1,721,127 research outputs found
One-Handed Covalent Helical Ladder Polymers: The Dawn of a Tailorable Class of Chiral Functional Materials
No full textIn the last decades, chemists have developed methods to synthesize helical molecular architectures using a combination of covalent and non-covalent interactions. Very recently, the new class of completely covalent, one-handed helical ladder polymers has vigorously emerged. Such polymers can be rationally and programmably obtained through an approach guided by the principles of chirality-assisted-synthesis (CAS) and making use synergically of two disciplines that have so far rarely interacted: non-planar chiral π-conjugated synthons and ladder polymer chemistry. The precise programmability of the 3D structure and new mechanical and chiroptical properties will lead to potential applications in areas such as enantiorecognition, catalysis, spintronics and chiral-related optoelectronics. This minireview examines the emerging field of one-handed helical ladder polymers, analyzing their synthesis, applications, and limitations
Free radical cyclopolymerization: A tool towards sequence control in functional polymers
No full textMonomers possessing two functionalities suitable for polymerization are intuitively associated to crosslinked macromolecules and their multiple applications. Suitably designed difunctional monomers can in fact be subjected to cyclopolymerization processes to form linear, soluble macromolecules. These processes achieve cyclic moieties of variable ring size which are embedded within the polymer backbone, affording peculiar properties of the resulting macromolecules, including recognition. The two functionalities are covalently linked by a “tether”, which can be appropriately designed in order to “imprint” elements of chemical information into the polymer backbone during the synthesis, and, in some cases, be removed by post polymerization reactions. The two functionalities can possess identical or even very different reactivities towards free radical polymerization; in the latter case, consequences and outcomes related to the sequence-controlled, precision synthesis of macromolecules have been recently demonstrated. In this Feature Article, we account about such recent developments related to the use of cyclopolymerization for sequence-controlled polymerization
Cyclic response of 3D printed metamaterials with soft cellular architecture: The interplay between as-built defects, material and geometric non-linearity
Full text linkThe paper investigates the cyclic response of soft cellular materials undergoing repeated local instabilities. Our focus is mainly on the coupling between material non-linearities, geometric non-linearity as well as defects induced by 3D printing. Two paradigmatic lattices (triangular and hexagonal), each with its own distinct deformation mode and defect sensitivity, are examined, and the emergence of as-built material and geometric defects in the form of microporosity, strut thickness reduction, and nodal dispersion is studied via computed tomography and optical analyses. Experiments are carried out on the base material and lattice specimens for given cycling strains and cycle ratios. Numerical models are developed to understand the individual role of the main constitutive aspects of the base material, e.g. damage, creep, and visco-elasticity, as well as to assess the role of defects in each architecture. The results show that the activation of local buckling combined with the engagement of material non-linearities has multiple outcomes. It leads to local storage of inelastic strain, which in turn perturbs the lattice geometry after the second cycle and severely impacts the subsequent response, e.g. softening; it reduces the tangent modulus at zero strain; and it also decreases the maximum and minimum cyclic stresses. The detriment is further fueled by geometric deviations caused by 3D printing. Furthermore, a theoretical model is presented to obtain stress bound estimates of the stabilized response, hence offering guidelines for the design of 3D printed soft metamaterials under cycling loading. The paper concludes with a systematic discussion on the coupled role of non-linearities (material and geometry) and defects, and on the accuracy of the numerical and theoretical models herein presented
Controlled Oxyanionic Polymerization of Propylene Oxide: Unlocking the Molecular-Weight Limitation by a Soft Nucleophilic Catalysis
No full textThe oxyanionic ring-opening polymerization of propylene oxide (PO) from an exogenous alcohol activated with benign (complexed) metal-alkali carboxylates is described. The equimolar mixture of potassium acetate (KOAc) and 18-crown-6 ether (18C6) is demonstrated to be the complex of choice for preparing poly(propylene oxide) (PPO) in a controlled manner. In the presence of 18C6/KOAc, hydrogen-bonded alcohols act as soft nucleophiles promoting the PO SN2 process at room temperature and in solvent-free conditions while drastically limiting the occurrence of parasitic hydrogen abstraction generally observed during the anionic ROP of PO. The resulting PPO displays predictable and unprecedented molar masses (up to 20 kg mol−1) with low dispersities (ĐM < 1.1), rendering the 18C6/KOAc complex the most performing activator for the oxyanionic polymerization of PO reported to date. Preliminary studies on the preparation of block and statistical copolyethers are also reported
Regioselective Pummerer rearrangement in [2.2]paracyclophanes
No full textWe investigated and rationalized a synthetic pathway to [2.2]paracyclophanedienes, that exploits the combination of the Pummerer rearrangement on a dithiacyclophane with a photochemical sulfur extrusion step and a base-catalyzed elimination step. The synthetic pathway is very effective for the symmetric, prototypical [2.2]paracyclophanediene. In the case of an asymmetric precursor, bearing two aromatic units with differing electronic properties, mass spectrometry coupled with gas chromatography analysis suggests that the Pummerer rearrangement installs the acetate groups on the methylene carbon atoms neighboring the perfluoroaryl moiety. The rearrangement occurs with a high regioselectivity. Such an unexpected result may be useful in the design of sophisticated [2.2]paracyclophane architectures for applications in catalysis and electronics
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
- …
