Quantifying perchlorate adsorption on Au(111) electrodes

Perchlorate adsorption on Au(1 1 1) was investigated by cyclic voltammetry and surface-enhanced infrared absorption spectroscopy. We found that the electrosorption valency of ClO4− on Au(1 1 1) is ∼ 0.6 and the total coverage of ClO4− on Au(1 1 1) is higher (∼ 0.15) than previously estimated (∼ 0.04). Based on the experimental adsorption isotherms obtained from infrared spectra and the reconstruction-free cyclic voltammograms, we proposed a mechanism for the ClO4− adsorption on Au(1 1 1).

The Chemical Space Project

One of the simplest questions that can be asked about molecular diversity is how many organic molecules are possible in total? To answer this question, my research group has computationally enumerated all possible organic molecules up to a certain size to gain an unbiased insight into the entire chemical space. Our latest database, GDB-17, contains 166.4 billion molecules of up to 17 atoms of C, N, O, S, and halogens, by far the largest small molecule database reported to date. Molecules allowed by valency rules but unstable or nonsynthesizable due to strained topologies or reactive functional groups were not considered, which reduced the enumeration by at least 10 orders of magnitude and was essential to arrive at a manageable database size. Despite these restrictions, GDB-17 is highly relevant with respect to known molecules. Beyond enumeration, understanding and exploiting GDBs (generated databases) led us to develop methods for virtual screening and visualization of very large databases in the form of a “periodic system of molecules” comprising six different fingerprint spaces, with web-browsers for nearest neighbor searches, and the MQN- and SMIfp-Mapplet application for exploring color-coded principal component maps of GDB and other large databases. Proof-of-concept applications of GDB for drug discovery were realized by combining virtual screening with chemical synthesis and activity testing for neurotransmitter receptor and transporter ligands. One surprising lesson from using GDB for drug analog searches is the incredible depth of chemical space, that is, the fact that millions of very close analogs of any molecule can be readily identified by nearest-neighbor searches in the MQN-space of the various GDBs. The chemical space project has opened an unprecedented door on chemical diversity. Ongoing and yet unmet challenges concern enumerating molecules beyond 17 atoms and synthesizing GDB molecules with innovative scaffolds and pharmacophores.

Measuring the forces involved in polyvalent adhesion of uropathogenic Escherichia coli to mannose-presenting surfaces

Mechanisms of bacterial pathogenesis have become an increasingly important subject as pathogens have become increasingly resistant to current antibiotics. The adhesion of microorganisms to the surface of host tissue is often a first step in pathogenesis and is a plausible target for new antiinfective agents. Examination of bacterial adhesion has been difficult both because it is polyvalent and because bacterial adhesins often recognize more than one type of cell-surface molecule. This paper describes an experimental procedure that measures the forces of adhesion resulting from the interaction of uropathogenic Escherichia coli to molecularly well defined models of cellular surfaces. This procedure uses self-assembled monolayers (SAMs) to model the surface of epithelial cells and optical tweezers to manipulate the bacteria. Optical tweezers orient the bacteria relative to the surface and, thus, limit the number of points of attachment (that is, the valency of attachment). Using this combination, it was possible to quantify the force required to break a single interaction between pilus and mannose groups linked to the SAM. These results demonstrate the deconvolution and characterization of complicated events in microbial adhesion in terms of specific molecular interactions. They also suggest that the combination of optical tweezers and appropriately functionalized SAMs is a uniquely synergistic system with which to study polyvalent adhesion of bacteria to biologically relevant surfaces and with which to screen for inhibitors of this adhesion.

