1,721,003 research outputs found
Accelerating effect of imidazolium ionic liquids on the singlet oxygen promoted oxidation of thioethers: A theoretical study
No full textA computational study of the catalytic activity exhibited by imidazolium based ionic liquids on the singlet oxygen promoted oxidation of thioethers is presented. The reaction of singlet oxygen with thioanisole and diethyl sulfide, in the absence and in the presence of 1-butyl-3-methylimidazolium cation, was followed along the reaction coordinate up to the formation of the persulfoxide intermediate that is widely recognized as the key intermediate in this process. In line with previous experimental observations, the results obtained show that the imidazolium cation strongly stabilizes the persulfoxide intermediate by hydrogen bonding thus depressing the unproductive intersystem crossing and favoring product formation. Evidence for a significant role played by exciplex intermediates in this reaction was also found. Surprisingly, the results for the singlet oxygen-sulfide system in the absence of imidazolium show that whereas diethyl sulfide can readily form the persulfoxide intermediate, from which S-oxidation products ensue, for thioanisole the persulfoxide formation is characterized by a high activation energy. A detailed investigation on the role played by the aromatic ring in this dramatic activation energy increase is presented suggesting, for the first time, a rationale for the well known low reactivity exhibited by aromatic sulfides in reactions with singlet oxygen. (C) 2012 Elsevier B.V. All rights reserved
ChemInform Abstract: Point‐Functionalization of Ionic Liquids: An Overview of Synthesis and Applications
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Going Beyond Counting First Authors in Author Co-citation Analysis
Full text linkThe 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
Full text link“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
Full text linkWe 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
Full text linkWe 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
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