Hélices e Espirais em Micro e Nanofibras Celulósicas

A celulose é o polímero renovável mais abundante do mundo. É conhecido pela sua excelente biocompatibilidade, propriedades térmicas e mecânicas. A celulose assim como os polipéptideos e o ADN, pertence a uma família de moléculas orgânicas que dão origem à formação de fases líquidas cristalinas (LCs) colestéricas. A Passiflora Edulis, tal como outras plantas trepadeiras, possui longas e flexíveis gavinhas que permitem à planta encontrar um suporte para se fixar. As gavinhas podem assumir a forma de espirais ou de hélices consoante sejam sustentadas por apenas uma ou por ambas as extremidades. As hélices apresentam muitas vezes duas porções helicoidais, uma esquerda e outra direita, separadas por um segmento recto denominado perversão. Este comportamento é consequência da curvatura intrínseca das gavinhas produzidas pela planta trepadeira. O mesmo comportamento pode ser observado em micro e nanofibras celulósicas fabricadas a partir de soluções líquido-cristalinas, numa escala três a quatro ordens de grandeza inferior à das gavinhas. Este facto sugere que o modelo físico utilizado tenha invariância de escala. Neste trabalho é feito o estudo de fibras e jactos que imitam as estruturas helicoidais apresentadas pelas gavinhas das plantas trepadeiras. As fibras e jactos são produzidos a partir de soluções líquidas cristalinas celulósicas. De modo a determinar as características morfológicas e estruturais, que contribuem para a curvatura das fibras, foram utilizadas técnicas de imagem por ressonância magnética (MRI), microscopia óptica com luz polarisada (MOP), microscopia electrónica de varrimento (SEM) e microscopia de força atómica (AFM) . A variação da forma das estruturas helicoidais com a temperatura parece ser relevante para o fabrico de membranas não tecidas para aplicação em sensores termo-mecânicos.

Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method

QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5–110.0% with variation coefficients not exceeding 8%. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12– 1.90 ng/g wet weight (0.30–4.70 µg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 l 1.20 ng/g in horse mackerel to 14.6 ± 2.8 ng/ g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups.

Analysis of polycyclic aromatic hydrocarbons in atmospheric particulate samples by microwaveassisted extraction and liquid chromatography

A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4±8.8 to 112.0±1.1%, for all the compounds except for naphthalene (62.3±18.0%) and anthracene (67.3±5.7%), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 0.0054 ng/m3 for benzo( a)anthracene to 0.089 ng/m3 for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 28 ng/m3.

Determination of free furfuryl alcohol in foundry resins by chromatographic techniques

Two chromatographic methods, gas chromatography with flow ionization detection (GC–FID) and liquid chromatography with ultraviolet detection (LC–UV), were used to determine furfuryl alcohol in several kinds of foundry resins, after application of an optimised extraction procedure. The GC method developed gave feasibility that did not depend on resin kind. Analysis by LC was suitable just for furanic resins. The presence of interference in the phenolic resins did not allow an appropriate quantification by LC. Both methods gave accurate and precise results. Recoveries were >94%; relative standard deviations were ≤7 and ≤0.3%, respectively for GC and LC methods. Good relative deviations between the two methods were found (≤3%).

Screening of carbamates and ureas in fresh and processed tomato samples using micowave-assisted extraction and liquid chromatography

An analytical method, based on microwave-assisted extraction and liquid chromatography with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20mL acetonitrile, for 10 minutes, at 60º C), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSDs<7%). Quantification limits between 6.5 and 39.6 µg=kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS.

Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography

Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.

Chromatographic techniques for the determination of free phenol in foundry resins

Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99–100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories.

Monitoring of ochratoxin a exposure of the Portuguese population through a nationwide urine survey — winter 2007

Ochratoxin A (OTA) is a mycotoxin produced by a variety of fungi, such as Penicillium verrucosum and Aspergillium spp., which has been found to have a wide number of potentially deadly toxic effects, and can enter the human organism through a variety of means. It then finds its way into the bloodstream and, after a lengthy process, is eventually excreted through the urine. It can thus be detected in its original form not only in blood samples but also in this biological medium. As such, and in an attempt to evaluate the exposure of the Portuguese population to this mycotoxin, morning urine samples were collected during the Winter of 2007, from each of five geographically distinct Portuguese locations — Bragança, Porto, Coimbra, Alentejo, and Algarve — and subjected to extraction by immunoaffinity columns and to OTA quantification through liquid chromatography coupled with fluorescence detection. Prevalent incidence was higher than 95% with Coimbra being the exception (incidence of 73.3%). In nearly all locations, the OTA content of most samples was found to be above the limit of quantification (LOQ) of 0.008 ng/ml. Indeed, excluding Coimbra, with an OTA content level of 0.014 ng/ml, all regions featured content values over 0.021 ng/ml.

