Development of new technologies for the selective removal of volatile compounds with applications in forensic science and natural aromas

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2015

Foodies in the UK: A Sense of Self, Connection and Belonging Beyond the Passion?

The global rise of the Foodie movement has attracted some research attention as well as critique in the food industry trend followers, but little research attention in marketing research. The present study looks at the ‘Foodie’ phenomenon in the UK and aims to extend how the notion has been coined in literature through a qualitative investigation of a sample of self-professed Foodies. The objective is to provide an in-depth understanding of what it means to be a Foodie at the individual and group levels, probing attitudes, motivations and self-awareness. Results indicate that the term Foodie cannot be used as an implicit definition of someone ‘simply interested in food’; the capacity of the Foodie may be dependent on individual involvement and the level of importance along the five emerging themes; these being: Learning and discovery; Pleasure and enjoyment; Inspirational influences; Quality; and Experiencing food as an individual and in connection with others. Findings imply that there might be different levels of Foodies, leading to a start on developing a Foodie Typology. The study poses implications for food marketers and researchers that can assist in more effective segmentation, efficient targeting and tailored positioning, as well as opportunities for future research.

Poetry and feminine crafts in the letters of the young Marquise of Alorna (1750-1839)

abstract : Taking as a starting point the association between embroidery and language conveyed by the Greek myth of Filomela and Procne, this article examines the relationship between social status and ornaments like embroidery and lace. In order to illustrate this relationship an example is selected form the letters exchanged between the Marquise of Alorna and her Father where a connection is established between the production of these 'feminine' crafts, women's culture and womens writing, in the XVIIIth Century

Inventories and concentration profiles of 137Cs in undisturbed soils in the northeast of Buenos Aires Province, Argentina

Inventories and vertical distribution of (137)Cs were determined in La Plata region undisturbed soils, Argentina. A mean inventory value of 891 ± 220 Bq/m(2) was established, which is compatible with the values expected from atmospheric weapon tests fallout. The study was complemented with pH, organic carbon fraction, texture and mineralogical soil analyses. Putting together Southern Hemisphere (137)Cs inventory data, it is possible to correlate these data with the mean annual precipitations. The large differences in (137)Cs concentration profiles were attributed to soil properties, especially the clay content and the pH values. A convection-dispersion model with irreversible retention was used to fit the activity concentration profiles. The obtained effective diffusion coefficient and effective convection velocity parameters values were in the range from 0.2 cm(2)/y to 0.4 cm(2)/y and from 0.23 cm/y to 0.43 cm/y, respectively. These data are in agreement with values reported in literature. In general, with the growth of clay content in the soil, there was an increase in the transfer rate from free to bound state. Finally, the highest transfer rate from free to bound state was obtained for soil pH value equal to 8.

Using remote experimentation in a large undergraduate course: initial findings

The use of remote labs in undergraduate courses has been reported in literature several times since the mid 90's. Nevertheless, very few articles present results about the correspondent learning gains obtained by students, and in what conditions those systems can be more efficient, thus suggesting a lack of data concerning their pedagogical effectiveness. This paper addresses such a gap by presenting some initial findings concerning the use of a remote lab (VISIR), in a large undergraduate course on Physics, with over 550 students enrolled.

Using VISIR in a large undergraduate course: preliminary assessment results

The use of remote labs in undergraduate courses has been reported in literature several times since the mid 90's. Nevertheless, very few articles present results about the learning gains obtained by students using them, especially with a large number of students, thus suggesting a lack of data concerning their pedagogical effectiveness. This paper addresses such a gap by presenting some preliminary results concerning the use of a remote laboratory, known as VISIR, in a large undergraduate course on Applied Physics, with over 500 students enrolled.

