Secondary ion yields produced by keV atomic and polyatomic ion impacts on a self-assembled monolayer surface

A suite of keV polyatomic or 'cluster' projectiles was used to bombard unoxidized and oxidized self-assembled monolayer surfaces. Negative secondary ion yields, collected at the limit of single ion impacts, were measured and compared for both molecular and fragment ions. In contrast to targets that are orders of magnitude thicker than the penetration range of the primary ions, secondary ion yields from polyatomic projectile impacts on self-assembled monolayers show little to no enhancement when compared with monatomic projectiles at the same velocity. This unusual trend is most likely due to the structural arrangement and bonding characteristics of the monolayer molecules with the Au(111). Copyright 1999 John Wiley & Sons, Ltd.     

Osculating spaces to secant varieties

We generalize the classical Terracini’s Lemma to higher order osculating spaces to secant varieties. As an application, we address with the so-called Horace method the case of thed-Veronese embedding of the projective 3-space. This research is part of the T.A.S.C.A. project of I.N.d.A.M., supported by P.A.T. (Trento) and M.I.U.R. (Italy).     

Selective synthesis of isobutanol by means of the Guerbet reaction: Part 2. Reaction of methanol/ethanol and methanol/ethanol/n-propanol mixtures over copper based/MeONa catalytic systems

The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst.     

Novel polymer-supported β-diketonate nickel catalysts for α-olefin activation

Styrene–divinylbenzene resins were used for the synthesis of different polymer-bound β-diketones, obtained by anchoring the chelating group through either the central or the lateral position. The heterogenized diketone ligand was subsequently reacted with Ni(COD)₂ analogously to the corresponding homogeneous catalysts active in α-olefin oligomerization. The heterogenized catalysts showed a good activity only when the central position of the chelate moiety was free. Heterogenization caused a significant change of selectivity: olefin oligomerization was accompanied by the formation of a large amount of polymeric products. This behavior is discussed in terms of steric effects caused by the bulky polymeric ligand. © 1998 John Wiley & Sons, Ltd.     

Polymeric photoinitiators based on side-chain benzoin methyl ether and tertiary amine moieties for fast UV curable coatings

The synthesis is reported of a new series of polymeric photoinitiators obtained by copolymerization of a-methylolbenzoin methyl ether acrylate (MBA) with different N,N-dialkylamino alkyl acrylates. The copolymers have been fully characterized and employed in the photoinitiated polymerization and crosslinking reactions of a standard acrylic formulation for clear curable coatings. The photoinitiation activity of the above systems has been measured by using microwave dielectrometry and differential photocalorimetry, and compared with that found for the corresponding low-molecular-weight models. The results clearly indicate that the copolymeric systems display a remarkable decrease of the induction period and an improved overall activity in the UV curing of the acrylic coatings. An interpretation of the experimental findings is also reported.     

Synthesis and thermal properties of NiSbS–As doped phase

The substitution of Sb with As in the NiSbS intermetallic compound was studied in the framework of evaluating a possible increase of the thermoelectric properties. Different NiSb_1?xAs_xS samples were synthesized with increasing amounts of As (0 < x < 0.66) employing a simple synthetic route using a muffle furnace. Scanning electron microscopy equipped with energy-dispersive X-ray spectroscopy was used to investigate the microstructure. X-ray powder diffraction techniques were employed in order to study the possible existence of a solid solution between NiSbS and NiAsS compounds, as well as to identify the crystal structure and determine the lattice parameters. All compounds were found to crystallise with the NiSbS prototype (cP12-P2₁3), with lattice parameters varying from a = 0.59341(7) nm (x = 0) to a = 0.56849(6) nm (x = 1). Good agreement with Vegard’s law was evidenced. Thermal measurements on NiSb_1?xAs_xS samples were carried out using DTA instruments to evaluate the thermal stability and the melting temperatures.     

A two-step conversion of alpha,beta-unsaturated ketones to their alpha-carbalkoxy or alpha-carbamoyl derivatives

Several enones are converted into their alpha-iodo derivatives in excellent yields and carbonylated with palladium catalysis in the presence of alcohol or amines to the alpha-carbonyl enones in satisfactory yields.     

A convergent scheme for a non local Hamilton Jacobi equation modelling dislocation dynamics

We study dislocation dynamics with a level set point of view. The model we present here looks at the zero level set of the solution of a non local Hamilton Jacobi equation, as a dislocation in a plane of a crystal. The front has a normal speed, depending on the solution itself. We prove existence and uniqueness for short time in the set of continuous viscosity solutions. We also present a first order finite difference scheme for the corresponding level set formulation of the model. The scheme is based on monotone numerical Hamiltonian, proposed by Osher and Sethian. The non local character of the problem makes it not monotone. We obtain an explicit convergence rate of the approximate solution to the viscosity solution. We finally provide numerical simulations.This work has been supported by funds from ACI JC 1041 “Mouvements d’interfaces avec termes non-locaux”, from ACI-JC 1025 “Dynamique des dislocations” and from ONERA, Office National d’Etudes et de Recherches. The second author was also supported by the ENPC-Région Ile de France.     

Existence results for rational normal curves

In this paper we study existence of rational normal curves inⁿ passing through p points and intersecting l codimension-twolinear spaces in n – 1 points each. If p + l = n + 3 andthe points and the linear spaces are general, then one expectsthe curve to exist, but this is not always the case. For p >0, our main result precisely describes in which cases the curveexists and in which it does not exist. Moreover, when thereis existence we also show that the curve is unique.