Influence of traffic emissions on the carcinogenic polycyclic aromatic hydrocarbons in outdoor breathable particles

Because polycyclic aromatic hydrocarbons (PAHs) have been proven to be toxic, mutagenic, and/or carcinogenic, there is widespread interest in analyzing and evaluating exposure to PAHs in atmospheric environments influenced by different emission sources. Because traffic emissions are one of the biggest sources of fine particles, more information on carcinogenic PAHs associated with fine particles needs to be provided. Aiming to further understand the impact of traffic particulate matter (PM) on human health, this study evaluated the influence of traffic on PM10 (PM with aerodynamic diameter <10 µm) and PM2.5 (PM with aerodynamic diameter <2.5 µm), considering their concentrations and compositions in carcinogenic PAHs. Samples were collected at one site influenced by traffic emissions and at one reference site using lowvolume samplers. Analysis of PAHs was performed by microwave-assisted extraction combined with liquid chromatography (MAE-LC); 17 PAHs, including 9 carcinogenic ones, were quantified. At the site influenced by traffic emissions, PM10 and PM2.5 concentrations were, respectively, 380 and 390% higher than at the background site. When influenced by traffic emissions, the total concentration of nine carcinogenic compounds (naphthalene, chrysene, benzo(a)anthracene, benzo(b) fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, dibenzo(a,h)anthracene, indeno(1,2,3-cd)pyrene, and dibenzo(a,l)pyrene) was increased by 2400 and 3000% in PM10 and PM2.5, respectively; these nine carcinogenic compounds represented 68 and 74% of total PAHs (ƩPAHs) for PM10 and PM2.5, respectively. All PAHs, including the carcinogenic compounds, were mainly present in fine particles. Considering the strong influence of these fine particles on human health, these conclusions are relevant for the development of strategies to protect public health.

Determination of ochratoxin A in bread: evaluation of microwave-assisted extraction using an orthogonal composite design coupled with response surface methodology

An analytical method using microwave-assisted extraction (MAE) and liquid chromatography (LC) with fluorescence detection (FD) for the determination of ochratoxin A (OTA) in bread samples is described. A 24 orthogonal composite design coupled with response surface methodology was used to study the influence of MAE parameters (extraction time, temperature, solvent volume, and stirring speed) in order to maximize OTA recovery. The optimized MAE conditions were the following: 25 mL of acetonitrile, 10 min of extraction, at 80 °C, and maximum stirring speed. Validation of the overall methodology was performed by spiking assays at five levels (0.1–3.00 ng/g). The quantification limit was 0.005 ng/g. The established method was then applied to 64 bread samples (wheat, maize, and wheat/maize bread) collected in Oporto region (Northern Portugal). OTAwas detected in 84 % of the samples with a maximum value of 2.87 ng/g below the European maximum limit established for OTA in cereal products of 3 ng/g.

Evaluation of atmospheric deposition and patterns of polycyclic aromatic hydrocarbons in façades of historic monuments of Oporto (Portugal)

Atmospheric pollution by motor vehicles is considered a relevant source of damage to architectural heritage. Thus the aim of this work was to assess the atmospheric depositions and patterns of polycyclic aromatic hydrocarbons (PAHs) in façades of historical monuments. Eighteen PAHs (16 PAHs considered by US EPA as priority pollutants, dibenzo[a,l]pyrene and benzo[j]fluoranthene) were determined in thin black layers collected from façades of two historical monuments: Hospital Santo António and Lapa Church (Oporto, Portugal). Scanning electron microscopy (SEM) was used for morphological and elemental characterisation of thin black layers; PAHs were quantified by microwave-assisted extraction combined with liquid chromatography (MAE-LC). The thickness of thin black layers were 80–110 μm and they contained significant levels of iron, sulfur, calcium and phosphorus. Total concentrations of 18 PAHs ranged from 7.74 to 147.92 ng/g (mean of 45.52 ng/g) in thin black layers of Hospital Santo António, giving a range three times lower than at Lapa Church (5.44– 429.26 ng/g; mean of 110.25 ng/g); four to six rings compounds accounted at both monuments approximately for 80–85% of ΣPAHs. The diagnostic ratios showed that traffic emissions were significant source of PAHs in thin black layers. Composition profiles of PAHs in thin black layers of both monuments were similar to those of ambient air, thus showing that air pollution has a significant impact on the conditions and stone decay of historical building façades. The obtained results confirm that historical monuments in urban areas act as passive repositories for air pollutants present in the surrounding atmosphere.

Response surface methodology applied to SPE for the determination of ibuprofen in various types of water samples

Over the last few years, there has been a growing concern about the presence of pharmaceuticals in the environment. The main objective of this study was to develop and validate an SPE method using surface response methodology for the determination of ibuprofen in different types of water samples. The influence of sample pH and sample volume on the ibuprofen recovery was studied. The effect of each studied independent variable is pronounced on the dependent variable (ibuprofen recovery). Good selectivity, extraction efficiency, and precision were achieved using 600 mL of sample volume with the pH adjusted to 2.2. LC with fluorescence detection was employed. The optimized method was applied to 20 water samples from the North and South of Portugal.

