Chiral gold(I) vs chiral silver complexes as catalysts for the enantioselective synthesis of the second generation GSK-hepatitis C virus inhibitor

The synthesis of a GSK 2nd generation inhibitor of the hepatitis C virus, by enantioselective 1,3-dipolar cycloaddition between a leucine derived iminoester and tert-butyl acrylate, was studied. The comparison between silver(I) and gold(I) catalysts in this reaction was established by working with chiral phosphoramidites or with chiral BINAP. The best reaction conditions were used for the total synthesis of the hepatitis C virus inhibitor by a four step procedure affording this product in 99% ee and in 63% overall yield. The origin of the enantioselectivity of the chiral gold(I) catalyst was justified according to DFT calculations, the stabilizing coulombic interaction between the nitrogen atom of the thiazole moiety and one of the gold atoms being crucial.

Binap-gold (I) versus Binap-silver trifluoroacetate complexes as catalysts in 1,3-dipolar cycloadditions of axomethine ylides

The 1,3-dipolar cycloaddition between azomethine ylides and alkenes is efficiently catalysed by [{(Sa)-Binap-Au(tfa)}2] (Binap=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl; tfa=trifluoroacetyl). Maleimides, 1,2-bis(phenylsulfonyl)ethylene, chalcone and nitrostyrene were suitable dipolarophiles even when using sterically hindered 1,3-dipole precursors. The results obtained in these transformations improve the analogous ones obtained in the same reactions catalysed by [Binap–Ag(tfa)]. In addition, computational studies have also been carried out to demonstrate both the high enantioselectivity exhibited by the chiral gold(I) complex, and the non-linear effect observed in this transformation.

Calibration of the length of a chain of single gold atoms

Using a scanning tunnelling microscope or mechanically controllable break junction it has been shown that it is possible to control the formation of a wire made of single gold atoms. In these experiments an interatomic distance between atoms in the chain of ∼3.6 Å was reported which is not consistent with recent theoretical calculations. Here, using precise calibration procedures for both techniques, we measure the length of the atomic chains. Based on the distance between the peaks observed in the chain length histogram we find the mean value of the interatomic distance before chain rupture to be 2.5±0.2 Å. This value agrees with the theoretical calculations for the bond length. The discrepancy with the previous experimental measurements was due to the presence of He gas, that was used to promote the thermal contact, and which affects the value of the work function that is commonly used to calibrate distances in scanning tunnelling microscopy and mechanically controllable break junctions at low temperatures.

Reutilización del Treebank de dependencias del euskera para la construcción del gold standard de la sintaxis superficial de la gramática de restricciones (CG)

El objetivo del trabajo consiste en reutilizar el Treebank de dependencias EPECDEP (BDT) para construir el gold standard de la sintaxis superficial del euskera. El paso básico consiste en el estudio comparativo de los dos formalismos aplicados sobre el mismo corpus: el formalismo de la Gramática de Restricciones (Constraint Grammar, CG) y la Gramática de Dependencias (Dependency Grammar, DP). Como resultado de dicho estudio hemos establecido los criterios lingüísticos necesarios para derivar la funciones sintácticas en estilo CG. Dichos criterios han sido implementados y evaluados, así en el 75% de los casos se derivan automáticamente las funciones sintácticas para construir el gold standard.

Understanding the structure of the first atomic contact in gold

We have studied experimentally jump-to-contact (JC) and jump-out-of-contact (JOC) phenomena in gold electrodes. JC can be observed at first contact when two metals approach each other, while JOC occurs in the last contact before breaking. When the indentation depth between the electrodes is limited to a certain value of conductance, a highly reproducible behaviour in the evolution of the conductance can be obtained for hundreds of cycles of formation and rupture. Molecular dynamics simulations of this process show how the two metallic electrodes are shaped into tips of a well-defined crystallographic structure formed through a mechanical annealing mechanism. We report a detailed analysis of the atomic configurations obtained before contact and rupture of these stable structures and obtained their conductance using first-principles quantum transport calculations. These results help us understand the values of conductance obtained experimentally in the JC and JOC phenomena and improve our understanding of atomic-sized contacts and the evolution of their structural characteristics.

Synthetic scope and DFT analysis of the chiral binap-gold (I) complex-catalyzed 1,3-dipolar cycloaddition of azlactones with alkenes

The 1,3-dipolar cycloaddition between glycine-derived azlactones with maleimides is efficiently catalyzed by the dimeric chiral complex [(Sa)-Binap·AuTFA]2. The alanine-derived oxazolone only reacts with tert-butyl acrylate giving anomalous regiochemistry, which is explained and supported by Natural Resonance Theory and Nucleus Independent Chemical Shifts calculations. The origin of the high enantiodiscrimination observed with maleimides and tert-butyl acrylate is analyzed using DFT computed at M06/Lanl2dz//ONIOM(b3lyp/Lanl2dz:UFF) level. Several applications of these cycloadducts in the synthesis of new proline derivatives with a 2,5-trans-arrangement and in the preparation of complex fused polycyclic molecules are described.

