55 research outputs found

    Idiopathic Recurrent Stupor, Still an Unsolved Issue

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    We report a case of unexplained recurrent stupor for which, given the current knowledge and the lack of easily available diagnostic tools, we were unable to reach a definite diagnosis. In the patient the syndrome was associated with an ominous prognosis. Worldwide accepted and easily available proceeding method is needed to manage patients with recurrent stupor for which a toxic origin may be suppose

    The Early Steps of Molecule-to-Material Conversion in Chemical Vapor Deposition (CVD): A Case Study

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    Transition metal complexes with \u3b2-diketonate and diamine ligands are valuable precursors for chemical vapor deposition (CVD) of metal oxide nanomaterials, but the metal-ligand bond dissociation mechanism on the growth surface is not yet clarified in detail. We address this question by density functional theory (DFT) and ab initio molecular dynamics (AIMD) in combination with the Blue Moon (BM) statistical sampling approach. AIMD simulations of the Zn \u3b2-diketonate-diamine complex Zn(hfa)2TMEDA (hfa = 1,1,1,5,5,5-hexafluoro-2,4-pentanedionate; TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine), an amenable precursor for the CVD of ZnO nanosystems, show that rolling diffusion of this precursor at 500 K on a hydroxylated silica slab leads to an octahedral-to-square pyramidal rearrangement of its molecular geometry. The free energy profile of the octahedral-to-square pyramidal conversion indicates that the process barrier (5.8 kcal/mol) is of the order of magnitude of the thermal energy at the operating temperature. The formation of hydrogen bonds with surface hydroxyl groups plays a key role in aiding the dissociation of a Zn-O bond. In the square-pyramidal complex, the Zn center has a free coordination position, which might promote the interaction with incoming reagents on the deposition surface. These results provide a valuable atomistic insight on the molecule-to-material conversion process which, in perspective, might help to tailor by design the first nucleation stages of the target ZnO-based nanostructures

    Manganese(II) Molecular Sources for Plasma-Assisted CVD of Mn Oxides and Fluorides: From Precursors to Growth Process

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    A viable route to manganese-based materials of high technological interest is plasma-assisted chemical vapor deposition (PA-CVD), offering various degrees of freedom for the growth of high-purity nanostructures from suitable precursors. In this regard, fluorinated \u3b2-diketonate diamine Mn(II) complexes of general formula Mn(dik)2\ub7TMEDA [TMEDA = N,N,N\u2032,N\u2032-tetramethylethylenediamine; Hdik = 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (Hhfa), or 1,1,1-trifluoro-2,4-pentanedione (Htfa)] represent a valuable option in the quest of candidate molecular sources for PA-CVD environments. In this work, we investigate and highlight the chemico-physical properties of these compounds of importance for their use in PA-CVD processes, through the use of a comprehensive experimental\u2013theoretical investigation. Preliminary PA-CVD validation shows the possibility of varying the Mn oxidation state, as well as the system chemical composition from MnF2 to MnO2, by simple modulations of the reaction atmosphere, paving the way to a successful utilization of the target compounds in the growth of manganese-containing nanomaterials for different technological applications

    Iconicity and dyslexia: theoretical issues and pedagogical implications

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    The present dissertation involves several branches of modern linguistics: iconicity, intended in its every facet, dyslexia, Specific Learning Disorders (SpLDs), and second language teaching. Of all the iconic properties, we favour those that involve language mostly at a phonological level, so that we may analyse their relationship with phonological deficits. We advance the hypothesis that iconicity constitutes a secondary access to phonological properties in case the primary one is impaired, as is the case with dyslexia. Thus, iconicity and sound symbolism represent a possible compensatory tool in second language learning – which, especially in the case of EnglishL2, constitutes a substantial difficulty for SpLD students. The present project aims to investigate this relationship and its possible exploitations in pedagogical, theoretical and methodological terms, and to create and test a teaching strategy involving iconic (or, more specifically, sound symbolic) instances of language. Furthermore, we present an experimental protocol on the effects of iconicity on University students with dyslexia

    A Gut-on-a-chip Model for Testing the Anti-inflammatory Effects of Active Compounds

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    Animal models are gold standards for testing active compounds on intestinal inflammatory conditions. However, the high costs involved cannot justify their use in all circumstances, such as in food and nutrition research. This study aimed to develop a gut-on-a-chip in vitro platform for screening the effect of anti-inflammatory compounds on gut inflammation. Because of its micrometre size, the chip allowed for reduced consumption of reagents. Furthermore, the use of constant media perfusion recreates the biological cues naturally present in the human body. CFD simulations were first performed to determine the effect of flow rate and shear stress on intestinal Caco-2 cells. These conditions were then tested and validated in vitro on a single-chamber chip to establish cell monolayers featuring tight junctions and other proteins. Co-cultures of Caco-2 with classically activated M1 macrophages were established in a double-chamber chip to represent the interaction between epithelial and immune cells. It was also found that damages of the intestinal barrier in vitro could be recreated via inflammatory triggers with TNF-α+LPS. Furthermore, this gut-on-a-chip was paired with a highly sensitive gene expression analysis for screening of over two hundred genes involved in human inflammation. To validate the functionality of the system, Dexamethasone and Mesalazine were used to modulate inflammation in both Caco-2 and M1 cells co-cultured in the gut-on-a-chip. To complement the study, Australian propolis was adopted as a natural product with anti-inflammatory properties. Regulations of genes involved in inflammatory mechanisms such as MAP2K6, COX2 and TNF were also recorded, resembling in vivo conditions. The findings suggest that the model developed in this study is functional and cost-effective and given the lowered consumption of reagents, this gut-on-a-chip could be used not only in the nutraceutical industry but also for the screening of expensive pharmaceuticals

