Piezoelectricity and ferroelectricity in amino acid glycine

Bioorganic ferroelectrics and piezoelectrics are becoming increasingly important in view of their intrinsic compatibility with biological environment and biofunctionality combined with strong piezoelectric effect and switchable polarization at room temperature. Here we study piezoelectricity and ferroelectricity in the smallest amino acid glycine, representing a broad class of non-centrosymmetric amino acids. Glycine is one of the basic and important elements in biology, as it serves as a building block for proteins. Three polymorphic forms with different physical properties are possible in glycine (α, β and γ), Of special interest for various applications are non-centrosymmetric polymorphs: β-glycine and γ-glycine. The most useful β-polymorph being ferroelectric took much less attention than the other due to its instability under ambient conditions. In this work, we could grow stable microcrystals of β-glycine by the evaporation of aqueous solution on a (111)Pt/Ti/SiO2/Si substrate as a template. The effects of the solution concentration and Pt-assisted nucleation on the crystal growth and phase evolution were characterized by X-ray diffraction analysis and Raman spectroscopy. In addition, spin-coating technique was used for the fabrication of highly aligned nano-islands of β-glycine with regular orientation of the crystallographic axes relative the underlying substrate (Pt). Further we study both as-grown and tip-induced domain structures and polarization switching in the β-glycine molecular systems by Piezoresponse Force Microscopy (PFM) and compare the results with molecular modeling and computer simulations. We show that β-glycine is indeed a room-temperature ferroelectric and polarization can be switched by applying a bias to non-polar cuts via a conducting tip of atomic force microscope (AFM). Dynamics of these in-plane domains is studied as a function of applied voltage and pulse duration. The domain shape is dictated by both internal and external polarization screening mediated by defects and topographic features. Thermodynamic theory is applied to explain the domain propagation induced by the AFM tip. Our findings suggest that β-glycine is a uniaxial ferroelectric with the properties controlled by the charged domain walls which in turn can be manipulated by external bias. Besides, nonlinear optical properties of β-glycine were investigated by a second harmonic generation (SHG) method. SHG method confirmed that the 2-fold symmetry is preserved in as-grown crystals, thus reflecting the expected P21 symmetry of the β-phase. Spontaneous polarization direction is found to be parallel to the monoclinic [010] axis and directed along the crystal length. These data are confirmed by computational molecular modeling. Optical measurements revealed also relatively high values of the nonlinear optical susceptibility (50% greater than in the z-cut quartz). The potential of using stable β-glycine crystals in various applications are discussed in this work.

Infection mechanism of Diplodia corticola

Diplodia corticola is regarded as the most virulent fungus involved in cork oak decline, being able to infect not only Quercus species (mainly Q. suber and Q. ilex), but also grapevines (Vitis vinifera) and eucalypts (Eucalyptus sp.). This endophytic fungus is also a pathogen whose virulence usually manifests with the onset of plant stress. Considering that the infection normally culminates in host death, there is a growing ecologic and socio-economic concern about D. corticola propagation. The molecular mechanisms of infection are hitherto largely unknown. Accordingly, the aim of this study was to unveil potential virulence effectors implicated in D. corticola infection. This knowledge is fundamental to outline the molecular framework that permits the fungal invasion and proliferation in plant hosts, causing disease. Since the effectors deployed are mostly proteins, we adopted a proteomic approach. We performed in planta pathogenicity tests to select two D. corticola strains with distinct virulence degrees for our studies. Like other filamentous fungi D. corticola secretes protein at low concentrations in vitro in the presence of high levels of polysaccharides, two characteristics that hamper the fungal secretome analysis. Therefore, we first compared several methods of extracellular protein extraction to assess their performance and compatibility with 1D and 2D electrophoretic separation. TCA-Acetone and TCA-phenol protein precipitation were the most efficient methods and the former was adopted for further studies. The proteins were extracted and separated by 2D-PAGE, proteins were digested with trypsin and the resulting peptides were further analysed by MS/MS. Their identification was performed by de novo sequencing and/or MASCOT search. We were able to identify 80 extracellular and 162 intracellular proteins, a milestone for the Botryosphaeriaceae family that contains only one member with the proteome characterized. We also performed an extensive comparative 2D gel analysis to highlight the differentially expressed proteins during the host mimicry. Moreover, we compared the protein profiles of the two strains with different degrees of virulence. In short, we characterized for the first time the secretome and proteome of D. corticola. The obtained results contribute to the elucidation of some aspects of the biology of the fungus. The avirulent strain contains an assortment of proteins that facilitate the adaptation to diverse substrates and the identified proteins suggest that the fungus degrades the host tissues through Fenton reactions. On the other hand, the virulent strain seems to have adapted its secretome to the host characteristics. Furthermore, the results indicate that this strain metabolizes aminobutyric acid, a molecule that might be the triggering factor of the transition from a latent to a pathogenic state. Lastly, the secretome includes potential pathogenicity effectors, such as deuterolysin (peptidase M35) and cerato-platanin, proteins that might play an active role in the phytopathogenic lifestyle of the fungus. Overall, our results suggest that D. corticola has a hemibiotrophic lifestyle, switching from a biotrophic to a necrotrophic interaction after plant physiologic disturbances.This understanding is essential for further development of effective plant protection measures.

