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Au25(SCnH2 n+1)18 Clusters in Biomimetic Membranes: Role of Size, Charge, and Transmembrane Potential in Direct Membrane Permeation
No full textGold nanoclusters and nanoparticles are promising materials for applications in nanomedicine, and therefore, understanding their interaction with cell membranes is of particular importance. A series of neutral and anionic Au25(SCnH2n+1)18 monolayer protected clusters (MPCs) (briefly, Cn0 and Cn- clusters), was embedded into two types of biomimetic membranes supported by mercury electrodes. The first was a dioleoylphosphatidylcholine (DOPC) self-assembled monolayer (SAM), whereas the second was a tethered bilayer lipid membrane (tBLM) obtained by first anchoring a thiolipid monolayer to the mercury surface and then self-assembling a DOPC monolayer on top of it. The diameter of these clusters, from 1.7 to 2.7 nm depending on the thiolate ligand, is smaller than the thickness of biomembranes and biomimetic membranes. Both neutral and anionic Au25(SCnH2n+1)18 MPCs can penetrate the lipid bilayer moiety of the tBLM, without disrupting it; in particular, anionic Au25 clusters require positive transmembrane potentials to do so. Neutral Au25 clusters exchange one electron with mercury in a DOPC SAM, where they can come in contact with the mercury surface, whereas they are prevented from doing so at the tBLM because of their inability to cross the hydrophilic chain separating the lipid bilayer moiety from the mercury surface. The potential of these Au25 clusters to penetrate directly the plasma membrane is particularly convenient for targeted drug delivery. They are highly stable, biocompatible, and catalytic, and their uniform size is of importance in nanomedicine. Moreover, they may induce an efficient energy transfer to 3O2, allowing applications in radiotherapy and antimicrobial activity.
Effect of a Strong Interfacial Electric Field on the Orientationof the Dipole Moment of Thiolated Aib-Oligopeptides Tetheredto Mercury on Either the N- or C-Terminus
No full textFour oligopeptides consisting of a sequence of R-aminoisobutyric acid (Aib) residues, thiolated
at either the N- or C-terminus by means of a -(CH2)2-SH anchor, were self-assembled on mercury, which
is a substrate known to impart a high fluidity to self-assembled monolayers (SAMs). The surface dipole
potential of these peptide SAMs was estimated in 0.1 M KCl aqueous solution at a negatively charged
electrode, where the interfacial electric field is directed toward the metal. To the best of our knowledge,
this is the first estimate of the surface dipole potential of peptide SAMs in aqueous solution. The procedure
adopted consisted in measuring the charge involved in the gradual expansion of a peptide-coated mercury
drop and then combining the resulting information with an estimate of the charge density experienced by
diffuse layer ions. The dipole moment of the tethered thiolated peptides was found to be directed toward
the metal, independent of whether they were thiolated at the C- or N-terminus. This result was confirmed
by the effect of these SAMs on the kinetics and thermodynamics of the Eu(III)/Eu(II) redox couple. The
combined outcome of these studies indicates that a strong interfacial electric field orients the dipole moment
of peptide SAMs tethered to mercury, even against their “natural” dipole moment
Incorporation of channel-forming peptides in a Hg-supported lipid bilayer
No full textThe channel-forming peptides gramicidin and alamethicin were incorporated in a mercury-supported lipid bilayer composed of a tethered thiolipid monolayer with a self-assembled dioleoylphosphatidylcholine monolayer on top of it. The thiolipid consists of a hexapeptide chain with a high tendency to form a 310-helical structure, which terminates at the N-terminus end with a sulfydryl group for anchoring to the metal while the C-terminus end is covalently linked to the polar head of dimyristolylphosphatidylethanolamine. The hexapeptide moiety has two triethyleneoxy side chains that impart a satisfactory hydrophilicity and are intended to keep the anchored thiolpeptide chains sufficiently apart, so as to accommodate water molecules and inorganic ions and to create a suitable environment for the incorporation of integral proteins. Changes in the conductance of this biomimetic membrane following the incorporation of gramicidin and alamethicin were detected by impedance spectroscopy. The surface dipole potential of the hexapeptide chain and the transmembrane potential of the lipid bilayer were estimated by using a simple electrostatic model of the mercury|solution interphase
Going Beyond Counting First Authors in Author Co-citation Analysis
Get PDFThe 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
Get PDF“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
Get PDFWe 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
Electrochemical and photoelectrochemical behavior of chlorophyll a films adsorbed on mercury
No full textDispelling the Myths Behind First-author Citation Counts
Get PDFWe 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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