon pisum (Harris), A. kondoi Shinji e Aphis craccivora Kock, presentes na cultura durante todo o período de estudo, com picos populacionais em novembro/1995, julho/1995, dezembro/1995 e abril/1996, respectivamente. Foram amostrados insetos predadores das famílias Coccinellidae, Syrphidae, Anthocoridae, Geocoridae e Chrysopidae, tendo as duas últimas ocorrência esporádica. Espécies da família Coccinellidae ocorreram durante todo o período amostral, apresentando o pico populacional no final de dezembro/1995, com precipitação de 20 mm e temperatura de 22,6ºC. A família Syrphidae alcançou maiores números em abril, à precipitação de 53 mm e temperatura de 21ºC. A família Anthocoridae não se manteve por todo o período amostral, porém um pico populacional ocorreu no final de dezembro nas mesmas condições que aquele apresentado pela família Coccinellidae. Os parasitóides da família Aphididae alcançaram pico em junho/1995, à temperatura de 16ºC.

Morfo-anatomia caulinear de nove espécies de Orchidaceae

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Os efeitos do FUNDEF nas políticas educacionais dos municípios mineiros

Este artigo tem por objetivo discutir os efeitos do FUNDEF sobre as políticas educacionais dos municípios de Minas Gerais. As análises estão balizadas em entrevistas realizadas com secretários municipais de educação de uma amostra de 22 municípios, entre novembro e dezembro de 2002. A análise leva em conta um conjunto de argumentos e hipóteses levantado pela literatura, o que inclui a tendência à busca de ganhos de escala e concentração de alunos e estabelecimentos; a possível melhora de remuneração e qualificação do corpo docente; o desenvolvimento de iniciativas de capacitação dos professores; a redução do uso dos recursos vinculados à educação para outros fins; o possível subinvestimento em educação infantil, ensino médio e educação de jovens e adultos, devido à sua exclusão do FUNDEF; e a possível insuficiência do valor de referência do Fundo.