868 resultados para Reactions in Polar Aprotic Media
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Long-lived light bullets fully localized in both space and time can be generated in novel photonic media such as multicore optical fiber or waveguide arrays. In this paper we present detailed theoretical analysis on the existence and stability of the discrete-continuous light bullets using a very generic model that occurs in a number of applications.
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Secondary pyrolysis in fluidized bed fast pyrolysis of biomass is the focus of this work. A novel computational fluid dynamics (CFD) model coupled with a comprehensive chemistry scheme (134 species and 4169 reactions, in CHEMKIN format) has been developed to investigate this complex phenomenon. Previous results from a transient three-dimensional model of primary pyrolysis were used for the source terms of primary products in this model. A parametric study of reaction atmospheres (H2O, N2, H2, CO2, CO) has been performed. For the N2 and H2O atmosphere, results of the model compared favorably to experimentally obtained yields after the temperature was adjusted to a value higher than that used in experiments. One notable deviation versus experiments is pyrolytic water yield and yield of higher hydrocarbons. The model suggests a not overly strong impact of the reaction atmosphere. However, both chemical and physical effects were observed. Most notably, effects could be seen on the yield of various compounds, temperature profile throughout the reactor system, residence time, radical concentration, and turbulent intensity. At the investigated temperature (873 K), turbulent intensity appeared to have the strongest influence on liquid yield. With the aid of acceleration techniques, most importantly dimension reduction, chemistry agglomeration, and in-situ tabulation, a converged solution could be obtained within a reasonable time (∼30 h). As such, a new potentially useful method has been suggested for numerical analysis of fast pyrolysis.
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We present the development and simplification of label-free fiber optic biosensors based on immobilization of oligonucleotides on dual-peak long period gratings (dLPGs). This improvement is the result of a simplification of biofunctionalization methodology. A one-step 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC)-mediated reaction has been developed for the straightforward immobilization of unmodified oligonucleotides on the glass fiber surface along the grating region, leading to covalent attachment of a 5´-phosphorylated probe oligonucleotide to the amino-derivatized fiber grating surface. Immobilization is achieved via a 5´phosphate-specific linkage, leaving the remainder of the oligonucleotide accessible for binding reactions. The dLPG has been tested in different external media to demonstrate its inherent ultrahigh sensitivity to the surrounding-medium refractive index (RI) achieving 50- fold improvement in RI sensitivity over the previously-published LPG sensor in media with RI’s relevant to biological assays. After functionalization, the dLPG biosensor was used to monitor the hybridization of complementary oligonucleotides showing a detectable oligonucleotide concentration of 4 nM. The proposed one-step EDC reaction approach can be further extended to develop fiber optic biosensors for disease analysis and medical diagnosis with the advances of label-free, real-time, multiplex, high sensitivity and specificity.
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Report published in the Proceedings of the National Conference on "Education and Research in the Information Society", Plovdiv, May, 2015
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With the development of social media tools such as Facebook and Twitter, mainstream media organizations including newspapers and TV media have played an active role in engaging with their audience and strengthening their influence on the recently emerged platforms. In this paper, we analyze the behavior of mainstream media on Twitter and study how they exert their influence to shape public opinion during the UK's 2010 General Election. We first propose an empirical measure to quantify mainstream media bias based on sentiment analysis and show that it correlates better with the actual political bias in the UK media than the pure quantitative measures based on media coverage of various political parties. We then compare the information diffusion patterns from different categories of sources. We found that while mainstream media is good at seeding prominent information cascades, its role in shaping public opinion is being challenged by journalists since tweets from them are more likely to be retweeted and they spread faster and have longer lifespan compared to tweets from mainstream media. Moreover, the political bias of the journalists is a good indicator of the actual election results. Copyright 2013 ACM.
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This paper introduces a quantitative method for identifying newly emerging word forms in large time-stamped corpora of natural language and then describes an analysis of lexical emergence in American social media using this method based on a multi-billion word corpus of Tweets collected between October 2013 and November 2014. In total 29 emerging word forms, which represent various semantic classes, grammatical parts-of speech, and word formations processes, were identified through this analysis. These 29 forms are then examined from various perspectives in order to begin to better understand the process of lexical emergence.
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The modulation instability (MI) in optical fiber amplifiers and lasers with anomalous dispersion leads to CW beam breakup and the growth of multiple pulses. This can be both a detrimental effect, limiting the performance of amplifiers, and also an underlying physical mechanism in the operation of MI-based devices. Here we revisit the analytical theory of MI in fiber optical amplifiers. The results of the exact theory are compared with the previously used adiabatic approximation model, and the range of applicability of the latter is determined. The same technique is applicable to the study of spatial MI in solid state laser amplifiers and MI in non-uniform media. © 2011 SPIE.
