1,720,958 research outputs found
Ring-opening polymerization of cyclic esters by phenoxy-thioether complexes derived from biocompatible metals
A series of novel Mg(ii) and Zn(ii) complexes of the form LMX or L2M, supported by phenoxy-thioether ligands bearing different substituents at the ortho position of the thiophenol rings [L- = 4,6-tBu2-OC6H2-2-CH2S(2-R-C6H4)-] [M = Zn, R = H, X = N(SiMe3)2 (1) and X = Et (2); M = Mg, X = n-Bu, R = H (3), R = CH3 (4), R = Br (5); M = Mg, R = H (6)], were synthesized and characterized. Reaction of the proper zinc precursor (Zn[N(SiHMe2)2]2 or ZnEt2) with one equiv. of the phenoxy-thioether proligand produced the corresponding amido (1) and Et (2) zinc complexes in high yields. The monoalkylmagnesium complexes (3-5) were all obtained by butane elimination reaction of the dialkylmagnesium reagent, Mg(n-Bu)2, with one equiv. of the proligand in good yields. The homoleptic complex 6 was obtained by reaction of 0.5 equiv of Mg(n-Bu)2 and the proper proligand. Variable temp. 1H NMR studies performed on 2 and 3 demonstrated that the named complexes are involved in fluxional processes concerning a fast conformational change of the six-membered metallacycle. DOSY (Diffusion Ordered SpectroscopY) 1H expts. and ligand scrambling strongly suggested that complexes 1-6 exist as dimeric species in soln. All complexes were active as catalysts in the ring-opening polymn. of cyclic esters. In particular, magnesium complexes showed superior ε-caprolactone and lactide ROP behavior in terms of activity, control of mol. wts. and mol. wt. distributions
Rare earth complexes of phenoxy-thioether ligands: synthesis and reactivity in the ring opening polymerization of cyclic esters
The potential of the phenoxy-thioether moieties as ancillary ligands in the coordination chem. of group 3 metals was explored. The amine elimination reactions between yttrium and scandium amido precursors {M [N(SiHMe2)2]3 (THF)n} with the proligands {4,6-tBu2-OC6H2-2-CH2S(2-R-C6H4)}H [R = H (L1-H), CH3 (L2-H), Br (L3-H), CF3 (L4-H)], bearing different substituents at the ortho position of the thiophenol aryl ring, were studied. The outcome of aminolysis reactions gave different results depending on the structure of the proligand and the reaction conditions. Heteroleptic scandium and yttrium amido complexes with general formula {(L)2M [N(SiHMe2)2] (THF)n} were prevailingly obtained from phenoxy-thioether proligands L1-H and L4-H. In contrast, homoleptic yttrium complexes bearing three phenoxy-thioether ligands were favored with L2-H and L3-H. The activities of all the synthesized complexes toward the ring-opening polymn. of ε-caprolactone and L- and rac-lactide were investigated, also in combination with an alc. as an external chain transfer agent. Polyesters with controlled mol. parameters (Mn, end groups) and low polydispersities were obtained. The monoinsertion adduct, produced by the reaction of {(L1)2ScN(SiHMe2)2} and 1 equiv. of ε-caprolactone, was isolated proving that a coordination-insertion mechanism of ring-opening polymn. was operative. In the polymn. of rac-lactide, yttrium complexes exerted a high degree of stereocontrol producing heterotactic polylactides (Pr up to 0.91)
Going Beyond Counting First Authors in Author Co-citation Analysis
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
“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
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
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
koamabayili/VECTRON-author-checklist: VECTRON author checklist
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
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