Electrochemical analysis of the performance of carbon supported Pd nanoparticles for direct formic acid fuel cells: from gold supported electrodes to catalyst-coated membranes

In this work carbon supported Pd nanoparticles were prepared and used as electrocatalysts for formic acid electrooxidation fuel cells. The influence of some relevant parameters such as the nominal Pt loading, the Nafion/total solids ratio as well as the Pd loading towards formic acid electrooxidation was evaluated using gold supported catalytic layer electrodes which were prepared using a similar methodology to that employed in the preparation of conventional catalyst coated membranes (CCM). The results obtained show that, for constant Pd loading, the nominal Pd loading and the Nafion percentage on the catalytic layer do not play an important role on the resulting electrocatalytic properties. The main parameter affecting the electrocatalytic activity of the electrodes seems to be the Pd loading, although the resulting activity is not directly proportional to the increased Pd loading. Thus, whereas the Pd loading is multiplied by a factor of 10, the activity is only twice which evidences an important decrease in the Pd utilization. In fact, the results obtained suggest the active layer is the outer one being clearly independent of the catalytic layer thickness. Finally, catalyst coated membranes with Pd catalyst loadings of 0.1, 0.5 and 1.2 mg cm-2 were also tested in a breathing direct formic acid fuel cell.

Colloidal gold immobilized on mesoporous silica as a highly active and selective catalyst for styrene epoxidation with H2O2

Colloidal gold nanoparticles were synthesized by different procedures affording suspensions with two different mean sizes (2 and 5 nm). Au catalysts were prepared by sol immobilization onto several silica frameworks with different 2D and 3D mesoporosities. The catalysts were tested in styrene oxidation reactions showing excellent efficiency and selectivity. The effect of nanoparticle size and mesoporous framework on the physical and catalytic properties of the final materials was studied. The most selective catalyst was prepared from the 5 nm Au nanoparticles and the more interconnected silica framework (3D mesoporosity).

Modeling contact formation between atomic-sized gold tips via molecular dynamics

The formation and rupture of atomic-sized contacts is modelled by means of molecular dynamics simulations. Such nano-contacts are realized in scanning tunnelling microscope and mechanically controlled break junction experiments. These instruments routinely measure the conductance across the nano-sized electrodes as they are brought into contact and separated, permitting conductance traces to be recorded that are plots of conductance versus the distance between the electrodes. One interesting feature of the conductance traces is that for some metals and geometric configurations a jump in the value of the conductance is observed right before contact between the electrodes, a phenomenon known as jump-to-contact. This paper considers, from a computational point of view, the dynamics of contact between two gold nano-electrodes. Repeated indentation of the two surfaces on each other is performed in two crystallographic orientations of face-centred cubic gold, namely (001) and (111). Ultimately, the intention is to identify the structures at the atomic level at the moment of first contact between the surfaces, since the value of the conductance is related to the minimum cross-section in the contact region. Conductance values obtained in this way are determined using first principles electronic transport calculations, with atomic configurations taken from the molecular dynamics simulations serving as input structures.

Superior performance of gold supported on doped CeO2 catalysts for the preferential CO oxidation (PROX)

Herein, the preferential oxidation of CO in excess hydrogen (PROX reaction) was studied over Au catalysts supported on ceria and Y or Nb doped ceria. Both supports and catalysts have been extensively characterized by a number of advanced techniques; XRD, N2-adsortion, Raman spectroscopy, XPS, and H2-TPR. The catalytic results showed that when an ideal mixture of H2 and CO is used for the PROX reaction the gold supported on pure ceria behaves better than the others samples. However, when a typical reformate gas composition containing CO2 and H2O is used, the gold supported on Nb doped sample behaves better than gold supported in pure ceria. It is suggested that niobium hampers the strong adsorption of CO2 and H2O in the active sites, thus improving the catalytic performance in real reformate gas.

Influence of tree hollow characteristics on the diversity of saproxylic insect guilds in Iberian Mediterranean woodlands

Saproxylic diversity assessment is a major goal for conservation strategies in woodlands and it should consider woodland composition and configuration at site and tree level as key modelling factors. However, in Mediterranean woodlands little is known about the relation with the environmental factors that structure their assemblages, especially those linked to tree hollow microhabitats. We assessed the diversity of Syrphidae (Diptera) and Coleoptera saproxylic guilds that co-occurred in tree hollows located in three different Iberian Mediterranean woodlands in the Cabañeros National Park (Spain). Furthermore, we evaluated how differences in tree hollow microenvironmental variables (understood as the physical and biotic characteristics of a hollow and tree individual) influenced saproxylic guild diversity both within and among woodland sites. We found that woodland sites that provided greater heterogeneity of trees and hollow microhabitats determined higher saproxylic guild diversity. Nevertheless, certain species or even complete guilds can be favoured in woodlands where some hollow microhabitats predominate as a consequence of historical tree management. In general, hollow volume was the main determining factor for saproxylic guild richness and abundance in woodland sites, and large hollow volume was usually related to higher diversity, which highlighted the importance of multi-habitat hollow trees. Moreover, saproxylic guilds also responded to other different microenvironmental variables, which indicated different ecological preferences among guilds. The conservation of saproxylic insects in Iberian Mediterranean areas must be addressed to protect woodland sites that provide high diversity and large numbers of tree hollow microhabitats, and practices to enhance microhabitat heterogeneity should even be encouraged.