Selective recognition in potentiometric transduction of amoxicillin by molecularly imprinted materials

The indiscriminate use of antibiotics in food-producing animals has received increasing attention as a contributory factor in the international emergence of antibiotic-resistant bacteria (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004). Numerous analytical methods for quantifying antibacterial residues in edible animal products have been developed over years (Woodward in Pesticide, veterinary and other residues in food, CRC Press, Boca Raton, 2004; Botsoglou and Fletouris in Handbook of food analysis, residues and other food component analysis, Marcel Dekker, Ghent, 2004). Being Amoxicillin (AMOX) one of those critical veterinary drugs, efforts have been made to develop simple and expeditious methods for its control in food samples. In literature, only one AMOX-selective electrode has been reported so far. In that work, phosphotungstate:amoxycillinium ion exchanger was used as electroactive material (Shoukry et al. in Electroanalysis 6:914–917, 1994). Designing new materials based on molecularly imprinted polymers (MIPs) which are complementary to the size and charge of AMOX could lead to very selective interactions, thus enhancing the selectivity of the sensing unit. AMOX-selective electrodes used imprinted polymers as electroactive materials having AMOX as target molecule to design a biomimetic imprinted cavity. Poly(vinyl chloride), sensors of methacrylic acid displayed Nernstian slopes (60.7 mV/decade) and low detection limits (2.9 × 10−5 mol/L). The potentiometric responses were not affected by pH within 4–5 and showed good selectivity. The electrodes were applied successfully to the analysis of real samples.

Thomsen-Friedenreich antigens in bladder cancer: evaluation of their prognostic value

