Sonogashira coupling on an extended gold surface in vacuo: reaction of phenylacetylene with iodobenzene on Au(111)

Temperature-programmed reaction measurements supported by scanning tunneling microscopy have shown that phenylacetylene and iodobenzene react on smooth Au(111) under vacuum conditions to yield biphenyl and diphenyldiacetylene, the result of homocoupling of the reactant molecules. They also produce diphenylacetylene, the result of Sonogashira cross-coupling, prototypical of a class of reactions that are of paramount importance in synthetic organic chemistry and whose mechanism remains controversial. Roughened Au(111) is completely inert toward all three reactions, indicating that the availability of crystallographically well-defined adsorption sites is crucially important. High-resolution X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure spectroscopy show that the reactants are initially present as intact, essentially flat-lying molecules and that the temperature threshold for Sonogashira coupling coincides with that for C−I bond scission in the iodobenzene reactant. The fractional-order kinetics and low temperature associated with desorption of the Sonogashira product suggest that the reaction occurs at the boundaries of islands of adsorbed reactants and that its appearance in the gas phase is rate-limited by the surface reaction. These findings demonstrate unambiguously and for the first time that this heterogeneous cross-coupling chemistry is an intrinsic property of extended, metallic pure gold surfaces: no other species, including solvent molecules, basic or charged (ionic) species are necessary to mediate the process.

Conformations and folding of lysozyme ions in vacuo.

Proton transfer reactivity of isolated charge states of the protein hen egg-white lysozyme shows that multiple distinct conformations of this protein are stable in the gas phase. The reactivities of the 9+ and 10+ charge state ions, formed by electrospray ionization of "native" (disulfide-intact) and "denatured" (disulfide-reduced) solutions, are consistent with values calculated for ions in their crystal structure and fully denatured conformations, respectively. Charge states below 8+ of both forms, formed by proton stripping, have similar or indistinguishable reactivities, indicating that the disulfide-reduced ions fold in the gas phase to a more compact conformation.

Protein-ligand binding free energy estimation using molecular mechanics and continuum electrostatics. Application to HIV-1 protease inhibitors.

A method is proposed for the estimation of absolute binding free energy of interaction between proteins and ligands. Conformational sampling of the protein-ligand complex is performed by molecular dynamics (MD) in vacuo and the solvent effect is calculated a posteriori by solving the Poisson or the Poisson-Boltzmann equation for selected frames of the trajectory. The binding free energy is written as a linear combination of the buried surface upon complexation, SASbur, the electrostatic interaction energy between the ligand and the protein, Eelec, and the difference of the solvation free energies of the complex and the isolated ligand and protein, deltaGsolv. The method uses the buried surface upon complexation to account for the non-polar contribution to the binding free energy because it is less sensitive to the details of the structure than the van der Waals interaction energy. The parameters of the method are developed for a training set of 16 HIV-1 protease-inhibitor complexes of known 3D structure. A correlation coefficient of 0.91 was obtained with an unsigned mean error of 0.8 kcal/mol. When applied to a set of 25 HIV-1 protease-inhibitor complexes of unknown 3D structures, the method provides a satisfactory correlation between the calculated binding free energy and the experimental pIC5o without reparametrization.

Observation touchant le vuide, faite pour la première fois en France , contenue en une lettre écrite à Monsieur Chanut,... Par Monsieur Petit intendant des fortifications, le 10 novembre 1646. Avec le discours qui en a esté imprimé Pologne sur le mesme sujet, en juillet 1647

Comprend : Demonstratio ocularis, Ioci sine locato, corporis successive moti in vacuo...

Una exploración del razonamiento cotidiano con lenguaje natural : silogismos con cuantificadores probabilísticos.

Nuestra investigación se ha planteado como objetivo general el contribuir a la elaboración de un marco teórico alternativo que permita explicar, desde una perspectiva estrictamente psicológica, la conducta de los sujetos humanos en tareas de inferencia silogística. Experimento I: participaron 71 estudiantes de COU; 36 eran mujeres y 35 varones. Edad media, 18 años y 4 meses. Experimento II: participaron 121 estudiantes de COU; 40 mujeres y 81 varones. La media de edad, 18 años y 7 meses. Experimento III: 32 estudiantes de Psicología; 17 chicas y 15 chicos. Edad media, 21 años y 7 meses. Experimento I: diseño factorial 2x2x4. Las VI fueron: contenido, con dos niveles: formal (las premisas de los silogismos contenían letras) y temático (las premisas tenían un carácter concreto); tipo de silogismo, con dos niveles: silogismo válido y silogismo no válido; versión, con cuatro niveles: mayoría-mayoría, bastantes-pocos, pocos no-varios y ninguno-alguno. La VD eran los juicios, la seguridad, la confianza subjetiva y las explicaciones. Experimento II: diseño factorial 2x2x2x4. Los factores fueron: consistencia, con dos niveles: consistente y no consistente; accesibilidad, con dos niveles: accesible y no accesible; tipo de silogismo, con dos niveles: válido y no válido; versión, con los mismos valores que en el experimento anterior. Las VD los juicios que el sujeto emitía, la seguridad y la explicación. Experimento III: diseño factorial 2x3x2x4. VI: contenido; bloque, con tres niveles que hacen referencia a tres períodos temporales; tipo de silogismo y versión. VD tasa de aciertos, tiempo de reacción y seguridad. Cuadernillos de elaboración propia, taquistoscopio, cronoscopio. Los juicios emitidos por los sujetos ante tareas de inferencia silogística, utilizando cuantificadores probabilísticos, muestran pautas similares a las obtenidas con metodología tradicional. Los sujetos presentan elevadas tasas de errores y no se adaptan a patrones o modelos formales. Si bien no se ha observado un efecto facilitador del contenido de las premisas en el razonamiento de los sujetos, éstos se ven afectados en gran medida por variables contextuales. La presentación taquistocópica de los ítems le sirve a los sujetos para sentirse más seguros. La inclusión de premisas en un texto mejora la ejecución de las tareas de inferencia silogística. Esto indica que el razonamiento humano no es un proceso que se realice 'in vacuo' sino que es dependiente del contexto sobre el que se efectúa la tarea. El razonamiento humano es impreciso, difuso, se basa en categorías mal definidas, utiliza cuantificadores probabilísticos ajenos a la lógica formal, es dependiente del contexto, presenta sesgos y heurísticos y se apoya en el uso y evaluación de escenarios mentales de los que se derivan consecuencias plausibles, en lugar de aplicar reglas que conducen a consecuencias necesarias. Consideramos que la tarea del psicólogo es 'comprender la naturaleza de la conducta inferencial más que juzgar si ésta es racional o irracional' y de ahí que planteemos la necesidad de que la investigación psicológica sobre el razonamiento profundice en el estudio de las variables que influyen en la conducta inferencial.

