1,720,986 research outputs found

    INTERFACIAL PROPERTIES OF IONIC LIQUIDS:ELECTRIC PROPERTIES OF THIN FILMS AND INTERACTION WITH MODEL MEMBRANES AND LIVING CELLS

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    Room-Temperature Ionic Liquids (ILs) have attracted considerable interest in recent years. This interest is motivated by the physico-chemical properties of these systems, tunable modifying the chemical structure of ions. Generally, ILs show chemical and thermal stability, i.e. they do not easily decompose or react. Furthermore, these compounds remain liquid over an extended range of temperatures, in which they show also a remarkably low volatility. The low vapor pressure of ILs, promote them as good solvents for the growing field of the ”Green Chemistry”, in substitution of the volatile organic compounds. The fact that ILs are composed solely by ions, and can have a quite wide electrochemical window, make them very interesting as electrolytes. For these purposes, this PhD thesis is devoted to the investigation of ILs in contact with solid interfaces, primary targets of interaction. To deepen the analysis of electric properties at the solid interface, thin layers of ILs deposited on conductive substrates were investigated by means of AFM. The ”Green” character of these compounds was investigated studying their interaction with biomembrane models and external membranes of living cells, by means of AFM and electrochemical methods. Because of their ionic nature, ILs can be used as electrolytes in several devices aimed at conversion and storage of energy, such as electrochemical supercapacitors, Graetzel solar cells and batteries. In these devices a key role is played by the interface between the surface of the electrodes and the electrolyte; in particular, structural-morphological and electrical properties of the first few nanometers of IL interacting with the solid electrode surface are expected to have the strongest impact on device performance. AFM morphological analysis of small quantity of [C 4 MIM] [NTf 2 ] IL, deposited on various insulating surfaces revealed a population of nanodroplets and new structures. Remarkably, the solid surfaces induce the organization of the ionic liquid into regular, lamellar solid-like nanostructures presenting a high degree of vertical structural order and high mechanical resistance to normal compressive stresses. Nanomechanical investigation reveals that the structures resist to normal compressive loads up to 1.5 MPa; beyond that limit, indentation, in discrete steps, occurs. Furthermore, lamellar [C 4 MIM] [NTf 2 ] islands are not affected when scanned by a biased AFM tip under the influence of an electric field as intense as 10 8 V/m, while the liquid nano-and micro-droplets are easily swept away. These results confirm the solid-like character of the ordered lamellar nanostructures observed when thin films of [C 4 MIM] [NTf 2 ] are deposited on solid surfaces, and suggest that these films may possess an insulating, dielectric behavior, at odd with the case of the bulk ionic liquids. Nanoscale impedance measurements (capacitance vs. distance) and electrostatic force spectroscopy (electric force vs. distance) between a conductive AFM tip and the IL structures confirmed that values of the dielectric constant (ε r = 3-5) are significantly smaller than those measured in the bulk liquid (ε r = 9-15). These results support the picture of solid-like ordered domains where the ion mobility is significantly inhibited with respect to the bulk liquid phase. These findings also highlight the potentialities of scanning probe techniques for the quantitative investigation of the interfacial electrical properties of thin ionic liquid films, suggesting that ILs at electrified solid surfaces may possess unexpected electrical and structural properties, thus influencing the behavior of photo-electrochemical devices. The ”green” character of ionic liquids (ILs) is dependent on their negligible vapor pressure but in contrast to their environmental behavior their intrinsic toxicity is not at present completely understood. Accordingly, although ILs will not evaporate which alleviates air pollution problems, a potential hazard of Ils to living organisms via aqueous media cannot be ruled out. A rigorous investigation on the interaction of ILs with biomaterials is required to provide information about their intrinsic toxicity. In order to test the biocompatible character of ILs, as a first objective, the interaction of various ILs with biological membrane (biomembrane) models was studied using electrochemical methods. A series of imidazolium based ILs were investigated whose interactions highlighted the role of anion and lateral side chain of cation during the interaction with dioleoyl phosphatidylcholine (DOPC) monolayer. It was shown that the hydrophobic and lipophilic character of the IL cations is a primary factor responsible for this interaction. The modifications of the Hg supported monolayer caused by ILs were simultaneously monitored electrochemically in a well controlled manner using rapid cyclic voltammetry (RCV), alternating current voltammetry (ACV), and electrochemical impedance spectroscopy (EIS). Hg supported monolayers provide an accurate analysis of the behavior of ILs at the interface of a biomembrane leading to a comprehensive understanding of the interaction mechanisms involved. At the same time, these experiments show that the Hg-phospholipid model is an effective toxicity sensing technique as shown by the correlation between literature in vivo toxicity data and the data from this study. Cell membrane is the main target of ILs interaction, depending on the lipophilicity of hydrophobic lateral chain of cation. In order to test the biocompatible character of ILs, the interaction of various imidazolium-based ILs with supported DOPC phospholipid bilayers (as models of the cell membrane) and living MDA-MB-231 cells (@37 ◦C) was investigated. Atomic Force Microscopy (AFM) was used to carry on a combined topographic and mechanical analysis of supported DOPC bilayers as well as of living cells. During the analysis of DOPC bilayers we have observed modifications in breakthrough force and membrane elasticity related to the ingress of lateral chains of cations in the bilayer, demonstrating agreement with electrochemical results. The parallel nanomechanical analysis performed on living cells interacting with ILs at various concentrations showed modifications of elasticity (effective Young’s modulus) and morphology of cells after exposure to ILs dispersed in their culture medium. The measurements confirmed the primary action of ILs on membrane and actin cytoskeleton, highlighting a subtoxic/toxic effect dependent on ILs concentration and chemical nature of cation. Our results may be helpful for filling existing gaps of knowledge about ionic liquids toxicity and their impact on living organisms. From these evidences, interaction of ILs with micro-organisms and single cells is an important step to assess the environmental sustainability of this novel and promising class of solvents and to attribute a ”green” label to it. Studying the interaction of ionic liquids, it has been recognized that the interface is a vital component. When the bulk symmetry of IL is broken by surfaces, the electrical properties are greatly affected, leading from a ion conductor to an insulator behavior. Also the interaction with biological entity is driven, in first instance, by surface interaction. Biomembrane models and cell membranes are affected by ILs that accumulate/penetrate the surface interface, leading to structural reorganization/damage of external membrane