RESUMO: Introdução. O cancro de bexiga é uma patologia comum que representa o 6° e o 5° cancro mais incidente em Portugal e na Itália, respetivamente. Em mais de metade dos casos ocorre reincidência durante o primeiro ano, requerendo acompanhamento clínico ao longo da vida. A instilação intravesical de Bacillus Calmette-Guérin (BCG) (uma estirpe atenuada do Mycobacterium bovis) representa uma imunoterapia eficaz no combate ao cancro de bexiga, no entanto, muitos aspetos da interação de BCG com as células tumorais bem como com as células do sistema imunitário permanecem por desvendar. As células tumorais de bexiga expressam frequentemente as formas sialiladas dos antigénios de Thomsen-Friedenreich (TF), i.e., sialil-T (sT) e sialil-Tn (sTn). Contudo ainda se desconhece o significado da sua expressão na malignidade tumoral e se afeta a eficácia da terapêutica BCG. Objetivo do estudo. Investigar o papel dos antigénios sT e sTn no fenótipo maligno de células de cancro de bexiga bem como na resposta mediada pelo sistema imunitário à terapia com BCG. Metodologia. Para tal, foram utilizadas as linhas celulares de cancro da bexiga HT1376 e MCR, geneticamente modificadas por transdução com vetores codificantes para as sialiltransferases ST3GAL1 ou ST6GALNAC1, de forma a expressar homogeneamente os antigénios sT ou sTn respetivamente. Estes modelos celulares foram estudados após confronto com BCG. O nível de BCG internalizado foi avaliado por citometria de fluxo. O perfil global de expressão genética dos modelos celulares antes e após incubação com BCG foi analisado pela tecnologia de microarray. O perfil de citocinas secretadas pelos modelos celulares após incubação com BCG, bem como de macrófagos estimulados pelo secretoma de células de cancro de bexiga que por sua vez foram estimuladas previamente por BCG, foi estudado pelo sistema multiplex de “imuno-esferas”. Resultados. A análise do transcritoma dos modelos celulares revelou que grupos de genes envolvidos em funções específicas foram modulados em paralelo nos dois modelos celulares, após transdução, independentemente da sialiltransferase expressa. Ou seja, em células que expressavam a sialiltransferase ST3GAL1 ou ST6GALNAC1, os genes envolvidos na regulação da segregação cromossómica e na reparação do DNA foram consistentemente regulados negativamente. Genes descritos na literatura como marcadores para o cancro de bexiga foram também modulados. A incubação com BCG resultou numa tendência ao aumento da expressão de genes relevantes na preservação e estabilidade genómica e menor malignidade, no entanto, apenas em células que expressavam sT ou sTn. Entre as dez citocinas testadas, apenas a IL-6 e IL-8 foram expressas pelas linhas celulares de cancro da bexiga, com indução destas após estimulação com BCG, e principalmente em células que expressavam ST3GAL1 ou ST6GALNAC1. Em macrófagos, citocinas inflamatórias, tais como IL-1β, IL-6 e TNFα, e a citocina anti-inflamatória IL-10, foram induzidas apenas pelo secretoma de células de cancro da bexiga confrontadas com BCG, com maior relevância quando estas expressavam ST3GAL1 ou ST6GALNAC1, prevendo a estimulação de macrófagos semelhantes aos de tipo M1 e uma melhor resposta à terapia com BCG. Conclusões. O efeito geral da expressão destas sialiltransferases e dos produtos enzimáticos sT ou sTn nas células de cancro de bexiga conduz a um fenótipo de maior malignidade. Contudo, a maior avidez de estas na produção de citocinas inflamatórias após confronto com BCG, bem como a maior capacidade de estimulação de macrófagos, predirá uma resposta à terapia com BCG mais eficaz em tumores que expressem os antigénios de TF sialilados. Tais conclusões são totalmente concordantes com os nossos mais recentes dados clínicos obtidos em colaboração, que mostram que em doentes com cancro de bexiga que expressam sTn respondem melhor a terapia BCG. ----------ABSTRACT: Background. Bladder cancer is a common malignancy representing the 6th and the 5th most incident cancer in Portugal and in Italy, respectively. More than half of the cases relapse within one year, requiring though a lifelong follow-up. Intravesical instillation of Bacillus Calmette-Guérin (BCG) (an attenuated strain of Mycobacterium bovis) represents an effective immunotherapy of bladder cancer, although many aspects of the interaction of BCG with cancer cells and host immune cells remain obscure. Bladder cancer cells often express the sialylated forms of the Thomsen-Friedenreich (TF), i.e., sialil-T (sT) e sialil-Tn (sTn). However, it’s still unknown the sense of such expression in tumour malignancy and in the BCG therapy efficacy. Aim of the study. To investigate the role of the sT and sTn antigens on the malignant phenotype of bladder cancer cells and the immune mediated response to BCG therapy. Experimental. We have utilized populations of the bladder cancer cell lines HT1376 and MCR, genetically modified by transduction with the sialyltransferases ST3GAL1 or ST6GALNAC1 to express homogeneously sT or sTn antigens. The level of BCG internalized was assessed by flow cytometry. The whole gene expression profile of BCG-challenged or unchallenged bladder cancer cell lines was studied by microarray technology. The profile of cytokines secreted by BCG-challenged bladder cancer cells and that of macrophages challenged by the secretome of BCG-challenged bladder cancer cells was studied by multiplex immune-beads assay. Results. Transcriptome analysis of the sialyltransferase-transduced cells revealed that groups of genes involved in specific functions were regulated in parallel in the two cell lines, regardless the sialyltransferase expressed. Namely, in sialyltransferase-expressing cells, genes involved in the proper chromosomal segregation and in the DNA repair were consistently down-regulated, while genes reported in literature as markers for bladder cancer were modulated. BCG-challenging induced a tendency to up-regulation of the genes preserving genomic stability and reducing malignancy, but only in cells expressing either sT or sTn. Among the ten cytokines tested, only IL-6 and IL-8 were expressed by bladder cancer cell lines and up-regulated by BCG-challenging, mainly in sialyltransferases-expressing cells. In macrophages, inflammatory cytokines, such as IL-1β, IL-6 and TNFα, and the antinflammatory IL-10 were induced only by the secretome of BCG-challenged bladder cancer cells, particularly when expressing either sialyltransferase, predicting the stimulation of M1-like macrophages and a better response to BCG therapy. Conclusions. The general effect of the expression of the two sialyltransferases and their products in the bladder cancer cells is toward a more malignant phenotype. However, the stronger ability of sialyltransferase expressing cells to produce inflammatory cytokines upon BCG-challenging and to stimulate macrophages predicts a more effective response to BCG in tumours expressing the sialylated TF antigens. This is fully consistent with our recent clinical data obtained in collaboration, showing that patients with bladder cancer expressing sTn respond better to BCG therapy.

