Search results for "ACTIVATION"

Ab initio study of structure and energetics of species involved in the 2,4-dinitro-toluene hydrogenation on Pd catalysts

2002

Abstract Quantum-mechanical calculations, at HF level, were performed to gain chemical–physical basis information on the 2,4-dinitro-toluene hydrogenation occurring over palladium catalysts. To investigate the surface characteristics of the species involved in the reaction system, simplified molecular models including small metal clusters were considered. Remarkable findings, useful to elucidate the reaction mechanism and important parameters, working in time dependent Monte-Carlo simulations of the title reaction, were obtained; inter alia: the molar standard free energies of the molecules involved in the reaction, the volume occupied by the species in solution phase and the qualitative or…

Unique distal size selectivity with a digold catalyst during alkyne homocoupling

2015

Metal-catalysed chemical reactions are often controlled by steric hindrance around the metal atom and it is rare that substituents far away of the reaction site could be differentiated during reaction, particularly if they are simple alkyl groups. Here we show that a gold catalyst is able to discriminate between linear carbon alkynes with 10 or 12 atoms in the chain during the oxidative homocoupling of alkynes: the former is fully reactive and the latter is practically unreactive. We present experimental evidences, which support that the distal size selectivity occurs by the impossibility of transmetallating two long alkyl chains in an A-framed, mixed-valence digold (I, III) acetylide compl…

Planar-Chiral 1,1 '-Diboryl Metallocenes: Diastereoselective Synthesis from Boryl Cyclopentadienides and Spin Density Analysis of a Diborylcobaltocene

2017

International audience; The reaction of nonsubstituted alkali metal cyclopentadienides with haloboranes leads to similar to 90:10 mixtures of isomeric diene products that can be deprotonated to give simple boryl cyclopentadienides. We extended this transformation to the sterically hindered lithium tert-butylcyclopentadienide 1 using FBMe(s)2 (Mes = 2,4,6-trimethylphenyl) and ClBCy2 as electrophiles. The boryl group is selectively introduced in the remote position to minimize steric congestion. The new boryl dienes are obtained as mixtures of isomers, and subsequent deprotonation with MeLi or LiHMDS affords the lithium 1,3-disubstituted cyclopentadienides Sa,b in yields over 95%. Direct asse…

Mutations affecting MHC class II binding of the superantigen streptococcal erythrogenic toxin A.

1993

Streptococcal pyrogenic exotoxin A (SPEA) is an important pathogenicity factor of group A streptococci. It is a member of the family of 'superantigens' produced by Staphylococcus aureus and Streptococcus pyogenes, and its T lymphocyte stimulating activity is involved in the pathogenesis of certain diseases caused by pyogenic streptococci. In this study we have generated nine mutant SPEA molecules by substituting amino acids in the regions of homology between different streptococcal and staphylococcal superantigens. An additional mutant was created by deletion of the 10 N-terminal amino acids. The mutants were expressed as fusion proteins. Several mutations led to a loss of function due to a…

Freezing without surrounding cryomedium preserves the endothelium and its function in human internal mammary arteries

2005

Abstract Purpose Cryopreserved human blood vessels may become important tools in bypass surgery. Optimal cryopreservation of an arterial graft should, therefore, preserve both histological and physiological characteristics of smooth muscle and endothelium comparable to the unfrozen artery. Methods Rings from human internal mammary arteries (IMA) were investigated in vitro either unfrozen or after immersion into a cryomedium (RPMI 1640 containing 1.8 M Me2SO and 0.1 M sucrose) and cryostorage with and without surrounding medium. Results In unfrozen IMA, neither contractile responses to noradrenaline (NA) nor endothelium-dependent relaxant responses to acetylcholine (ACH) was modified after e…

Incorporation of ATP synthetase into long-term stable liposomes of a polymerizable synthetic sulfolipid

1981

Vortex-system ordering during magnetisation measurements in YBa2Cu3O7−δ films at low temperatures

2007

Abstract Zero-field-cooling dc magnetisation relaxation measurements performed on optimally doped epitaxial YBa 2 Cu 3 O 7− δ films with the external magnetic field H oriented parallel to the c -axis reveal the ordering of the creeping vortex-system in the low temperature T domain, due to the macroscopic currents induced in the sample. This dynamic ordering manifests itself through the appearance of a maximum in the T variation of the normalised vortex-creep activation energy. The location of this maximum in the H – T plane describes a well-defined current induced order–disorder line. Our results suggest the absence of a static elastic vortex glass in disordered high-temperature superconduc…

Superconductivity in high‐quality (Hg 0.9 Re 0.1 )Ba 2 CaCu 2 O 6+ δ HTSC thin films

2004

High-quality epitaxial (Hg0.9Re0.1)Ba2CaCu2O6+δ (HgRe-1212) HTS thin films were successfully prepared using pulsed laser deposition (PLD) of the Re0.1Ba2CaCu2O6+δ precursor and subsequent Hg vapor annealing. The thin films exhibit a sharp superconducting transition at Tc ≈ 120 K. The resistive transitions have been investigated in magnetic fields up to 6 T parallel and perpendicular to the c-axis. We have determined the activation energy of thermally activated flux-motion for both magnetic field orientations. (© 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Vortex-creep activation energy in YBa2Cu3O7/PrBa2Cu3O7 superlattices

2010

Abstract YBa 2 Cu 3 O 7 /PrBa 2 Cu 3 O 7 (YBCO/PBCO) superlattices with a different ratio of the superconducting and insulating layer thicknesses were prepared by high pressure dc sputtering. The vortex-creep activation energy U 0 was determined by analyzing the in-plane resistive transition of 200 μm wide bridges with the external magnetic field B oriented along the c axis. It was found that U 0 is proportional to the thickness of the YBCO layers, and does only weakly depend on the PBCO layer thickness, when the latter exceeds two unit cells. We observed a change in the variation of U 0 with the current I in the specimen: U 0 exhibits a plateau in the low- I region, then decreases signific…

Electrochemical impedance spectroscopy of polyelectrolyte multilayer modified gold electrodes: influence of supporting electrolyte and temperature.

2005

Electrochemical impedance spectroscopy and cyclic voltammetry are employed to characterize poly(styrenesulfonate)/poly(allylamine hydrochloride) multilayers assembled onto cysteamine-modified gold surfaces. The influence of the supporting electrolyte and temperature on the impedance response is studied because of both its practical interest and the need to test further the capillary membrane model recently developed by Barreira et al. [J. Phys. Chem. B 2004, 108, 17973]. The results obtained are interpreted quite satisfactorily in terms of this model, thus providing additional support to its usefulness for the description of ionic transport through polyelectrolyte multilayers. It is observe…