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.

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).

The influence of surfactant loading level in a montmorillonite on the thermal, mechanical and rheological properties of EVA nanocomposites

In this work, montmorillonite (Mt) has been organically modified with ethyl hexadecyl dimethyl ammonium (EHDDMA) in 20, 50, 80 and 100% of the nominal exchange capacity (CEC) of the Mt. A full characterization of the organo-montmorillonite (OMt) obtained has been made, including thermal analysis, X-Ray Diffraction, elemental analysis CHN and nitrogen adsorption. According to the results, 12% in mass of the surfactant added is strongly retained by the Mt. When the mass percentage of EHDDMA exchanged in the OMt is increased up to this level, the interactions OMt–EHDDMA are steeply reduced depending on the EHDDMA content. Clay polymer nanocomposites (CPN) were prepared by melt mixing of EVA and different loads of OMt. The CPN were compress molded to obtain 1 mm thick sheets, which have been characterized according to their mechanical, thermal and rheological behaviors. The major changes in the structure of the OMt are obtained for low contents of EHDDMA. Nevertheless, the CPN containing OMt exchanged at 20 and 50% of the CEC show relatively low effect of the EHDDMA while the mechanical response and rheological behavior of CPN with OMt modified at 80 and 100% of the CEC are much more pronounced.

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.

Methane dry reforming over Ni supported on pine sawdust activated carbon: Effects of support surface properties and metal loading

The influence of metal loading and support surface functional groups (SFG) on methane dry reforming (MDR) over Ni catalysts supported on pine-sawdust derived activated carbon were studied. Using pine sawdust as the catalyst support precursor, the smallest variety and lowest concentration of SFG led to best Ni dispersion and highest catalytic activity, which increased with Ni loading up to 3 Ni atoms nm-2. At higher Ni loading, the formation of large metal aggregates was observed, consistent with a lower "apparen" surface area and a decrease in catalytic activity. The H2/CO ratio rose with increasing reaction temperature, indicating that increasingly important side reactions were taking place in addition to MDR.

Electrocatalytic reduction of CO2 to formate using particulate Sn electrodes: Effect of metal loading and particle size

The development of electrochemical processes for the conversion of CO2 into value-added products allows innovative carbon capture & utilization (CCU) instead of carbon capture & storage (CCS). In addition, coupling this conversion with renewable energy sources would make it possible to chemically store electricity from these intermittent renewable sources. The electroreduction of CO2 to formate in aqueous solution has been performed using Sn particles deposited over a carbon support. The effect of the particle size and Sn metal loading has been evaluated using cyclic voltammetry and chronoamperometry. The selected electrode has been tested on an experimental filter-press type cell system for continuous and single pass CO2 electroreduction to obtain formate as main product at ambient pressure and temperature. Experimental results show that using electrodes with 0.75 mg Sn cm−2, 150 nm Sn particles, and working at a current density of 90 mA cm−2, it is possible to achieve rates of formate production over 3.2 mmol m−2 s−1 and faradaic efficiencies around 70% for 90 min of continuous operation. These experimental conditions allow formate concentrations of about 1.5 g L−1 to be obtained on a continuous mode and with a single pass of catholyte through the cell.

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%).

Model of an Arizona gold mine.

no.1(1922)

Gold Company Claims, Witwatersrand, South Africa, 1895 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Bacon's new map of the Witwatersrand goldfields in the districts of Pretoria and Heidelberg, Transvaal, S. A. R. : shewing the main and other reefs, with the farms, gold mining company's claims and concessions : from information in the Surveyor-General's Department. It was published by G. W. Bacon & Co. in 1895. Scale [ca. 1:88,992].The image inside the map neatline is georeferenced to the surface of the earth and fit to the Universal Transverse Mercator (UTM Zone 35S, meters, WGS 1984) projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, roads, railroads, cities and other human settlements, administrative boundaries, farms, homesteads, main reefs, other reefs, probable connections, and mills. Includes also notes and inset: "Enlarged map of the farms Lanlaagte, Turffontein, Dornfontein & Elandsfontein, shewing the boundaries of the principal deep level gold mining coys. on the Witwatersrand goldfields" and a geological profile of the area north of Magaliesberg to the south of Witwatersrange.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.