Assessment by doppler ultrasound of entheseal lesions in spondyloarthritis : a longitudial study to determine structural damage and disease activity lesions

RESUMO: Enthesitis is the hallmark of spondyloarthritis (SpA), and is observed in all subtypes. Wide information on SpA abnormalities, including synovitis, tendinitis and enthesitis, can be efficiently perceived by Doppler ultrasound. Furthermore, several studies on imaging of enthesis showed that imaging techniques are better than clinical examination to detect enthesis alterations; and vascularized enthesitis detected by Doppler ultrasound appears to be a valuable diagnostic tool to confirm SpA diagnosis. However, data published until now concerning entheseal elementary alterations that characterize SpA enthesitis (enthesis inflammatory activity) or enthesopathy (permanent structural changes) reflect rather the authors’ empiric opinion than a methodological validation process. In this sense it seems crucial to identify elementary entheseal lesions associated with activity or damage, in order to improve monitoring and treatment response in SpA patients. The development of better assessment tools is today a challenge and a need in SpA. The first study of this thesis focused on the analysis of the reliability of inter-lector and inter-ultrasonography equipment of Madrid sonography enthesitis index (MASEI). Fundamental data for the remaining unrolling project validity. In the second and third studies we concerned about two entheseal elemental lesions: erosions and bursa. In literature erosions represent a permanent structural damage, being useful for monitoring joint injury, disease activity and therapeutic response in many rheumatic diseases; and to date, this concept has been mostly applied in rheumatoid arthritis (RA). Unquestionably, erosion is a tissue-related damage and a structural change. However, the hypothesis that we decided to test was if erosions represent a permanent structural change that can only grow and worsen over time, as occurs in RA, or a transitory alteration. A longitudinal study of early SpA patients was undertaken, and the Achilles enthesis was used as a model. Our results strongly suggested that previously detected erosions could disappear during the course of the disease, being consistent with the dynamic behavior of erosion over time. Based on these striking results it seems reasonable to suggest that the new-bone formation process in SpA could be associated with the resolution of cortical entheseal erosion over time. These results could also be in agreement with the apparent failure of anti-tumor necrosis factor (TNF) therapies to control bone proliferation in SpA; and with the relation of TNF-α, Dickkopf-related protein 1 (Dkk-1) and the regulatory molecule of the Wnt signaling pathway in the bone proliferation in SpA. In the same model, we then proceeded to study the enthesis bursa. Interestingly, the Outcome Measures in Rheumatology Clinical Trials (OMERACT) enthesopathy definition does not include bursa as an elementary entheseal lesion. Nonetheless, bursa was included in 46% of the enthesis studies in a recently systematic literature review, being in agreement with the concept of “synovio-entheseal complex” that includes the link between enthesitis and osteitis in SpA. It has been clarified in recent data that there is not only a close functional integration of the enthesis with the neighboring bone, but also a connection between enthesitis and synovitis. Therefore, we tried to assess the prevalence and relevance of the bursa-synovial lesion in SpA. Our findings showed a significant increase of Achilles bursa presence and thickness in SpA patients compared to controls (healthy/mechanical controls and RA controls). These results raise awareness to the need to improve the enthesopathy ultrasonographic definition. In the final work of this thesis, we have explored new perspectives, not previously reported, about construct validity of enthesis ultrasound as a possible activity outcome in SpA. We performed a longitudinal Achilles enthesis ultrasound study in patients with early SpA. Achilles ultrasound examinations were performed at baseline, six- and twelve-month time periods and compared with clinical outcome measures collected at basal visit. Our results showed that basal erythrocyte sedimentation rate (ESR) and C-reactive protein (CRP) are higher in patients with Doppler signal in enthesis, and even that higher basal ESR, CRP and Ankylosing Spondylitis Disease Activity Score (ASDAS) predicted a higher Doppler signal (an ultrasound alteration accepted as representative of inflammation) six months later. Patients with very high disease activity assessed by ASDAS (>3.5) at baseline had significantly higher Achilles total ultrasound score verified at the same time; and ASDAS <1.3 predicted no Doppler signal at six and twelve months. This seems to represent a connection between classical biomarkers and clinical outcomes associated with SpA activity and Doppler signal, not only at the same time, but also for the following months. Remarkably, patients with inactive disease (ASDAS < 1.3) at baseline had no Doppler signal at six and twelve months. These findings reinforce the potential use of ultrasound related techniques for disease progression assessment and prognosis purposes. Intriguingly, Ankylosing Spondylitis Disease Activity Index (BASDAI) didn’t show significant differences between different cut-offs concerning ultrasound lesions or Doppler signal, while verified with ASDAS. These results seem to indicate that ASDAS reflects better than BASDAI what happens in the enthesis. The work herein discussed clearly shows the potential utility of ultrasound in enthesis assessment in SpA patients, and can be important for the development of ultrasound activity and structural damage scores for diagnosis and monitoring purposes. Therefore, local promotion of this technique constitutes a medical intervention that is worth being tested in SpA patients for diagnosis, monitoring and prognosis purposes.