Sustainability study of the application of geosynthetic clay liners in hostile and aggressive environments

This paper discusses the sustainable performance of geosynthetic clay liners (GCLs) which are popularly specified as “leachate retaining” or as “water proofing” membranes in the geo-environmental construction industry. Geosynthetic clay liners (GCLs) are composite matting comprising of bentonite clay with two covering geosynthetics. These are innovative labour saving construction material, developed over the last three decades. The paper outlines the variety of Geosynthetic Clay Liners (GCLs) can be classified essentially into two distinctly different forms viz; (a) air dry (< 8% m/c) with granular or powdered bentonite or (b) bentonite cake factory prehydrated to a moisture content (~40% m/c) beyond its shrinkage limit and vacuum extruded as a clay cake to enhance its sustainable performance. The dominant mineral in bentonite clay is the three-layered (2:1) clay mineral montmorillonite. High quality bentonites need to be used in the GCL manufacture. Sodium montmorillonite has the desired characteristic of high swelling capacity, high cation exchange capacity and the consequently very low hydraulic conductivity, providing the basis for the hydraulic sealing medium in GCLs. These encapsulate the active montmorillonite clay minerals which depend on the water and chemical balance between the sealing element and the surrounding geo environment. Quantitative mineralogical analyses and an assessment of the adsorbed cation regime, diffusion coefficients and clay leachate compatibility must necessarily be an integral part of the site appraisal to ensure acceptable long term sustainability and performance. Factors influencing the desired performance of bentonite in the GCLs placed in difficult construction and hostile chemical environments are discussed in this paper. Accordingly, the performance specifications for GCLs are identified and the appropriateness of enhancing the cation exchange capacity with polymer treatment and the need for factory prehydration of the untreated sodium bentonite is emphasised. The advantage of factory prehydrating the polymer treated bentonite to fluid content beyond its shrinkage limit and subsequently factory processing it to develop laminated clay is to develop a GCL that has enviable sealing characteristics with a greater resistance to geochemical attack and cracking. Since clay liners are buried in the ground as base liners, capping layer or as structural water proofing membrane, they can easily avoid strict quality and performance monitoring being “out of sight, out of mind!”. It is very necessary that barrier design for leachate containment must necessarily be in accordance with legislative requirement Assessment of long term hydraulic conductivities and clay-leachate compatibility assessment is deemed necessary. The derogatory factors affecting the sustainable performance of the bentonite in GCLs placed in difficult construction and hostile chemical environments are discussed. Sustainability concepts incorporated in waste management practice must aim to achieve 100% recycling and fully implement the handling of solid waste in developing countries with relatively lower labour costs.

Observed bodies generate object-based spatial codes

Contemporary studies of spatial and social cognition frequently use human figures as stimuli. The interpretation of such studies may be complicated by spatial compatibility effects that emerge when researchers employ spatial responses, and participants spontaneously code spatial relationships about an observed body. Yet, the nature of these spatial codes – whether they are location- or object-based, and coded from the perspective of the observer or the figure – has not been determined. Here, we investigated this issue by exploring spatial compatibility effects arising for objects held by a visually presented whole-bodied schematic human figure. In three experiments, participants responded to the colour of the object held in the figure’s left or right hand, using left or right key presses. Left-right compatibility effects were found relative to the participant’s egocentric perspective, rather than the figure’s. These effects occurred even when the figure was rotated by 90 degrees to the left or to the right, and the coloured objects were aligned with the participant’s midline. These findings are consistent with spontaneous spatial coding from the participant’s perspective and relative to the normal upright orientation of the body. This evidence for object-based spatial coding implies that the domain general cognitive mechanisms that result in spatial compatibility effects may contribute to certain spatial perspective-taking and social cognition phenomena.