    Indici strutturali e di competizione per la caratterizzazione di popolamenti cedui di castagno

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    Structural and competition indexes to characterise chestnut coppice stands. Structure, tree density and variation of tree specific composition are parameters useful to describe both natural dynamics and competition processes. In the field forestry, synthetic indices descriptive of both specific - structural diversity and competition are used, especially for high forests. In the present paper, the relations between silvicultural treatment and some synthetic indices descriptive of thinned chestnuts coppice stands differently aged are analysed. The main goals of the paper are: i) to verify the application of some in coppice stands, to evaluate their adaptation to differentiate and quantify the structural complexity, stand dynamics and competition processes as a function of past silvicultural history; ii) to ascertain the utility of the indices for the planning of future thinnings. The study was carried out in three experimental plots of the “Altopiano delle Pizzorne, (Lu)”. The stands analysed are differently aged (43 and 64 years) and as for silvicultural background which affected both the present structure and the ongoing competitive process. The detailed of stands structure analysis was carried out within experimental areas (1200m2), besides manserational parameters, data necessary to determine the competition indices were acquired. Data analysis led to determine synthetic indices of distributive, structural and specific diversity. The analysed stands show a one-storied, monospecifici structure with a tree distribution from regular to random and reduced level of individual competition. The chosen indices describe the effect of the applied treatment and show that the analysed stands are not characterized by the clustered distribution typical of coppices. The active silvicultural treatment determines the simplification of the stand structure. Furthermore, the selected indices, synthetic and easy to calculate, represent a useful operational instrument in silvicultural planning.</span

    The Intra-urban Location Rationale(s) of Knowledge-creating Services: Two Italian Case-studies

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    Recently, a debate has developed within the economic geography about agglomeration economies, which ensues from the transition from industrial to the knowledgedriven economy and from a deterministic to an evolutionary approach. While it is recognized that agglomeration economies are more important than location economies in the new context, their nature is being still questioned, especially between New Economic Geography and Evolutionary Economic Geography. This paper aims at contributing to that debate through novel or barely explored epistemological and methodological approaches. Our results, while confirming the importance of agglomeration economies, shed new light on the role of location economies especially at the intra-urban scale

    THE INTRAURBAN LOCATION RATIONALE(S) OF THE KNOWLEDGE-CREATING SERVICES: TWO ITALIAN CASE-STUDIES

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    Recently, a debate has developed within the economic geography about agglomeration economies, which ensues from the transition from industrial to the knowledgedriven economy and from a deterministic to an evolutionary approach. While it is recognized that agglomeration economies are more important than location economies in the new context, their nature is being still questioned, especially between New Economic Geography and Evolutionary Economic Geography. This paper aims at contributing to that debate through novel or barely explored epistemological and methodological approaches. Our results, while confirming the importance of agglomeration economies, shed new light on the role of location economies especially at the intra-urban scale

    MODELING THE FIRST ACTIVATION STAGES OF THE Fe(hfa)2TMEDA CVD PRECURSOR ON A HEATED GROWTH SURFACE

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    Iron oxide-based functional nanostructures are important technological materials that can be fruitfully obtained with high purity and tailored phase composition/morphology by Chemical Vapor Deposition (CVD). In this context, previous works have experimentally demonstrated the suitability of the Fe(II) diketonate-diamine complex Fe(hfa)2TMEDA as CVD precursor. However, further progress in the field strongly depends on the understanding of mechanisms governing the molecule-to-materials conversion, a goal that can be achieved by advanced computational methods. In this work, structural optimization of the Fe(hfa)2TMEDA molecule on a model CVD growth surface was performed to provide an insight on the physisorption geometry at 0 K. The first stages of thermally activated surface processes were then investigated by first principles molecular dynamics simulation, which revealed interesting aspects of the precursor behaviour at temperatures conditions typically adopted in Fe2O3 deposition experiments. Whereas the physisorbed complex maintains its octahedral geometry, high temperature interactions with the surface lead to drastic perturbations of the molecular structure and significant weakening of the coordination bonds of the metal center with the diamine ligands. Our results provide key elements for the fundamental knowledge of the temperatureinduced behaviour of this precursor on a heated substrate, which may help the understanding of its CVD activation mechanisms and decomposition pathways
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