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Two new types of phenolic resin-derived synthetic carbons with bi-modal and tri-modal pore-size distributions were used as supports for Pd catalysts. The catalysts were tested in chemoselective hydrogenation and hydrodehalogenation reactions in a compact multichannel flow reactor. Bi-modal and tri-modal micro-mesoporous structures of the synthetic carbons were characterised by N2 adsorption. HR-TEM, PXRD and XPS analyses were performed for characterising the synthesised catalysts. N2 adsorption revealed that tri-modal synthetic carbon possesses a well-developed hierarchical mesoporous structure (with 6.5 nm and 42 nm pores), contributing to a larger mesopore volume than the bi-modal carbon (1.57 cm3 g-1versus 1.23 cm3 g-1). It was found that the tri-modal carbon promotes a better size distribution of Pd nanoparticles than the bi-modal carbon due to presence of hierarchical mesopore limitting the growth of Pd nanoparticles. For all the model reactions investigated, the Pd catalyst based on tri-modal synthetic carbon (Pd/triC) show high activity as well as high stability and reproducibility. The trend in reactivities of different functional groups over the Pd/triC catalyst follows a general order alkyne ≫ nitro > bromo ≫ aldehyde.
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New media platforms have changed the media landscape forever, as they have altered our perceptions of the limits of communication, and reception of information. Platforms such as Facebook, Twitter and WhatsApp enable individuals to circumvent the traditional mass media, converging audience and producer to create millions of ‘citizen journalists’. This new breed of journalist uses these platforms as a way of, not only receiving news, but of instantaneously, and often spontaneously, expressing opinions and venting and sharing emotions, thoughts and feelings. They are liberated from cultural and physical restraints, such as time, space and location, and they are not constrained by factors that impact upon the traditional media, such as editorial control, owner or political bias or the pressures of generating commercial revenue. A consequence of the way in which these platforms have become ingrained within our social culture is that habits, conventions and social norms, that were once informal and transitory manifestations of social life, are now infused within their use. What were casual and ephemeral actions and/or acts of expression, such as conversing with friends or colleagues or swapping/displaying pictures, or exchanging thoughts that were once kept private, or maybe shared with a select few, have now become formalised and potentially permanent, on view for the world to see. Incidentally, ‘traditional’ journalists and media outlets are also utilising new media, as it allows them to react, and disseminate news, instantaneously, within a hyper-competitive marketplace. However, in a world where we are saturated, not only by citizen journalists, but by traditional media outlets, offering access to news and opinion twenty-four hours a day, via multiple new media platforms, there is increased pressure to ‘break’ news fast and first. This paper will argue that new media, and the culture and environment it has created, for citizen journalists, traditional journalists and the media generally, has altered our perceptions of the limits and boundaries of freedom of expression dramatically, and that the corollary to this seismic shift is the impact on the notion of privacy and private life. Consequently, this paper will examine what a reasonable expectation of privacy may now mean, in a new media world.
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The traditional way of understanding television content consumption and viewer reactions may be simply summarised: information about the program, viewing at airing time, and interpersonal discussion after the program. In our digital media environment due to crossmedia consumption and platform shifts, the actual trend in audiovisual, and traditionally television content consumption is changing, the viewer’s journey is different across contents and platforms. Content is becoming independent from the platform and the medium is increasingly in the hands of technologically empowered viewers. Our objective is to uncover how traditional content expressly manufactured for television (series, reality shows, sports) can now be consumed via other platforms, and how and to what extent audiovisual content consumption is complemented or replaced by other forms (text, audio). In our exploratory research we identify the typical patterns of interaction and synergies of consumption across classical media content. In this study we used a multimethodology qualitative research design with three research phases including focus groups, online content analysis, and viewers’ narratives. Overall, the Video Star stays alive, but has to deal with immediate reactions and has to change according to his or her audiences’ wishes
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An awareness of mercury (Hg) contamination in various aquatic environments around the world has increased over the past decade, mostly due to its ability to concentrate in the biota. Because the presence and distribution of Hg in aquatic systems depend on many factors (e.g., pe, pH, salinity, temperature, organic and inorganic ligands, sorbents, etc.), it is crucial to understand its fate and transport in the presence of complexing constituents and natural sorbents, under those different factors. An improved understanding of the subject will support the selection of monitoring, remediation, and restoration technologies. The coupling of equilibrium chemical reactions with transport processes in the model PHREEQC offers an advantage in simulating and predicting the fate and transport of aqueous chemical species of interest. Thus, a great variety of reactive transport problems could be addressed in aquatic systems with boundary conditions of specific interest. Nevertheless, PHREEQC lacks a comprehensive thermodynamic database for Hg. Therefore, in order to use PHREEQC to address the fate and transport of Hg in aquatic environments, it is necessary to expand its thermodynamic database, confirm it and then evaluate it in applications where potential exists for its calibration and continued validation. The objectives of this study were twofold: 1) to develop, expand, and confirm the Hg database of the hydrogeochemical PHREEQC to enhance its capability to simulate the fate of Hg species in the presence of complexing constituents and natural sorbents under different conditions of pH, redox, salinity and temperature; and 2) to apply and evaluate the new database in flow and transport scenarios, at two field test beds: Oak Ridge Reservation, Oak Ridge, TN and Everglades National Park, FL, where Hg is present and is of much concern. Overall, this research enhanced the capability of the PHREEQC model to simulate the coupling of the Hg reactions in transport conditions. It also demonstrated its usefulness when applied to field situations.