Effect of oxygen adsorption on the chiral pt{531} surface

The adsorption of oxygen on the chiral Pt{531} surface was studied by high-resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). After the surface is annealed in oxygen (3 x 10(-7) mbar), three O 1s peaks are observed in XPS. One peak, at 529.5 eV, is assigned to chemisorbed oxygen; it disappears after annealing in vacuo to temperatures above 900 K. The other two peaks at 530.8 and 532.3 eV are stable up to at least 1250 K. They are associated with oxide clusters on the surface. These clusters readily react with coadsorbed carbon monoxide at temperatures between 315 and 620 K.

Durability assessment of PbTe/II-IV infrared filters (Space Shuttle 1st LDEF)

Residual stress having been further reduced, selected infrared coatings composed of thin films of (PbTe/ ZnS (or ZnSe) can now be made which comply with the durability requirements of MIL-48616 whilst retaining transparency. Such improved durability is due to the sequence:- i) controlled deposition, followed by ii) immediate exposure to air, followed by iii) annealing in vacuo to relieve stress. (At the time of writing we assume the empiric procedure "exposure to air/annealing in vacuo" acts to relieve the inherent stresses of deposition). As part of their testing, representative sample filters prepared by the procedure are being assembled for the shuttle's 1st Long Duration Exposure Facility (to be placed in earth orbit for a considerable period and then recovered for analysis). The sample filters comprise various narrowband-designs to permit deduction of the constituent thin film optical properties. The Reading assembly also contains representative sample of the infrared crystals, glasses, thin-film absorbers and bulk absorbers, and samples of shorter-wavelength filters prepared similarly but made with Ge/SiO. Findings on durability and transparency after exposure will be reported.

Conformational behavior of different possible ways of oligoglycine formation in a solvent-free environment

The possible ways for glycine oligopeptide formation in gas phase, both in the extended P-strand like conformation and folded 2(7)-ribbon like conformations are analyzed using quantum chemical calculations. We focus on the sequential formation of peptide bond through upgradation of the immediate lower order molecule and observe the consequences in other related processes like oligoglycine formation through simultaneous peptide linkage of n glycine monomers and interchange of molecular conformation through peptide linkage. A comparison is made between the structures and binding energies obtained for both conformers. All binding energies are increased by the zero-point energy contribution. The role of electron correlation effects is briefly analyzed. The folded 2(7)-ribbon-like conformations in vacuo are found to be more stable in comparison to the extended structure. (c) 2007 Elsevier B.V. All rights reserved.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

Spherical particles of phenolic resin treated with iron oxide

This paper describes the preparation and characterization of phenolic resins' thermospheres covered by a magnetic phase of iron oxide. The thermospheres were prepared by allowing phenol and formaldehyde to react under dispersion polymerization conditions and the iron oxide phase was incorporated in situ onto the phenolic resin particles by adding concentrated NH3 to FeCl2 in DMSO. This reaction was conducted at 70 degrees C under nitrogen atmosphere in a controlled temperature vessel, and the modified resin was isolated and dried in vacuo. Both pure and modified resins were characterized by DRX, TG- DTA, and MEV/ EDX. The modified particles were attracted by a magnetic field, indicating the fixation of magnetic iron oxide. No diffraction peaks were observed in DRX analysis; thermal analysis ( DTA) of both pure and modified resins presented exothermic events between 300 and 680 degrees C, and 300 and 570 degrees C, respectively, indicating the microstructure of the resin was modified after the treatment. Thermogravimetric analysis ( TGA) of the pure resin registered a 2.0% residue, compared to 8.0% for the modified resin. These residues correspond to about 7.0% of fixed iron oxide. MEV/ EDX analyses confirm the modification of the resins by the process of fixing iron oxide.