L'adoption d'une innovation technopédagogique par une communauté enseignante universitaire

Résumé: L'adoption d'une innovation technopédagogique par une communauté enseignante universitaire La thèse traite de l'adoption d'une innovation technopédagogique par une communauté enseignante universitaire. Cette étude longitudinale, réalisée dans le cadre d'une recherche-action, vise à comprendre la dynamique globale du processus d'adoption d'une innovation. Le cadre de réflexion théorique de l'étude provient de la recherche en management, en systèmes d'information et en éducation. Il tient à la fois compte des motivations et des besoins des individus (dimension individuelle), de la compatibilité des technologies de l'information selon les théories usuelles de l'apprentissage (dimension pédagogique) et du type de soutien à offrir aux utilisatrices-utilisateurs (dimension organisationnelle). Le modèle d'accompagnement émergeant de cette recherche se compose de cycles itératifs au cours desquels un groupe définit et résout un problème, puis réfléchit successivement aux enjeux émergents d'un cycle à l'autre. Le modèle tient explicitement compte des trois éléments clés suivants: l'individu, la pédagogie et l'organisation qui forment une dynamique systémique indissociable et en interaction les unes les autres pendant toute la durée du processus d'adoption de l'innovation. Il met aussi en lumière la nécessité de stimuler une réflexion critique grâce au concours de ressources externes crédibles pour déterminer la compatibilité des technologies à partir d'expériences concrètes. Une telle démarche participative systématique permet d'accroître la cohésion des idées du groupe par le dialogue et les débats d'opinions_ Par ailleurs, la proximité avec notre milieu de recherche sur une période de deux ans offre la possibilité de saisir plusieurs facettes de la dynamique organisationnelle. Lorsque l'on réalise une étude longitudinale qui met en évidence l'incidence d'événements concomitants, on constate la fragilité du processus et la réversibilité de la décision d'adoption. L'intention d'adoption évolue constamment au gré des expériences des individus et du contexte qui évolue lui-même. L'établissement de relations partenariales avec les groupes intéressés représente une activité essentielle pour pallier ou neutraliser les effets indésirables d'événements concomitants.||Abstract: This thesis deals with a university teaching community adopting a technological/pedagogical innovation. This longitudinal study--part of an action-research study--aims at gaining understanding of the overall dynamics involved in adopting an innovation. The study's conceptual framework derives from management, information-systems, and teaching research. It takes into account the motivations and needs of individuals (individual dimension), the compatibility of information technologies according to current learning theories (pedagogical dimension), and the type of support to be offered to users (organizational dimension). The companion model issuing from this research work comprises iterative cycles during which a group defines and solves a problem and then successively reflects on the issues emerging from one cycle to the next. The model takes explicit account of three key elements: the individual, pedagogical approach, and organization form an indissociable system dynamic in which all dimensions interact during the entire process of adopting innovation. It also sheds light on the need to stimulate critical reflection about the combination of credible external resources so that tangible experiences can be used to determine technology compatibility. This kind of systematic participative process yields greater cohesiveness of group ideas through dialogue and discussion. Moreover, the proximity to our research setting over two years provides the opportunity to seize the many facets of organizational dynamics. During the course of a longitudinal study that highlights the incidence of concomitant events, the fragility of the process and reversibility of the adoption decision become apparent. The adoption intention constantly fluctuates through the experiences of individuals and the context, which also changes. Establishing partnership relations with interested groups stands out as an essential activity in attenuating or counteracting the undesirable effects produced by concomitant events.

An embodied approach to language: the role of bodily feedback in discourse processing

Theories of embodied cognition argue that language processing arises not from amodal symbols that redescribe sensorimotor and affective experiences, but from partial simulations (reenactments) of modality-specific states. Recent findings on processing of words and sentences support such a stance emphasizing that the role of the body in the domain of language comprehension should not be overlooked or dismissed. The present research was conducted to extend prior work in two important ways. First, the role of simulation was tested with connected discourse rather than words or sentences presented in isolation. Second, both “online” and “offline” measures of discourse comprehension were taken. In Experiments 1 and 2 participants’ facial postures were manipulated to show that preparing the body for processing of emotion-congruent information improves discourse comprehension. In Experiment 3 the direction of body posture was manipulated to show that implicit properties of simulations, such as spatial dimension or location, are at least somewhat involved in processing of large language segments such as discourse. Finally, in Experiments 4 and 5 participants’ body movement and body posture were manipulated to show that even understanding of language describing metaphorical actions physically impossible to perform involves constructing a sensorimotor simulation of the described event. The major result was that compatibility between embodiment and language strongly modulated performance effectiveness in experiments on simulation of emotion and metaphorical action. The effect of simulation on comprehension of discourse implying spatial dimension was fragile. These findings support an embodied simulation account of cognition suggesting that sensorimotor and affective states are at least partially implicated in “online” and “offline” discourse comprehension.

