Flame Temperature Effect on the Structure of SiC Nanoparticles Grown by Laser Pyrolysis

Small SiC nanoparticles (10 nm diameter) have been grown in a flow reactor by CO₂ laser pyrolysis from a C₂H₂ and SiH₄ mixture. The laser radiation is strongly absorbed by SiH₄ vibration. The energy is transferred to the reactive medium and leads to the dissociation of molecules and the subsequent growth of the nanoparticles. The reaction happens with a flame. The purpose of the experiments reported in this paper is to limit the size of the growing particles to the nanometric scale for which specific properties are expected to appear. Therefore the effects of experimental parameters on the structure and chemical composition of nanoparticles have been investigated. For a given reactive mixture and gas velocity, the flame temperature is governed by the laser power. In this study, the temperature was varied from 875°C to 1100°C. The chemical analysis of the products indicate that their composition is a function of the temperature. For the same C/Si atomic ratio in the gaseous phase, the C/Si ratio in the powder increases from 0.7 at 875°C up to 1.02 at 1100°C, indicating a growth mechanism limited by C₂H₂ dissociation. As expected, X-ray diffraction has shown an improved crystallisation with increasing temperature. Transmission electron microscopy observations have revealed the formation of 10 nm grains for all values of laser power (or flame temperature). These grains appear amorphous at low temperature, whereas they contain an increasing number of nanocrystals (2 nm diameter) when the temperature increases. These results pave the way to a better control of the structure and chemical composition of laser synthesised SiC nanoparticles in the 10 nm range.     

Determination of limonene oxidation products using SPME and GC-MS

Limonene is a common component found in consumer goods ranging from beverages to cleaning compounds. Limonene oxidation products, however, have a less desirable flavor and fragrance. Early detection of limonene oxide formation would aid quality control. A method is developed to determine the concentration of limonene oxide in essential oils and beverages using solid-phase microextraction (SPME). A headspace sampling technique is used to reduce or eliminate the presence of less volatile components. Several different SPME fibers are tested, varying in polymer thickness, polymer cross-linking and bonding, and polarity of the polymer. For each fiber tested, the sampling time is optimized for reproducible results. The 7-microm-thick bonded poly(dimethylsiloxane) fiber provides the best results. External standards are used for quantitation.     

An Alternative Method for Anomeric Deacetylation of Per-acetylated Carbohydrates

An alternative method for anomeric deacetylation of fully acetylated carbohydrates has been developed using imidazole in methanol.     

A New Asterosaponin from the Starfish Culcita novaeguineae

A new asterosaponin named novaeguinoside A, along with a known saponin, asteronyl pentaglycoside sulfate, was isolated from the starfish Culcita novaeguineae. The new compound was identitied to be sodium 6α-O-{β-D-fucopyranosyl-(1→2)-β-D-fucopyranosyl-(1→4)-[β-D-quinovopyranosyl-(1→2)]-β-D-xylopyranosyl-(1→3)-[β-D-quinovopyranosyl}-5α-pregn-9(11)-en-20-one-3β-yl-sulfate by extensive spectral analysis and chemical evidence.     

Mechanical properties of clay‐reinforced polyamide

Intercalated and exfoliated nanocomposites were prepared by extrusion and injection of polyamide‐6 and highly swollen or slightly swollen montmorillonite, respectively. The microstructure of the nanocomposites has been studied previously. In this article, we investigated the influence of the preferential orientation of the montmorillonite sheets on the mechanical properties of the nanocomposites. Dynamic mechanical analysis and tensile tests showed that the elastic modulus depends mainly on the filler loading. A parallel coupling could well account for the behavior of the nanocomposites. The calculated elastic and storage moduli of montmorillonite were set to 140 and 40 GPa, respectively. Compression tests were performed to study the anisotropy of the mechanical properties. The elastic modulus and flow strain were sensitive to the filler orientation. A Tandon–Weng approach was applied to consider the geometry of the filler. In all low‐deformation tests, no significant difference between intercalated and exfoliated systems was observed. Finally, the influence of the dispersion and exfoliation state of the filler on the ultimate properties of the nanocomposites (tensile tests) is discussed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 272–283, 2002     

Electrochemical investigations of amino acids at solid electrodes: Part I. Sulfur components: Cystine,cysteine, methionine

The electrochemical oxidation of sulfur amino acids has been investigated by ac measurements and cyclic voltammetry at solid electrodes (Au, vitreous carbon). Electrochemical oxidation proceeds first in the adsorbed state and second by diffusion at metal electrodes. Electrochemical oxidation is catalyzed by a labile metal oxide. At vitreous carbon electrode oxidation in the adsorbed state is only present in the case of methionine. XPS studies have shown the presence of

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as intermediate species. To explain the experimental results a reaction path is proposed.     