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The concentration of C37-C39 long-chain alkenones and alkenes were determined in surface water and surface sediment samples from the subpolar waters of the Southern Ocean. Distributions of these compounds were similar in both sample sets indicating little differential degradation between or within compound classes. The relative amounts of the tri- to tetra-unsaturated C37 alkenones increased with increasing temperature for temperatures below 6°C similar to the di- and tri-unsaturated C37 alkenones. The C37 di-, tri-, and tetra-unsaturated methyl alkenones are used in paleotemperature calculations via the U37K and the U37K ratios. In these datasets, the relative abundances of the C37:2 and the C37.3 alkenones as a proportion of the total C37 alkenones were opposite and strongly related to temperature (the latter with more scatter), but the abundance of the C37:4 alkenone showed no relationship with temperature. The original definition of U37K includes the abundance of 37:4 in both the numerator and denominator, and thus it is perhaps not surprising that there is considerable scatter in the values obtained for U37K at low temperatures. Of the two, we suggest that U37K' is the better parameter for use in paleotemperature estimations, even in cold locations. U37K' values in the sediments fall on virtually the same regression line obtained for the water column samples of Sikes and Volkman (1993, doi:10.1016/0016-7037(93)90120-L), indicating that their calibration is suitable for use in Southern Ocean sediments. The comparison of water column data with sedimentary temperature estimates suggests that the alkenone distributions are dominated by contributions from the summer when the biomass of Emiliania huxleyi and presumably flux to the sediment, is expected to be high.
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Colistin, a cationic polypeptide antibiotic, has reappeared in human medicine as a last-line treatment option for multidrug-resistant Gram-negative bacteria (MDR-GNB). Colistin is widely used in veterinary medicine for the treatment of gastrointestinal infections caused by Enterobacteriaceae. GNB resistant to colistin owing to chromosomal mutations have already been reported both in human and veterinary medicine, however several recent studies have just identified a plasmid-mediated mcr-1 gene encoding for colistin resistance in Escherichia coli colistin resistance. The discovery of a non-chromosomal mechanism of colistin resistance in E. coli has led to strong reactions in the scientific community and to concern among physicians and veterinarians. Colistin use in food animals and particularly in pig production has been singled out as responsible for the emergence of colistin resistance. The present review will focus mainly on the possible link between colistin use in pigs and the spread of colistin resistance in Enterobacteriaceae. First we demonstrate a possible link between Enterobacteriaceae resistance emergence and oral colistin pharmacokinetics/pharmacodynamics and its administration modalities in pigs. We then discuss the potential impact of colistin use in pigs on public health with respect to resistance. We believe that colistin use in pig production should be re-evaluated and its dosing and usage optimised. Moreover, the search for competitive alternatives to using colistin with swine is of paramount importance to preserve the effectiveness of this antibiotic for the treatment of MDR-GNB infections in human medicine.
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Coverage of corruption in the Hungarian media was analyzed using four online news portals. Three of them, Magyar Nemzet Online (short name: MNO, web: mno.hu), Népszava (web: nepszava.hu) and Heti Világgazdaság (web: hvg.hu) are also available as newspapers but the content of these papers is different from the online form to a certain extent. The news portal Origo (web: origo.hu) has no print version.
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This thesis is split into three sections based on three different areas of research. In the first section, investigations into the α-alkylation of ketones using a novel chiral auxiliary is reported. This chiral auxiliary was synthesised containing a pyrrolidine ring in the chiral arm and was applied in the preparation of α-alkylated ketones which were obtained in up to 92% ee and up to 63% yield over two steps. Both 3-pentanone and propiophenone based ketones were used in the investigation with a variety of both alkyl and benzyl based electrophiles. The novel chiral auxiliary was also successful when applied to Michael and aldol reactions. A diamine precursor en route to the chiral auxiliary was also applied as an organocatalyst in a Michael reaction, with the product obtained in excellent enantioselectivity. In the second section, investigations into potential anti-quorum sensing molecules are reported. The bacteria Pseudomonas aeruginosa is an antibiotic-resistant pathogen that demonstrates cooperative behaviours and communicates using small chemical molecules in a process termed quorum sensing. A variety of C-3 analogues of the quorum sensing molecules used by P. aeruginosa were synthesised. Expanding upon previous research within the group, investigations were carried out into alternative protecting group strategies of 2-heptyl-4-(1H)- quinolone with the aim of improving the yields of products of cross-coupling reactions. In the third section, investigations into fluorination and trifluoromethylation of 2-pyrones, pyridones and quinolones is reported. The incorporation of a fluorine atom or a trifluoromethyl group into a molecule is important in pharmaceutical drug discovery programmes as it can lead to increased lipophilicity and bioavailability, however late-stage incorporation is rarely reported. Both direct fluorination and trifluoromethylation were attempted. Eight trifluoromethylated 2-pyrones, five trifluoromethylated 2-pyridones and a trifluoromethylated 2-quinolone were obtained in a late-stage synthesis from their respective iodinated precursors using methyl fluorosulfonyldifluoroacetate as a trifluoromethylating reagent.