Tips and Tricks for the Surface Engineering of Well-Ordered Morphologically Driven Silver-Based Nanomaterials

Particularly-shaped silver nanostructures are successfully applied in many scientific fields, such as nanotechnology, catalysis, (nano)engineering, optoelectronics, and sensing. In recent years, the production of shape-controlled silver-based nanostructures and the knowledge around this topic has grown significantly. Hence, on the basis of the most recent results reported in the literature, a critical analysis around the driving forces behind the synthesis of such nanostructures are proposed herein, pointing out the important role of surface-regulating agents in driving crystalline growth by favoring (or opposing) development along specific directions. Additionally, growth mechanisms of the different morphologies considered here are discussed in depth, and critical points highlighted.     

Deformations of arithmetically Cohen-Macaulay subvarieties of pn

We show that every arithmetically Cohen-Macaulay two-codimensional subscheme ofP ⁿ can be deformed to a reduced union of two-codimensional linear subvarieties. This problem (classical for curves with the name of Zeuthen problem) was solved for curves by F.Gaeta.     

Computation of the Maslov index and the spectral flow via partial signatures

Given a smooth Lagrangian path, both in the finite and in the infinite dimensional (Fredholm) case, we introduce the notion of partial signatures at each isolated intersection of the path with the Maslov cycle. For real-analytic paths, we give a formula for the computation of the Maslov index using the partial signatures; a similar formula holds for the spectral flow of real-analytic paths of Fredholm self-adjoint operators on real separable Hilbert spaces. As applications of the theory, we obtain a semi-Riemannian version of the Morse index theorem for geodesics with possibly conjugate endpoints, and we prove a bifurcation result at conjugate points along semi-Riemannian geodesics. To cite this article: R. Giambò et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Multilayered Cu–Ti deposition on silicon substrates for chemiresistor applications

Abstract

On the perspective to develop CuO–TiO₂ MOS, multilayered Cu and Ti thin layers were alternatively deposited on silicon wafers using 25?keV Ar?+?ion beam sputtering and, subsequently, oxidized by thermal annealing in air at 400?°C for 24?h. The deposited films have variable ratios of the Cu and Ti % at. One of the main goal is to obtain such multilayers avoiding the presence of Cu–Ti–O compounds. The samples were characterized in terms of composition (by RBS and SIMS analyses) and morphology (by AFM and SEM investigations). In particular, SIMS maps allows to observe the spatial distribution and thickness of each phase of the Cu/Ti multilayers, and further to observe Cu diffusion and mixing with Ti, as well as phase separation of CuO and TiO₂ in the samples. The reasons of this effect represent an open issue that has to investigated, in order to improve the MOS fabrication.     

ZnS bubble clusters with onion-like structures

Following recent studies which showed that the most stable structures for (ZnS)(n) clusters (n= 10-47) are the so-called "bubble clusters", in which all the atoms are three-coordinated, we have used simulated annealing techniques to find the most stable structure for a larger cluster, (ZnS)(60). We find an onion-like structure, with one small cluster enclosed inside a bigger one. The inner cluster has the structure of a sodalite cage. Bonding between the inner and the outer clusters creates a network of four-coordinated atoms.     

Aldol condensations over reconstructed Mg-Al hydrotalcites: structure-activity relationships related to the rehydration method

Two different rehydration procedures in the liquid or gas phase have been applied to reconstruct mixed oxides derived from calcined hydrotalcite-like materials to be used as catalysts for aldol condensation reactions. The as-synthesized hydrotalcite, its decomposition product, as well as the reconstructed solids upon rehydration were characterized by XRD, N(2) adsorption, He pycnometry, FTIR, SEM, TEM, (27)Al MAS-NMR and CO(2)-TPD (TPD=temperature-programmed desorption). Compared to the Mg-Al mixed oxide rehydrated in the gas phase (HT-rg), that rehydrated in the liquid phase (HT-rl) exhibits a superior catalytic performance with respect to the aldol condensation of citral with ketones to yield pseudoionones and in the self-aldolization of acetone. The textural properties of HT-rl and HT-rg differ strongly and determine the catalytic behavior. A memory effect led to a higher degree of reconstruction of the lamellar structure when the mixed oxide was rehydrated in the gas phase rather than in the liquid phase, although liquid-phase rehydration under fast stirring produced a surface area that was 26 times greater. This contrasts to typical statements in the literature claiming a higher degree of reconstruction in the presence of large amounts of water in the medium. CO(2)-TPD shows that the number of OH(-) groups and their nature are very similar in HT-rg and HT-rl, and cannot explain the markedly different catalytic behavior. Accordingly, only a small fraction of the available basic sites in the rehydrated samples is active in liquid-phase aldol condensations. Our results support the model in which only basic sites near the edges of the hydrotalcite platelets are partaking in aldol reactions. Based on this, reconstructed materials with small crystallites (produced by exfoliation during mechanical stirring), that is, possessing a high external surface area, are beneficial in the reactions compared to larger crystals with a high degree of intraplatelet porosity.     

Enantiomeric resolution of anti-HIV agents on a cellulose derivative chiral stationary phase

Summary Anti-HIV enantiomeric 1H, 3H-thiazolo[3, 4-a] benzimidazoles have been stereospecifically analyzed by elution on a column of cellulose tris-(4-methyl-phenylbenzoate)ester adsorbed on macroporous silica (Chiralcel^R OJ).The enantiomeric resolution of the compounds examined is linked to a complex and competitive contribution of different factors.     

Influence of organic modifier and temperature on the enantiomeric separation of γ-lactams by HPLC

Summary A high-performance liquid chromatographic method is reported for the resolution of the enantiomers of a series of fused -lactams (2,7-diaza-3-oxo[3.3.0]octan-6-ones) with probable anti-HIV and anticancer activity. Resolution was achieved on a Chiralcel^® OD column, cellulose tris-(3,5-dimethylphenyl carbamate) adsorbed on macroporous silica gel; mixtures ofn-hexane and isopropyl alcohol in different proportions were used as the mobile phase. The analysis was studied at different temperatures.