Unexpected end‐groups of poly(acrylic acid) prepared by RAFT polymerization

Low‐molecular‐weight poly(acrylic acid) (PAA) was synthesized by reversible addition fragmentation chain transfer polymerization with a trithiocarbonate as chain‐transfer agent (CTA). With a combination of NMR spectroscopy and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry, the PAA end‐groups of the polymer were analyzed before and after neutralization by sodium hydroxide. The polymer prior to neutralization is made up of the expected trithiocarbonate chain‐ends and of the H‐terminated chains issued from a reaction of transfer to solvent. After neutralization, the trithiocarbonates are transformed into thiols, disulfides, thiolactones, and additional H‐terminated chains. By quantifying the different end‐groups, it was possible to demonstrate that fragmentation is the rate limiting step in the transfer reaction. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5439–5462, 2004     

Surface chemical studies of the influence of In and Al on the decomposition of TEG on GaAs(100)

The interaction of triethylgallium (TEG) with the Ga-stabilized GaAs(100) surface in the presence of In and Al has been investigated using AES (Auger electron spectroscopy), HREELS (high resolution electron energy loss spectroscopy) and TDS (thermal desorption spectroscopy) techniques. Al is shown to greatly increase the saturation surface coverage of TEG on the surface and to suppress the desorption of TEG and diethylgallium (DEG). Etching of the surface Al by TEG is observed, resulting in the formation of gas phase Al organic species. Alkyl migration from GA to Al centres occurs, and the presence of Al substantially enhances the irreversible deposition of C. In is found to enhance DEG desorption and to lower the temperature at which absorbed ethyl groups decompose to gas phase ethene. Computer modelling has been carried out to extract kinetic parameters from measured thermal desorption spectra. These parameters are then used to calculate expected partial growth rates of GaAs during the growth of Ga_xAl_1−xAs and Ga_xIn_1−xAs using TEG. The data provide a molecular level understanding of the GaAs pa rtial growth rate variations arising during the deposition of III–V ternary materials.     

An aqueous route to organically functionalized silica diatom skeletons

Diatomaceous earth was functionalized by grafting organotrialkoxysilane precursors onto the surface of the porous silica cell walls of this biomineral. Vinyl- and mercapto-containing structures were prepared in aqueous media without disruption of the diatomic architecture. Successful grafting of the organic moieties was confirmed using solid state ²⁹Si MAS NMR spectroscopy, and the presence of the intact diatom framework by scanning electron microscopy. The sorption properties of mercaptopropyl-functionalized diatoms towards heavy metals was studied by measuring the accessibility and diffusion rates of mercury(II) species to the binding sites (-SH) by the means of electrochemical methods.     

Selected-area growth of carbon nanotubes by the combination of focused ion beam and chemical vapor deposition techniques.

In this article, we report a technique for growing carbon nanotubes in a more controllable fashion, which enables us to synthesize nanotubes directly in various forms of designed patterns. This nanofabrication process is based on a combination of focused ion beam (FIB) and chemical vapor deposition (CVD) techniques. In this process, arrays of conductive patterns were first deposited on silicon substrates by directing a gaseous compound (C(9)H(16)Pt) via the capillary needle-sized nozzles within a FIB system. The substrates were then coated with catalyst and further modified by the FIB to localize the position of the catalyst. Finally, the growth of carbon nanotubes on the designed substrates was carried out by CVD of hydrocarbon gases. This fabrication technique has the advantage of positioning carbon nanotubes in selected locations. This may open up opportunities for the direct synthesis of carbon nanotubes onto almost any substrate material, thus allowing fabrication of carbon nanotube-based devices.     

Influence of surface energy and relative humidity on AFM nanomechanical contact stiffness

The effects of surface functionality and relative humidity (RH) on nanomechanical contact stiffness were investigated using atomic force acoustic microscopy (AFAM), a contact scanned-probe microscopy (SPM) technique. Self-assembled monolayers (SAMs) with controlled surface energy were studied systematically in a controlled-humidity chamber. AFAM amplitude images of a micropatterned, graded-surface-energy SAM sample revealed that image contrast depended on both ambient humidity and surface energy. Quantitative AFAM point measurements indicated that the contact stiffness remained roughly constant for the hydrophobic SAM but increased monotonically for the hydrophilic SAM. To correct for this unphysical behavior, a viscoelastic damping term representing capillary forces between the tip and the SAM was added to the data analysis model. The contact stiffness calculated with this revised model remained constant with RH, while the damping term increased strongly with RH for the hydrophilic SAM. The observed behavior is consistent with previous studies of surface energy and RH behavior using AFM pull-off forces. Our results show that surface and environmental conditions can influence accurate measurements of nanomechanical properties with SPM methods such as AFAM.     

Uniqueness and continuous dependence on the initial data for a class of non-linear shallow shell problems

This note is concerned with the non-linear shallow shell model introduced in 1966 by W.T. Koiter, and later studied by M. Bernadou and J.T. Oden. We show the uniqueness of the solution to the dynamical model and that this solution is continuous with respect to the initial data. To cite this article: J. Cagnol et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Efficient synthesis of an imidazole-substituted delta-amino acid by the integration of chiral technologies

Two methods to produce (2S)-5-amino-2-(1-n-propyl-1H-imidazol-4-ylmethyl)-pentanoic acid were investigated. Diastereoisomeric salt resolution, using the quinidine salt, gave the desired intermediate in 98% ee and 33% yield. Asymmetric hydrogenation of various substrates gave high conversions, with up to 83% ee. Integration of these two approaches via asymmetric hydrogenation of a quinidine salt substrate followed by crystallization provided the desired intermediate in 94% ee and 76% yield.