Antioxidant properties of hydroxycinnamic acids: a review of structure- activity relationships

Hydroxycinnamic acids (HCAs) are important phytochemicals possessing significant biological properties. Several investigators have studied in vitro antioxidant activity of HCAs in detail. In this review, we have gathered the studies focused on the structure-activity relationships (SARs) of these compounds that have used medicinal chemistry to generate more potent antioxidant molecules. Most of the reports indicated that the presence of an unsaturated bond on the side chain of HCAs is vital to their activity. The structural features that were reported to be of importance to the antioxidant activity were categorized as follows: modifications of the aromatic ring, which include alterations in the number and position of hydroxy groups and insertion of electron donating or withdrawing moieties as well as modifications of the carboxylic function that include esterification and amidation process. Furthermore, reports that have addressed the influence of physicochemical properties including redox potential, lipid solubility and dissociation constant on the antioxidant activity were also summarized. Finally, the pro-oxidant effect of HCAs in some test systems was addressed. Most of the investigations concluded that the presence of ortho-dihydroxy phenyl group (catechol moiety) is of significant importance to the antioxidant activity, while, the presence of three hydroxy groups does not necessarily improve the activity. Optimization of the structure of molecular leads is an important task of modern medicinal chemistry and its accomplishment relies on the careful assessment of SARs. SAR studies on HCAs can identify the most successful antioxidants that could be useful for management of oxidative stress-related diseases.

Contribuição para o estudo de compostos desreguladores endócrinos (EDC) em estações de tratamento de águas residuais

Desde os anos 90 que se suspeita que um vasto leque de compostos, que estão presentes no ambiente aquático é susceptível de causar disrupção endócrina, podendo provocar efeitos adversos na nível do sistema reprodutor de vários organismos, de entre os quais os surfactantes não-iónicos alquifenois polietoxilatos(APEO), estrogénios, compostos organoclorados, entre outros. Estes, têm sido amplamente utilizados nos últimos 50 anos numa vasta diversidade de aplicações domésticas e comerciais. Durante o tratamento de águas residuais urbanas e industriais, os APEO são degradados sucessivamente até formas menos biodegradáveis, como por exemplo o NP (nonilfenol) e o OP (octilfenol), acabando por ser descarregados no ambiente aquático. A informação disponível, relativamente ao efeito das elevadas descargas nos meios receptores e da sua potencial toxicidade é ainda muito limitada, nomeadamente em sistemas aquáticos. Por outro lado, a informação sobre remoção de EDC em estações de tratamento de águas residuais (ETAR) é igualmente muito escassa, circunstância que impede a realização de estimativas de balanços materiais, indispensáveis à previsão dos correspondentes impactes nos meios hídricos, pelo que, este estudo teve como principal objectivo, a avaliação do potencial estrogénico de um efluente de uma ETAR com tratamento terciário. O presente estudo foi realizado na ETAR de Chelas, em Lisboa (Portugal). O efluente da ETAR é caracterizado por não ser só, efluente doméstico mas também ser constituído por quantidades significativas de efluente industrial. A escolha desta ETAR para realizar este estudo recaiu também na sua linha de tratamento, isto é, a ETAR possui tratamento terciário com remoção de azoto e desinfecção final do efluente através de U.V. De forma a detectar e quantificar o potencial estrogénico de uma água seleccionaramse compostos específicos, isto é alguns EDC “alvo”, nomeadamente: (i) nonilfenol e octilfenol (NP e OP); (ii) bisfenol A (BPA) e (iii) 17 β-estradiol (E2). Foram utilizadas três técnicas diferentes para identificar e quantificar os EDC seleccionados ELISA, LC-MS-MS e HPLC. As técnicas foram igualmente comparadas. Em todos os casos, isto é, independentemente da técnica analítica usada ficou demonstrado que os EDC seleccionados estavam presentes no efluente da ETAR,variando as suas concentrações de composto para composto e também ao longo da linha de tratamento da ETAR, e que ainda são descarregadas, no Estuário do Tejo,níveis de concentrações que poderão causar efeitos fisiológicos na vida animal. Contudo, devido ao elevado nível de diluição existente no Estuário do Tejo (caudais muito grandes) os efeitos nos organismos poderão não ser relevantes e,ou imediatos. Os níveis mais elevados de APE (NP e OP) foram detectados no afluente à ETAR e os menores no efluente da ETAR. O valor mais elevado de E2 foi registado após a decantação primária. A variação de E2 ao longo da linha de tratamento foi pouco significativa, facto este que poderá estar relacionado também com a “cross-reactivity”, bem como a própria actividade microbiológica existente numa água residual. Os maiores valores para o BPA foram obtidos nas lamas primárias (acima dos limites de detecção), tendo sido registada uma redução significativa deste composto ao longo da linha de tratamento, o que poderá indicar que a ETAR de Chelas remove eficientemente este composto.

Da condição da génese do erro em enfermagem à segurança do cliente em serviços de urgência

Mestrado em Intervenção Sócio-Organizacional na Saúde - Área de especialização: Políticas de Administração e Gestão de Serviços de Saúde