Excimer-laser-assisted RF glow-discharge deposition of amorphous and microcrystalline silicon thin films

We combine the deposition of Hydrogenated amorphous Silicon (a-Si:H) by rf glow discharge with XeCl-excimer laser irradiation of the growing surface in order to obtain different kinds of silicon films in the same deposition system. In-situ UV-visible ellipsometry allows us to measure the optical properties of the films as the laser fluence is increased from 0 up to 180 mJ/cm² in separate depositions. For fixed glow-discharge conditions and a substrate temperature of 250° C we observe dramatic changes in the film structure as the laser fluence is increased. With respect to a reference a-Si:H film (no laser irradiation) we observe at low laser fluences (15–60 mJ/cm²) that the film remains amorphous but demonstrates enchanced surface roughness and bulk porosity. At intermediate fluences (80–165 m/Jcm²), we obtain an amorphous film with an enhanced density with respect to the reference film. Finally, at high fluences (165–180 mJ/cm²), we obtain microcrystalline films. The in-situ ellipsometry measurements are complemented by ex-situ measurements of the dark conductivity, X-ray diffraction, and Elastic Recoil Detection Analysis (ERDA). Simulation of the temperature profiles for different film thicknesses and for three laser fluences indicates that crystallization occurs if the surface temperature reaches the melting point of a-Si:H ( 1420 K). The effects of laser treatment on the film properties are discussed by taking into account the photonic and thermal effects of laser irradiation.Presented at LASERION 93, Munich, June 21–23, 1993     

Three new flavonol malonylrhamnosides from Ribes alpinum.

Three new flavonol malonylrhamnosides, 3-O-(4"-O-malonyl)-alpha-L-rhamnopyranosides of mearnsetin, myricetin and quercetin respectively, together with the corresponding mearnsitrin, myricitrin, quercitrin and the 4-O-methyl phloracetophenone 2-O-beta-D-glucopyranoside, were isolated from the leaves of Ribes alpinum and fully characterized by spectrocopic methods including 2D NMR.     

Characterization of low-molecular weight peptides in champagne wine by liquid chromatography/tandem mass spectrometry

This paper reports the use of an on-line LC–ESI–MS/MS method for the identification and quantification of di- and tripeptides in champagne wine without laborious sample pretreatment. The identification of these compounds, in their underivatised form, is based on identical retention times and ESI–MS spectra to those of reference standards. The presence of nine dipeptides (Arg–Ile, Ile–Arg, Ile–Val, Lys–Phe, Lys–Tyr, Phe–Lys, Tyr–Gln, Tyr–Lys, Val–Ile) and the absence of two tripeptides (Phe–Arg–Arg and Lys–Met–Asn) have been evidenced in the matrix. Calibration curves for each analyte were established using Phe–Arg as internal standard. The calibration curves were linear in the concentration range 0.1–10 mg L⁻¹ with a determination coefficient, r², better than 0.992. The accuracy for the calibration standard was estimated at between 92 and 102%. This method allows high recovery and satisfies the necessary requirements with respect to accuracy, repeatability and sensitivity. The first application of this analytical method to the measurement of di- and tri-peptides in different vintages of champagne wine is reported. Compositional changes in the peptides occurred depending on the vintage.     

Asymmetric synthesis of tetrahydropalmatine via tandem 1,2-addition/cyclization

[Reaction: see text]. The enantioselective synthesis of both enantiomers of tetrahydropalmatine (2) (ee = 98%), a natural alkaloid belonging to the tetrahydroprotoberberine family, is described. The key step of this total synthesis is based on our tandem 1,2-addition/ring-closure methodology employing lithiated methylbenzamide and benzaldehyde SAMP or RAMP hydrazones as substrates. An initial route was investigated for the formation of N- and 3-substituted dihydroisoquinolones starting from 2-substituted benzaldehyde SAMP hydrazones, but although high diastereoselectivity was achieved, only disappointing yields were obtained. In our subsequent synthetic strategy, 2,3-dimethoxy-6-methylbenzamide 6 and 3,4-dimethoxybenzaldehyde SAMP or RAMP hydrazone 19 gave the dihydroisoquinolones 20 in high diastereomeric purity (de > or = 96%) and reasonable yield (54-55%), taking into account the complex functionalities established in one step. Cleavage of the N-N bond of the chiral auxiliary and reduction of the carbonyl group of the amide moiety were performed in the same step, and the resulting tetrahydroisoquinolines 22 (ee = 99%) were N-functionalized by treatment with various electrophiles to investigate the ring closure by Pummerer, Friedel-Crafts, and Pomeranz-Fritsch reactions. The Pummerer cyclization led to the formation of (S)-(-)-2 with slight racemization (ee = 89%), whereas the Friedel-Crafts reaction proved to be unsuccessful. Finally, Pomeranz-Fritsch-type cyclization afforded the desired title compound (R)-(+)-2 in excellent enantioselectivity in 9% overall yield over seven steps and after optimization of the last step (S)-(-)-2 in 17% overall yield.