Um modelo para a melhoria da qualidade dos recursos humanos das autarquias locais

Dissertação de Mestrado, Gestão Empresarial, Faculdade de Economia, Universidade do Algarve, 2004

Real-time scheduling in multicore : time- and space-partitioned architectures

Tese de doutoramento, Informática (Engenharia Informática), Universidade de Lisboa, Faculdade de Ciências, 2014

As representações das equipas de avaliação externa da IGEC na dimensão relativa à autoavaliação das escolas

Relatório de estágio de mestrado, Ciências da Educação (Especialização em Administração Educacional), Universidade de Lisboa, Instituto de Educação, 2014

Reestruturação produtiva e desenvolvimento local : o caso do Município de Toledo, Estado do Paraná, Brasil

Tese de doutoramento, Geografia (Planeamento Regional e Urbano), Universidade de Lisboa, Instituto de Geografia e Ordenamento do Território, 2016

Medicinal chemistry approaches to malaria drug discovery

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2016

Play it Again

Tese de doutoramento, Belas-Artes (Pintura), Universidade de Lisboa, Faculdade de Belas-Artes, 2016

Broadband Green's Function and Applications to Fast Electromagnetic Analysis of High-Speed Interconnects

Thesis (Ph.D.)--University of Washington, 2015

Investigation of the impact of feeding Lactobacillus plantarum CRL 1815 encapsulated in microbially derived polymers on the rat faecal microbiota

AIMS: The aim of this study was to evaluate the impact of the administration of microencapsulated Lactobacillus plantarum CRL 1815 with two combinations of microbially derived polysaccharides, xanthan : gellan gum (1%:0·75%) and jamilan : gellan gum (1%:1%), on the rat faecal microbiota. METHODS AND RESULTS: A 10-day feeding study was performed for each polymer combination in groups of 16 rats fed either with placebo capsules, free or encapsulated Lact. plantarum or water. The composition of the faecal microbiota was analysed by fluorescence in situ hybridization and temporal temperature gradient gel electrophoresis. Degradation of placebo capsules was detected, with increased levels of polysaccharide-degrading bacteria. Xanthan : gellan gum capsules were shown to reduce the Bifidobacterium population and increase the Clostridium histolyticum group levels, but not jamilan : gellan gum capsules. Only after administration of jamilan : gellan gum-probiotic capsules was detected a significant increase in Lactobacillus-Enterococcus group levels compared to controls (capsules and probiotic) as well as two bands were identified as Lact. plantarum in two profiles of ileum samples. CONCLUSIONS: Exopolysaccharides constitute an interesting approach for colon-targeted delivery of probiotics, where jamilan : gellan gum capsules present better biocompatibility and promising results as a probiotic carrier. SIGNIFICANCE AND IMPACT OF STUDY: This study introduces and highlights the importance of biological compatibility in the encapsulating material election, as they can modulate the gut microbiota by themselves, and the use of bacterial exopolysaccharides as a powerful source of new targeted-delivery coating material.

Electrospun medicated shellac nanofibers for colon-targeted drug delivery

Medicated shellac nanofibers providing colon-specific sustained release were fabricated using coaxial electrospinning. A solution of 7.5 g shellac and 1.5 g of ferulic acid (FA) in 10 mL ethanol was used as the core fluid, and a mixture of ethanol and N,N-dimethylformamide (8/10 v/v) as the shell. The presence of the shell fluid was required to prevent frequent clogging of the spinneret. The diameters of the fibers (D) can be manipulated by varying the ratio of shell to core flow rates (F), according to the equation D = 0.52F−0.19. Scanning electron microscopy images revealed that fibers prepared with F values of 0.1 and 0.25 had linear morphologies with smooth surfaces, but when the shell fluid flow rate was increased to 0.5 the fiber integrity was compromised. FA was found to be amorphously distributed in the fibers on the basis of X-ray diffraction and differential scanning calorimetry results. This can be attributed to good compatibility between the drug and carrier: IR spectra indicated the presence of hydrogen bonds between the two. In vitro dissolution tests demonstrated that there was minimal FA release at pH 2.0, and sustained release in a neutral dissolution medium. The latter occurred through an erosion mechanism. During the dissolution processes, the shellac fibers were gradually converted into nanoparticles as the FA was freed into solution, and ultimately completely dissolved.