Influence of sludge retention time on filtration performance and biomass characteristics in a hollow fiber membrane bioreactor

In this study, the filtration process and the biomass characteristics in a laboratory-scale submerged membrane bioreactor (MBR) equipped with a hollow fiber (HF) microfiltration membrane were studied at different solid retention times (SRT). The MBR was fed by synthetic wastewater and the organic loading rate (OLR) was 0.5, 0.2, 0.1, and 0.08 kg COD kg VSS−1 d−1 for 10, 30, 60, and 90 days of SRT, respectively. The hydraulic retention time was 8.4 h and the permeate flux was 6 L m−2 h−1(LMH). Data analysis confirmed that at all the studied SRTs, the HF-MBR operated very good obtaining of high quality permeates. Chemical Oxygen Demand (COD) removal efficiencies were higher than 95%. The best filtration performance was reached at SRT of 30 d. On the other hand, the respirometric analysis showed that biomass was more active and there was more biomass production at low SRTs. The concentration of soluble extracellular polymeric substances (EPS) decreased with increasing SRT. A decrease of soluble EPS caused a decrease of membrane fouling rate, decreasing the frequency of chemical cleanings. The floc size decreased with SRT increasing. At high SRTs, there was more friction among particles due to the increase of the cellular density and the flocs broke decreasing their size.

What can physical, biotic and chemical features of a tree hollow tell us about their associated diversity?

Tree hollows are keystone structures for saproxylic fauna and host numerous endangered species. However, not all tree hollows are equal. Many variables including physical, biotic and chemical ones, can characterise a tree hollow, however, the information that these could provide about the saproxylic diversity they harbour has been poorly explored. We studied the beetle assemblages of 111 Quercus species tree hollows in four protected areas of the Iberian Peninsula. Three physical variables related to tree hollow structure, and two biotic ones (presence of Cetoniidae and Cerambyx species recognised as ecosystem engineers) were measured in each hollow to explore their relative effect on beetle assemblages. Moreover, we analysed the chemical composition of the wood mould in 34 of the hollows, in order to relate beetle diversity with hollow quality. All the environmental variables analysed (physical and biological) showed a significant influence on saproxylic beetle assemblages that varied depending on the species. Furthermore, the presence of ecosystem engineers affected both physical and chemical features. Although wood mould volume, and both biotic variables could act as beetle diversity surrogate, we enhance the presence of Cetoniidae and Cerambyx activity (both easily observable in the field) as indicator variables, even more if both co-occur as each affect to different assemblages. Finally, assimilable carbon and phosphorous contents could act as indicator for past and present beetle activity inside the cavity that could become a useful tool in functional diversity studies. However, an extension of this work to other taxonomic groups would be desirable.

Mercury determination in urine samples by gold nanostructured screen-printed carbon electrodes after vortex-assisted ionic liquid dispersive liquid–liquid microextraction

A novel approach is presented to determine mercury in urine samples, employing vortex-assisted ionic liquid dispersive liquid–liquid microextraction and microvolume back-extraction to prepare samples, and screen-printed electrodes modified with gold nanoparticles for voltammetric analysis. Mercury was extracted directly from non-digested urine samples in a water-immiscible ionic liquid, being back-extracted into an acidic aqueous solution. Subsequently, it was determined using gold nanoparticle-modified screen-printed electrodes. Under optimized microextraction conditions, standard addition calibration was applied to urine samples containing 5, 10 and 15 μg L−1 of mercury. Standard addition calibration curves using standards between 0 and 20 μg L−1 gave a high level of linearity with correlation coefficients ranging from 0.990 to 0.999 (N = 5). The limit of detection was empirical and statistically evaluated, obtaining values that ranged from 0.5 to 1.5 μg L−1, and from 1.1 to 1.3 μg L−1, respectively, which are significantly lower than the threshold level established by the World Health Organization for normal mercury content in urine (i.e., 10–20 μg L−1). A certified reference material (REC-8848/Level II) was analyzed to assess method accuracy finding 87% and 3 μg L−1 as the recovery (trueness) and standard deviation values, respectively. Finally, the method was used to analyze spiked urine samples, obtaining good agreement between spiked and found concentrations (recovery ranged from 97 to 100%).

Silica Microparticles Supported Gold and Copper Ferrite Nanoparticles: A Magnetically Recyclable Bimetallic Catalyst for Sonogashira Reaction

Novel silica supported gold and copper ferrite nanoparticles (NPs) have been synthesized, characterized and used as a separable dual catalyst in Sonogashira type reaction. These Au.CuFe2O4@Silica NPs show a high efficiency as catalyst in the alkynylation not only of aryl iodides but also aryl bromides. By using only 0.5 mol% loading and t-BuOK as base in N,N-dimethylacetamide as solvent, aryl iodides react at 115 ºC in 1 d, whereas for aryl bromides the cross-coupling takes place at 130 ºC in 2 d. The catalyst can be successfully recycled using an external magnet for four consecutive runs.