    Going Beyond Counting First Authors in Author Co-citation Analysis

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    The present study examines one of the fundamental aspects of author co-citation analysis (ACA) - the way co-citation counts are defined. Co-citation counting provides the data on which all subsequent statistical analyses and mappings are based, and we compare ACA results based on two different types of co-citation counting - the traditional type that only counts the first one among a cited work's authors on the one hand and a non-traditional type that takes into account the first 5 authors of a cited work on the other hand. Results indicate that the picture produced through this non-traditional author co-citation counting contains more coherent author groups and is therefore considerably clearer. However, this picture represents fewer specialties in the research field being studied than that produced through the traditional first-author co-citation counting when the same number of top-ranked authors is selected and analyzed. Reasons for these effects are discussed

    Variations on the Author

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    “Variations on the Author” discusses two of Eduardo Coutinho’s recent films (Um Dia na Vida, from 2010, and Últimas Conversas, posthumously released in 2015) and their contribution to the general question of documentary authorship. The director’s filmography is characterized by a consistent yet self-effacing form of authorial self-inscription: Coutinho often features as an interviewer that rather than express opinions propels discourses; an interviewer that is good at listening. This mode of self-inscription characterizes him as an author who is not expressive but who is nonetheless markedly present on the screen. In Um Dia na Vida, however, Coutinho is completely absent form the image, while Últimas Conversas, on the contrary, includes a confessional prologue that moves the director from the margins to the center of his films. This article examines the ways in which these works stand out in the filmography of a director who offers new insights into the notion of cinematic authorship

    Appropriate Similarity Measures for Author Cocitation Analysis

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    We provide a number of new insights into the methodological discussion about author cocitation analysis. We first argue that the use of the Pearson correlation for measuring the similarity between authors’ cocitation profiles is not very satisfactory. We then discuss what kind of similarity measures may be used as an alternative to the Pearson correlation. We consider three similarity measures in particular. One is the well-known cosine. The other two similarity measures have not been used before in the bibliometric literature. Finally, we show by means of an example that our findings have a high practical relevance.information science;Pearson correlation;cosine;similarity measure;author cocitation analysis

    Dispelling the Myths Behind First-author Citation Counts

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    We conducted a full-scale evaluative citation analysis study of scholars in the XML research field to explore just how different from each other author rankings resulting from different citation counting methods actually are, and to demonstrate the capability of emerging data and tools on the Web in supporting more realistic citation counting methods. Our results contest some common arguments for the continued use of first-author citation counts in the evaluation of scholars, such as high correlations between author rankings by first-author citation counts and other citation counting methods, and high costs of using more realistic citation counting methods that are not well-supported by the ISI databases. It is argued that increasingly available digital full text research papers make it possible for citation analysis studies to go beyond what the ISI databases have directly supported and to employ more sophisticated methods

    Author Index

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    koamabayili/VECTRON-author-checklist: VECTRON author checklist

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    We have done our best to complete the author checklist relating to the use of animals in the hut study. Note that the objective for the hut study was to evaluate the IRS treatment applications for residual efficacy against Anopheles mosquitoes, including the local An. coluzzii mosquito population. Cows were only used to attract mosquitoes into the huts and no tests were carried out directly on the cows. The author checklist is intended for use with studies where experiments are carried out on animals, which is why we have had such difficulty in completing this for the hut study, as many of the questions do not relate to how the cows were used

    Osservazioni sul funzionamento di macchine e meccanismi nel teatro antico

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    Indagine letteraria e sui reperti archeologici riconducibili a meccanismi per effetti speciali nel teatro antico. Parallelo tra le tecnologie meccaniche alla base del funzionamento dei teatrini di automi e del teatro stabile
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