A water-soluble tetraazaperopyrene dye as strong G-quadruplex DNA binder

The interactions of the water-soluble tetraazaperopyrene dye 1 with ct-DNA, duplex-[(dAdT)12⋅(dAdT)12], duplex-[(dGdC)12⋅(dGdC)12] as well as with two G-quadruplex-forming sequences, namely the human telomeric 22AG and the promotor sequence c-myc, were investigated by means of UV/visible and fluorescence spectroscopy, isothermal titration calorimetry (ITC) and molecular docking studies. Dye 1 exhibits a high affinity for G-quadruplex structures over duplex DNA structures. Furthermore, the ligand shows promising G-quadruplex discrimination, with an affinity towards c-myc of 2×107 m−1 (i.e., Kd=50 nm), which is higher than for 22AG (4×106 m−1). The ITC data reveal that compound 1 interacts with c-myc in a stoichiometric ratio of 1:1 but also indicate the presence of two identical lower affinity secondary binding sites per quadruplex. In 22AG, there are two high affinity binding sites per quadruplex, that is, one on each side, with a further four weaker binding sites. For both quadruplex structures, the high affinity interactions between compound 1 and the quadruplex-forming nucleic acid structures are weakly endothermic. Molecular docking studies suggest an end-stacking binding mode for compound 1 interacting with quadruplex structures, and a higher affinity for the parallel conformation of c-myc than for the mixed-hybrid conformation of 22AG. In addition, docking studies also suggest that the reduced affinity for duplex DNA structures is due to the non-viability of an intercalative binding mode

The Detection and Location of Hydrido Ligands in High Nuclearity Osmium and Ruthenium Carbonyl Clusters: A Critical Survey

Hydrido carbonyl clusters represent powerful molecular models for the co-adsorption of carbon monoxide and hydrogen on metal surfaces, a key step in several catalytic processes. Over the past two decades a considerable number of such species have been reported in the literature. In this paper, the structural chemistry of high nuclearity osmium and ruthenium hydrido carbonyl clusters is critically reviewed. Particular emphasis is placed on the limits of the various indirect methods of hydride location in clusters, and an alternative interpretation of the results of spectroscopic studies performed for samples of some Ru and Os clusters in solution is given

Configuring electronic states in an atomically precise array of quantum boxes

Communication.-- et al.A 2D array of electronically coupled quantum boxes is fabricated by means of on-surface self-assembly assuring ultimate precision of each box. The quantum states embedded in the boxes are configured by adsorbates, whose occupancy is controlled with atomic precision. The electronic interbox coupling can be maintained or significantly reduced by proper arrangement of empty and filled boxes.The authors would like to acknowledge financial support from the Swiss Nanoscience Institute (SNI), Swiss National Science Foundation (Grants Nos. 200020-149713 and 206021-121461), the Spanish Ministry of Economy (Grant No. MAT2013-46593-C6-4-P), the Basque Government (Grant No. IT621-13), the São Paulo Research Foundation (Grant No. 2013/04855-0), Swiss Government Excellence Scholarship Program, Netherlands Organization for Scientific Research NWO (Chemical Sciences, VIDI-Grant No. 700.10.424), the European Research Council (ERC-2012-StG 307760-SURFPRO), University of Basel, University of Heidelberg, Linköping University, University of Groningen, Paul Scherrer Institute, and the Japan Science and Technology Agency (JST) “Precursory Research for Embryonic Science and Technology (PRESTO)” for a project of “Molecular technology and creation of new function.”Peer Reviewe

Toward a Neutral Single-Component Amidinate Iodide Aluminum Catalyst for the CO₂ Fixation into Cyclic Carbonates