Toxic substances in blood: an analysis of current recommendations under a Bayesian (decision) approach

This article extends existing discussion in literature on probabilistic inference and decision making with respect to continuous hypotheses that are prevalent in forensic toxicology. As a main aim, this research investigates the properties of a widely followed approach for quantifying the level of toxic substances in blood samples, and to compare this procedure with a Bayesian probabilistic approach. As an example, attention is confined to the presence of toxic substances, such as THC, in blood from car drivers. In this context, the interpretation of results from laboratory analyses needs to take into account legal requirements for establishing the 'presence' of target substances in blood. In a first part, the performance of the proposed Bayesian model for the estimation of an unknown parameter (here, the amount of a toxic substance) is illustrated and compared with the currently used method. The model is then used in a second part to approach-in a rational way-the decision component of the problem, that is judicial questions of the kind 'Is the quantity of THC measured in the blood over the legal threshold of 1.5 μg/l?'. This is pointed out through a practical example.

(Re)writing the other/self : autoethnography in the transcultural arena of representation

Abstract: In Imperial Eyes Mary Louise Pratt (1992: 7, emphasis original) defines autoethnography as "instances in which colonized subjects undertake to represent themselves in ways that engage with the colonizer's own terms ... in response to or in dialogue with . . . metropolitan representations." Although Pratt's conceptualization of autoethnography has much to offer post-colonial studies, it has received little attention in the field. In this thesis, I interrogate Pratt's notion of autoethnography as a theoretical tool for understanding the self-representations of subordinate peoples within transcultural terrains of signification. I argue that autoethnography is a concept that allows us to move beyond some theoretical dualisms, and to recognize the (necessary) coexistence of subordinate peoples' simultaneous accommodation of and resistance to dominant representations of themselves. I suggest that even when autoethnographic expressions seem to rely on or to reproduce dominant knowledges, their very existence as speech acts implicitly resists dominant discourses which objectify members of oppressed populations and re-create them as Native Informants. I use Pratt's concept to analyze two books by Islamic feminist sociologist Fatima Memissi. Memissi's Dreams ofTrespass and Scheherazade Goes West illustrate the simultaneity of accommodation and disruption evident in autoethnographic communication. Across the two books, Memissi shows herself renegotiating the discourses which discipline her (and her speech). She switches back and forth between the positions of reader and author, demonstrates the reciprocity of the disciplinary gaze (she looks back at her dominants, reading their own reading of her representation of her social group), and provides a model of autoethnographic dialogue.

The new woman, femininity and modernity in Margery Allingham's detective novels of the 1930s /

This thesis examines Death of a Ghost (1934), Flowers for the Judge (1935), Dancers in Mourning (1937), and The Fashion in Shrouds (1938), a group of detective novels by Margery Allingham that are differentiated from her other work by their generic hybridity. The thesis argues that the hybrid nature of this group of Campion novels enabled a highly skilled and insightful writer such as Allingham to negotiate the contradictory notions about the place of women that characterized the 1930s, and that in dOing so, she revealed the potential of one of the most popular and accessible genres, the detective novel of manners, to engage its readers in a serious cultural dialogue. The thesis also suggests that there is a connection between Allingham's exploration of modernity and femininity within these four novels and her personal circumstances. This argument is predicated upon the assumption that during the interwar period in England several social and cultural attitudes converged to challenge long-held beliefs about gender roles and class structure; that the real impact of this convergence was felt during the 1930s by the generation that had come of age in the previous decade-Margery Allingham's generation; and that that generation's ambivalence and confusion were reflected in the popular fiction of the decade. These attitudes were those of twentieth-century modernity--contradiction, discontinuity, fragmentation, contingency-and in the context of this study they are incorporated in a literary hybrid. Allingham uses this combination of the classical detective story and the novel of manners to examine the notion of femininity by juxtaposing the narrative of a longstanding patriarchal and hierarchical culture, embodied in the image of the Angel in the House, with that of the relatively recent rights and freedoms represented by the New Woman of the late nineteenth-century. Pierre Bourdieu's theory of social difference forms the theoretical foundation of the thesis's argument that through these conflicting narratives, as well as through the lives of her female characters, Allingham questioned the Hsocial myth" of the time, a prevailing view that, since the First World War, attitudes toward the appropriate role and sphere of women had changed.