New multivalent calixarene-based ligands for protein recognition and inhibition

One of the challenges that concerns chemistry is the design of molecules able to modulate protein-protein and protein-ligand interactions, since these are involved in many physiological and pathological processes. The interactions occurring between proteins and their natural counterparts can take place through reciprocal recognition of rather large surface areas, through recognition of single contact points and single residues, through inclusion of the substrates in specific, more or less deep binding sites. In many cases, the design of synthetic molecules able to interfere with the processes involving proteins can benefit from the possibility of exploiting the multivalent effect. Multivalency, widely spread in Nature, consists in the simultaneous formation between two entities (cell-cell, cell-protein, protein-protein) of multiple equivalent ligand-recognition site complexes. In this way the whole interaction results particularly strong and specific. Calixarenes furnish a very interesting scaffold for the preparation of multivalent ligands and in the last years calixarene-based ligands demonstrated their remarkable capability to recognize and inhibit or restore the activity of different proteins, with a high efficiency and selectivity in several recognition phenomena. The relevance and versatility of these ligands is due to the different exposition geometries of the binding units that can be explored exploiting the conformational properties of these macrocycles, the wide variety of functionalities that can be linked to their structure at different distances from the aromatic units and to their intrinsic multivalent nature. With the aim of creating new multivalent systems for protein targeting, the work reported in this thesis regards the synthesis and properties of glycocalix[n]arenes and guanidino calix[4]arenes for different purposes. Firstly, a new bolaamphiphile glycocalix[4]arene in 1,3-alternate geometry, bearing cellobiose, was synthesized for the preparation of targeted drug delivery systems based on liposomes. The formed stable mixed liposomes obtained by mixing the macrocycle with DOPC were shown to be able of exploiting the sugar units emerging from the lipid bilayer to agglutinate Concanavalin A, a lectin specific for glucose. Moreover, always thanks to the presence of the glycocalixarene in the layer, the same liposomes demonstrated through preliminary experiments to be uptaken by cancer cells overexpressing glucose receptors on their exterior surface more efficiently respect to simple DOPC liposomes lacking glucose units in their structure. Then a small library of glycocalix[n]arenes having different valency and geometry was prepared, for the creation of potentially active immunostimulants against Streptococcus pneumoniae, particularly the 19F serotype, one of the most virulent. These synthesized glycocalixarenes bearing β-N-acetylmannosamine as antigenic unit were compared with the natural polysaccharide on the binding to the specific anti-19F human polyclonal antibody, to verify their inhibition potency. Among all, the glycocalixarene based on the conformationally mobile calix[4]arene resulted the more efficient ligand, probably due its major possibility to explore the antibody surface and dispose the antigenic units in a proper arrangement for the interaction process. These results pointed out the importance of how the different multivalent presentation in space of the glycosyl units can influence the recognition phenomena. At last, NMR studies, using particularly 1H-15N HSQC experiments, were performed on selected glycocalix[6]arenes and guanidino calix[4]arenes blocked in the cone geometry, in order to better understand protein-ligand interactions. The glycosylated compounds were studied with Ralstonia solanacearum lectin, in order to better understand the nature of the carbohydrate‐lectin interactions in solution. The series of cationic calixarene was employed with three different acidic proteins: GB1, Fld and alpha synuclein. Particularly GB1 and Fld were observed to interact with all five cationic calix[4]arenes but showing different behaviours and affinities.

The palace of pleasure; an anthology of the novella.

Mode of access: Internet.

Vanadate conformation variations in vanadium pentoxide nanostructures

We report the comparative structural-vibrational study of nanostructures of nanourchins, nanotubes, and nanorods of vanadium oxide. The tube walls comprise layers of vanadium oxide with the organic surfactant intercalated between atomic layers. Both Raman scattering and infrared spectroscopies showed that the structure of nanourchins, nanotubes, and nanorods of vanadium oxide nanocomposite are strongly dependent on the valency of the vanadium, its associated interactions with the organic surfactant template, and on the packing mechanism and arrangement of the surfactant between vanadate layers. Accurate assignment of the vibrational modes to the V-O coordinations has allowed their comparative classification and relation to atomic layer structure. Although all structures are formed from the same precursor, differences in vanadate conformations due to the hydrothermal treatment and surfactant type result in variable degrees of crystalline order in the final nanostructure. The nanotube-containing nanourchins contain vanadate layers in the nanotubes that are in a distorted γ- V5+ conformation, whereas the the nanorods, by comparison, show evidence for V5+ and V4+ species-containing ordered VOx lamina.

