SiC bonding in ( C 60 ) n Si m clusters

This paper deals with a new type of SiC bonding where silicon atom seems to bridge C₆₀ molecules. We have studied films obtained by deposition of (C₆₀)_nSi_m clusters prepared in a laser vaporization source. Prior deposition, free ionized clusters were studied in a time-of-flight mass spectrometer. Mixed clusters (C₆₀)_nSi_m were clearly observed. Abundance and photofragmentation mass spectroscopies revealed the relatively high stability of the (C₆₀)_nSi _n ⁺ , (C₆₀)_nSi _{n - 1} ⁺ and (C₆₀)_nSi _{n - 2} ⁺ species. This observation is in favor of the arrangement of these complexes as polymers where the C₆₀ cages may be bridged by a silicon atom. Free neutral clusters are then deposited onto substrate making up a nanogranular thin film (≃ 100 nm). The film is probed by Auger and X-ray photoemission spectroscopies, but above all by surface enhanced Raman scattering. The results suggest an unusual chemical bonding between silicon and carbon and the environment of the silicon atom is expected to be totally different from the sp³ lattice: ten or twelve carbon neighbors might surround silicon atom. The bonding is discussed to the light of the so-called fullerene polymerization as observed for pure fullerite upon laser irradiation. This opens a new route for bridging C₆₀ molecules together with an appreciable energy bonding, since the usual van der Waals bonding in fullerite could be replaced by an ionocovalent bond. Such an assumption must be checked in the future by XAS and EXAFS experiments. Received 15 November 2000     

The role of nanocellulose fibers, starch and chitosan on multipolysaccharide based films

Thin nanocomposite films of thermoplastic starch, chitosan and cellulose nanofibers (bacterial cellulose or nanofibrillated cellulose) were prepared for the first time by solvent casting of water based suspensions of the three polysaccharides. The role of the different bioploymers on the final properties (thermal stability, transparency, mechanical performance and antimicrobial activity) of the films was related with their intrinsic features, contents and synergic effects resulting from the establishment of interactions between them. Thermoplastic starch displays an important role on the thermal stability of the films because it is the most stable polysaccharide; however it has a negative impact on the mechanical performance and transparency of the films. The addition of chitosan improves considerably the transparency (up to 50 % transmittance for 50 % of chitosan, in respect to the amount of starch), mechanical performance and antimicrobial properties (at least 25 % of chitosan and no more than 10 % of cellulose nanofibers are required to observe bacteriostatic or bactericidal activity) but decrease their thermal stability. The incorporation of cellulose nanofibers had the strongest positive impact on the mechanical properties of the materials (increments of up to 15 and 30 MPa on the Young′s modulus and Tensile strength, respectively, for films with 20 % of BC or NFC). Nonetheless, the impact in thermal stability and mechanical performance of the films, promoted by the addition of chitosan and cellulose nanofibres, respectively, was higher than the expected considering their percentage contents certainly because of the establishment of strong and complex interactions between the three polysaccharides.     

Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups

This Communication describes the use of CuInS₂/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.     

Quantum Dot‐Catalyzed Photoreductive Removal of Sulfonyl‐Based Protecting Groups

This Communication describes the use of CuInS₂/ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl‐protected phenols. For a series of aryl sulfonates with electron‐withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD‐binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor–acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.     

Interpretation of micromechanical measurements on butyl acrylate,vinyl acetate based systems: Role of interfaces in “polymer-polymer composites”

Films were obtained by coalescence of different types of latex particles; the purpose of this work was to get informations on the geometric arrangement (so called “morphology”) of the different phases and on the role of interfaces. Such informations are difficult to get by direct investigations (weak contrast in Transmission Electron Microscopy, poor information provided by X-ray measurements on amorphous polymers …) the analysis of experimental data obtained in high resolution mechanical spectrometry appears powerful: it is possible, for instance, to estimate the profile gradient of composition at the interface. Comparison is made between the morphology of the different phases in some films and the correspondent structure of particles.     

Simulation of the ion beam-plasma interaction processes for point-like ions in doped DT plasmas

The purpose of this work is to study the interaction between an ion beam and a doped deuterium-tritium (DT) plasma in a fast ignition nuclear fusion context. In order to analyze the influence of the dopants in the interaction process, we present a physical model to carry out spatial-temporal simulations of the stopping of an ion beam interacting with a doped plasma target, the plasma heating processes, and the formation of the ignition regions. We perform a set of numerical experiments where different concentrations of dopants are added to a fully ionized DT plasma. These simulations allow us to characterize the increase in the stopping power and the maximum temperatures achieved with the presence of impurities, as well as the reduction of the heated and ignition regions. This reduction in the ignition region indicates difficulties for the formation of an efficient hot spot when there are dopants in the DT plasma.     

A spectroscopic database for water vapor adapted to spectral properties at high temperature, and moderate resolution

The prediction of infrared spectral radiance from high temperature media such as combustion gases requires spectroscopic data for triatomic molecules like water vapor and carbone dioxyde. At temperature above 2000 K, water vapor spectrum is composed of hundreds of thousands lines making practical computations uneasy. We have set up a spectroscopic database for water vapor, based on three existing lines compilations. This database is well suited to computation of remote sensing spectra where hot gases emission is seen through atmospheric paths. The database enables efficient computation of water vapor spectra between 600 and 6600 cm⁻¹ at moderate spectral resolution (5 cm⁻¹). It has been used to compute parameters of a statistical narrow band model which are used in practical applications.     

A generalization of local divergence measures

In this paper we propose a generalization of the concept of the local property for divergence measures. These new measures will be called g-local divergence measures, and we study some of their properties. Once this family is defined, a characterization based on Ling’s theorem is given. From this result, we obtain the general form of g-local divergence measures as a function of the divergence in each element of the reference set; this study is divided in three parts according to the cardinality of the reference set: finite, infinite countable or non-countable. Finally, we study the problem of componible divergence measures as a dual concept of g-local divergence measures.     

Characterization off-vectors of families of convex sets inR d Part I: Necessity of Eckhoff’s conditions

LetK=K ₁,...,K_n be a family ofn convex sets inR ^d . For 0≦i<n denote byf _i the number of subfamilies ofK of sizei+1 with non-empty intersection. The vectorf(K) is called thef-vectors ofK. In 1973 Eckhoff proposed a characterization of the set off-vectors of finite families of convex sets inR ^d by a system of inequalities. Here we prove the necessity of Eckhoff's inequalities. The proof uses exterior algebra techniques. We introduce a notion of generalized homology groups for simplicial complexes. These groups play a crucial role in the proof, and may be of some independent interest.