A new iodide aluminum complex ({AlI(κ⁴-naphbam)}, 3) supported by a tetradentate amidinate ligand derived from a naphthalene-1,8-bisamidine precursor (naphbamH, 1) was obtained in quantitative yield via reaction of the corresponding methyl aluminum complex ({AlMe(κ⁴-naphbam)}, 2) with 1 equiv of I₂ in CH₂Cl₂ at room temperature. Complexes 2 and 3 were tested and found to be active as catalysts for the cyclic carbonate formation from epoxides at 80 °C and 1 bar of CO₂ pressure. A first series of experiments were carried out with 1.5 mol % of the alkyl complex 2 and 1.5 mol % of tetrabutylammonium iodide (TBAI) as a cocatalyst; subsequently, the reactions were carried out with 1.5 mol % of iodide complex 3 as a single-component catalyst. Compound 3 is one of the first examples of a nonzwitterionic halide single-component aluminum catalyst producing cyclic carbonates. The full catalytic cycle with characterization of all minima and transition states was characterized by quantum chemistry calculations (QCCs) using density functional theory. QCCs on the reaction mechanism support a reaction pathway based on the exchange of the iodine contained in the catalyst by 1 equiv of epoxide, with subsequent attack of I⁻ to the epoxide moiety producing the ring opening of the epoxide. QCCs triggered new insights for the design of more active halide catalysts in future explorations of the field

Covalent assembly of a two-dimensional molecular ‘‘sponge’’ on a Cu(111) surface:Confined electronic surface states in open and closed pores

We present a new class of on-surface covalent reactions, formed between diborylene-3,4,9,10-tetraaminoperylene and trimesic acid on Cu(111), which gives rise to a porous 2D-'sponge'. This aperiodic network allowed the investigation of the dependence of electron confinement effects upon pore size, shape and even in partial confinement

STM fingerprint of molecule–adatom interactions in a self-assembled metal–organic surface coordination network on Cu(111)

7 páginas, 5 figuras, 3 tablas.-- El pdf del artículo es la versión pre-print.A novel approach of identifying metal atoms within a metal–organic surface coordination network using scanning tunnelling microscopy (STM) is presented. The Cu adatoms coordinated in the porous surface network of 1,3,8,10-tetraazaperopyrene (TAPP) molecules on a Cu(111) surface give rise to a characteristic electronic resonance in STM experiments. Using density functional theory calculations, we provide strong evidence that this resonance is a fingerprint of the interaction between the molecules and the Cu adatoms. We also show that the bonding of the Cu adatoms to the organic exodentate ligands is characterised by both the mixing of the nitrogen lone-pair orbitals of TAPP with states on the Cu adatoms and the partial filling of the lowest unoccupied molecular orbital (LUMO) of the TAPP molecule. Furthermore, the key interactions determining the surface unit cell of the network are discussed.This work was financially supported by the European Union through the Marie Curie Research Training Network PRAIRIES (MRTN-CT-2006-035810). Support from the Swiss National Science Foundation, the National Center of Competence in Research (NCCR) ‘‘Nanoscale Science’’ and the Wolfermann Naegeli Stiftung is also acknowledged. MP is also grateful for support from the Swedish Research Council (VR).Peer reviewe

La importancia de la personalidad del traductor en los itinerarios de especialidad y en la selección de personal

Treball Final de Grau en Traducció i Interpretació. Codi: TI0983. Curs acadèmic: 2016/2017A pesar de que a simple vista no lo pueda parecer, la personalidad de los traductores influye mucho más de lo que se cree en el proceso traductor y en la toma de decisiones, como han puesto de manifiesto estudios empíricos. Para analizar cuáles son las diferencias individuales en la personalidad de los traductores en la elección del itinerario de especialidad, se ha llevado a cabo un estudio con los estudiantes de los cuatro itinerarios de traducción de la Universidad Jaume I, a fin de ver si podemos identificar los rasgos típicos de los estudiantes de cada itinerario. Además, dada la gran importancia de la personalidad en las tareas de traducción, también se ha entrevistado a responsables de tres agencias de traducción para ver si la personalidad de los traductores es un factor relevante a la hora de reclutar personal. Se ha comprobado así que sí hay algunos rasgos comunes en la personalidad de los estudiantes de cada itinerario y que realmente esta cuestión no es un factor relevante en las agencias de traducción, sino que se valora, sobre todo, el trabajo diario y la calidad de las pruebas de traducción