A novel porous polymer-ionic liquid composite with poly(2-hydroxyethyl methacrylate) (PHEMA) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) has been synthesized by γ-irradiation without heat or chemical initiators. The products can be reversibly converted into organogels. The composites are potential candidates for electrochemical applications. The use of γ-radiation can be a simple and versatile alternative way to obtain these materials.

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Electrospun fibers of poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2) with exceptional electro-optical performance are obtained. The I/T characteristics measured in fibers with 7-15 μm diameter and 1 mm length show a semiconductor behavior; their thermal activation energy is 0.5 eV and the dark conductivity at RT is 5 × 10-9 (Ω cm)-1. Besides exhibiting a photosensitivity of about 60 under white light illumination with a light power intensity of 25 mW · cm-2, the fibers also attain RT photoluminescence in the cyan, yellow, and red wavelength range under ultraviolet, blue, and green light excitation, respectively. Optical microscope images of F8T2 reveal homogeneous electrospun fibers, which are in good agreement with the uniformly radial fluorescence observed. The production of electrospun fibers from poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-bithiophene] (F8T2) obtained without a carrier polymer is reported. The obtained fibers are shown to have properties suitable for organic fiber photovoltaic and sensors applications. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In the present work one host natural matrix - agar - has been doped with magnesium triflate (Mg(CF3SO3)2) with the goal of developing electrolytes for the fabrication of solid-state devices. The resulting samples have been represented by the notation Agar nMg(CF3SO3)2, where n represents the percentage of the magnesium triflate salt proportion in the electrolyte samples. The samples investigated, with n between 0.00% and 37.56%, have been obtained as transparent and thin films. The samples have been characterized by conductivity measurements, thermal analysis, cyclic voltammetry, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The agar-based electrolytes were also tested as ionic conductor in an electrochromic device with the following configuration: glass/indium tin oxide (ITO)/WO 3/agar-based electrolyte/CeO2-TiO2/ITO/glass. © 2013 Copyright Taylor and Francis Group, LLC.

Two synthetic strategies of tetrathiomolybdate-metal clusters with the potential to be used as NMR structural probes for the location of the metal cofactor in the orange protein (ORP) are described. The first strategy is based on the substitution reaction in which small organic ligands bind directly to the metal centre in a molybdenumcopper hetero-dinuclear cluster. Interaction between [PPh4]2[MoS4CuCl] and either aliphatic [beta-mercaptoethanol (b-me)] or aromatic [o-aminobenzenethiol (abt)] thiols in the presence of a strong base resulted in the formation of [Ph4P]2[S2MoS2Cu(b-me)] (1a) and [Et4N]2[S2MoS2Cu(abt)]center dot H2O center dot 0.25DMF (1b), which can be used to obtain intermolecular NOEs. The compound 1a readily hydrolyzed to [Ph4P]2[OSMoS2Cu(b-me)] (1ahydro) in contact with a protic solvent. The second strategy consisted of the incorporation of cadmium into tetrathiomolybdate ([MoS4]2), which gives rise to the trinuclear cluster compound [PPh4]2[(MoS4)2Cd] (2). All clusters were characterized spectroscopically and their structure determined by X-ray diffraction. The NMR spectroscopic data are consistent with the formation of a complex with a 1:1 ratio of {MoS4Cu} and thiol. The 113Cd NMR chemical shift of compound 2 is consistent with the cadmium having a tetrahedral geometry and coordinated by four sulfur ligands. The tetraphenylphosphonium cation in compound 1a was replaced by a tetramethylammonium countercation originating in the water-soluble compound [Me4N-1a]. Solubility in aqueous buffers is a requirement for incorporating this cluster into apo-ORP. These compounds will be used to identify the exact location of the ORP heterometallic cluster using NMR methodologies.

This work presents an experimental study concerning the post-punching behaviour of flat slabs strengthened with a new technique based on post-tensioning with anchorages by bonding using an epoxy adhesive. This strengthening technique proved efficient with respect to ultimate and serviceability states. Five slab specimens were tested in the post-punching range and it was found that the post-punching resistance was on average 78{%} of the punching resistance. This paper reports the development of strand forces and slab displacements from the beginning of the tests, including the bond stresses developed at several stages of the loading process. It was observed that top reinforcement bars were capable of transmitting post-punching loads to the prestressing strands. Taking this into account and based on the load bath envisaged from the column to the slab, expressions for the vertical load capacities corresponding to the parts of the load path are presented and compared with the experimental results, showing their ability to predict both ultimate loads and modes of failure. Compared with other strengthening techniques, the one proposed here not only upgrades ultimate and serviceability behaviour but also adds post-punching resistance, which is a great advantage in the event of progressive collapse, since it may avoid the collapse of an entire structure, thus reducing the risk of material and human losses.

Ferritins are ubiquitous and can be found in practically all organisms that utilize Fe. They are composed of 24 subunits forming a hollow sphere with an inner cavity of ~80 A in diameter. The main function of ferritin is to oxidize the cytotoxic Fe(2+) ions and store the oxidized Fe in the inner cavity. It has been established that the initial step of rapid oxidation of Fe(2+) (ferroxidation) by H-type ferritins, found in vertebrates, occurs at a diiron binding center, termed the ferroxidase center. In bacterial ferritins, however, X-ray crystallographic evidence and amino acid sequence analysis revealed a trinuclear Fe binding center comprising a binuclear Fe binding center (sites A and B), homologous to the ferroxidase center of H-type ferritin, and an adjacent mononuclear Fe binding site (site C). In an effort to obtain further evidence supporting the presence of a trinuclear Fe binding center in bacterial ferritins and to gain information on the states of the iron bound to the trinuclear center, bacterial ferritin from Desulfovibrio vulgaris (DvFtn) and its E130A variant was loaded with substoichiometric amounts of Fe(2+), and the products were characterized by Mossbauer and EPR spectroscopy. Four distinct Fe species were identified: a paramagnetic diferrous species, a diamagnetic diferrous species, a mixed valence Fe(2+)Fe(3+) species, and a mononuclear Fe(2+) species. The latter three species were detected in the wild-type DvFtn, while the paramagnetic diferrous species was detected in the E130A variant. These observations can be rationally explained by the presence of a trinuclear Fe binding center, and the four Fe species can be properly assigned to the three Fe binding sites. Further, our spectroscopic data suggest that (1) the fully occupied trinuclear center supports an all ferrous state, (2) sites B and C are bridged by a mu-OH group forming a diiron subcenter within the trinuclear center, and (3) this subcenter can afford both a mixed valence Fe(2+)Fe(3+) state and a diferrous state. Mechanistic insights provided by these new findings are discussed and a minimal mechanistic scheme involving O-O bond cleavage is proposed.