Transgresión de las identidades tradicionales de género mediante la representación gráfica de mujeres protagonistas para videojuegos desarrollada por niños y niñas

El artículo identifica y analiza el discurso predominante que poseen 12 niños y 7 niñas de 7° y 8° año básico pertenecientes a 4 establecimientos educacionales en la ciudad de Talca en Chile, en torno a la transgresión de las identidades tradicionales de la mujer en los videojuegos. Para ello durante el 1° semestre del año 2014 al interior de un programa de formación de profesores/as en Artes Visuales se implementa una estrategia didáctica centrada en la expresión gráfica denominada “Crea tu propia personaje para videojuego”. Haciendo partícipes a niños y niñas junto a profesionales en formación de una propuesta metodológica basada en la Investigación-Acción enmarcada en las prácticas profesionales. Concluyendo tras el análisis semántico de dibujos y relatos, que las imágenes representativas de la mujer en los videojuegos transgreden las identidades tradicionales de género al interior de un marco androcéntrico predominante.

Les verbes causatifs dans les textes scientifiques : essai de typologie

La causalité est une des notions les plus fondamentales de la vie humaine. La vulgarisation scientifique se base sur l’établissement fréquent de relations causales par le truchement d'indices linguistiques. Ainsi, la causalité y est perceptible à l'aide de marques explicites, se manifestant au niveau lexical. Dans de nombreuses situations, afin de valider la relation causale, il faut récupérer des termes plus ou moins explicites qui apparaissent au niveau morphosyntaxique. Viennent enfin les procédés implicites d’expression de la cause ou "la causalité non marquée" linguistiquement.  

Grammar in dictionaries revisited: the case of verbs with se

This paper is a study about the way in which se structures are represented in 20 verb entries of nine dictionaries of Spanish language. There is a large number of these structures and they are problematic for native and non native speakers. Verbs of the analysis are middle-high frequency and, in the most part of the cases, very polysemous, and this allows to observe interconnections between the different se structures and the different meanings of each verb. Data of the lexicographic analysis are cross-checked with corpus analysis of the same units. As a result, it is observed that there is a large variety in the data which are offered in each dictionary and in the way they are offered, inter and intradictionary. The reasons range from the theoretical overall of each Project to practical performance. This leads to the conclusion that it is necessary to further progress in the dictionary model it is being handled, in order to offer lexico-grammatical phenomenon such as se verbs in an accurate, clear and exhaustive way.

Lo que los trabajadores quieren vs. lo que las empresas necesitan. Implementación de las anclas de carrera de Edgar Schein en un contact centre

El compromiso laboral entre los trabajadores y las organizaciones es uno de los activos con mayor poder explicativo para consolidar un alto desempeño e incrementar la productividad. Para lograr eso es fundamental conocer cuáles son las vocaciones de los trabajadores actuales y futuros y de qué manera estas motivaciones de carrera encuentran articulación con la misión y la visión de la compañía. El problema es que las empresas fallan sistemáticamente en este proceso. El modelo de anclas de carrera (ac) de Edgar Schein es una metodología que permite conocer cuáles son las motivaciones de carrera de los individuos. Este documento tiene como propósito establecer un vínculo entre las ac y los procesos de selección, vinculación, y retención del capital humano en un contact centre que se desempeña en Bogotá, Colombia. Para alcanzar este propósito, se implementó el modelo de ac en una muestra de 116 trabajadores del área de gestión de esta compañía. El informe presenta el análisis de resultados y las propuestas sugeridas por los autores a la gerencia de la compañía.