Monstrum : the vampire in the detective story /

My approach to the vampire detective highlights its connections to the private detective's story and reveals the monstrous investigators' debt to early feminist forms of detection -specifically in their reformation of the' other' and of traditional forms of power and authority. Seen in this light the movement of horror's imaginary 'other' into the rational world of detection can be seen as not an abrupt breach of detection's realist conventions, but an almost seamless transition into symbolic spaces that point to the detective's primary function -- to make sense of the senseless. It is in this light that I explore the monster that is a detective as a symbol that is also a sense-maker, and a quintessential postmodern figure. I argue that the distinctions between monsters and 'others', and between popular narratives and postmodern religion have faded, culminating in a character that can not only model 'otherness' as an exemplary condition, but also provide strategies for modeling the form of active postmodern subjectivity that postmodern theorist Jim Collins' (1989) conceives of as heretical activity.

Will the "fight" ever end? : a critical reading of the metaphors and discourses that construct HIV/AIDS in an African context

In this thesis, I critically examine the discourses that inform how we conceptualise HIV/AIDS in Sub-Saharan Africa as they are produced in a sample of Canadian news articles, two nonfiction texts - Stephanie Nolen's 28 Stories of AIDS in Africa and Jonathan Morgan and the Bambanani Women's Group's Long Life ... Positive HIV Stories - as well as two literary texts - John Le Carre's popular fiction novel The Constant Gardener and an anthology of stories and poems from Southern Africa titled Nobody Ever Said AIDS, compiled and edited by Nobantu Rasebotsa, Meg Samuelson and Kylie Thomas. Paying particular attention to the role of metaphor in discursive formation, I have found that military metaphors, usually used in conjunction with biomedical discourses, continue to dominate what is said about HIV/AIDS. However, the use of military metaphors to conceptualise HIV/AIDS contributes to stigma and limits the effectiveness of responses to the pandemic. I argue that accessing alternative metaphors and discourses, such as biopsychosocial discourse, can lead to a more layered - and more beneficial - conceptualisation of HIV/AIDS, encouraging a more active response to the pandemic.

Relationship between photoperiod, plasma concentration of ionic calcium and the histology of the prolactin-secreting cells of the rostral pars distalis of the pituitary gland, the corpuscles of stannius and the ultimobranchial gland in the goldfish, Carassius auratus L. /

The relationship between photoperiod, plasma concentration of ionic calcium and the histology of the prolactin-secreting cells of the rostral pars distalis of the pituitary gland, the Corpuscles of Stannius and the Ultimobranchial gland were investigated. Neither the plasma concentration of ionic calcium nor histologically apparent prolactin cell activity could be correlated with photoperiod. Some evidence of a photoperiodic effect on both the Corpuscles of Stannius and the Ultimobranchial gland was obtained. The expected reciprocal relationship between the activity of these glands was not obvious at the histological level . Quantitative and qualitative analysis at the light microscope level revealed, however, that the hormone prolactin-secreting eta cells of the rostral pars distalis and the hypocalcin-secreting cells of the Corpuscles of Stannius may be arranged in a lamellar pattern comprized of synchronous bands of cells in like-phase of a secretory cycle consisting of four stages - synthesis, storage, release and reorganization. Such synchronized cell cycles in these glands have not heretofore been described in literature. It is suggested that the maintenance of at least 255? of the cells in any one phase of the cycle ensures a supply of the required hormone at all times.