Etudes stereochimiques dans la serie du silacyclopentane: synthese de dimethyl-1,2 alcoxy-1 silacyclopentanes a stereoisomere preferentiel

The stereoselective alcoholysis of 1,2-dimethyl-1-chlorosilacyclopentane and the catalytic alcoholysis of 1,2-dimethylsilacyclopentane are described.     

Comparison of water-soluble CdTe nanoparticles synthesized in air and in nitrogen

It is commonly believed that high-quality CdTe nanoparticles with strong luminescence can only be prepared under the protection of an inert gas such as nitrogen or argon. Here, we report the preparation of highly luminescent CdTe nanoparticles in air and compare their luminescence properties with CdTe nanoparticles made in nitrogen. We find that both water-soluble CdTe nanoparticles made in air and in nitrogen exhibit strong photoluminescence as well as upconversion luminescence at room temperature. However, differences do exist between the particles made in air and those made in nitrogen. In particular, the particles prepared in air display a faster growth rate, grow to larger sizes, and display stronger electron coupling relative to the particles prepared in nitrogen. X-ray photoelectron spectroscopy analysis indicates that the oxygen content in the nanoparticles synthesized in air is higher that that in particles synthesized in N(2), likely resulting in a higher availability of excess free cadmium. Cytotoxicity measurements reveal that the particles made in air appear slightly more toxic, possibly due to the excess of free cadmium.     

Electron paramagnetic resonance study of the mononuclear Al species formed in the reaction of Al atoms and cyclopropylamine at 77 k in an adamantane matrix

Ground-state Al atoms have been reacted with cyclopropylamine (CpNH2) in an adamantane matrix at 77 K. The four paramagnetic species generated in the reaction have been studied by electron paramagnetic resonance (EPR) spectroscopy and their magnetic parameters extracted from the EPR spectra. The isotropic Al hyperfine interactions (hfis) for these radicals vary from 801 to 962 MHz and are consistent with values previously reported for structurally similar Al-centered radicals. The major species formed in the reaction has a highly anisotropic a tensor indicative of an Al-centered radical with a substantial amount of the unpaired spin density residing in the Al 3p orbital. In addition, there is EPR evidence that the insertion products, CpNH(AlH) and CpAlNH2, are formed in the reaction, suggesting that Al atoms can activate the N-H and C-N bonds of amines. It has been shown that a molecule of CpNH2 coordinates to CpNH(AlH), causing the Al, N and H hfi of the N-H insertion product to decrease. The values of the nuclear hfis calculated for the insertion products, using a density functional theory (DFT) method, are comparable to the experimental values.     

Near infrared diode laser spectroscopy of C2H2, H2O, CO2 and their isotopologues and the application to TDLAS, a tunable diode laser spectrometer for the martian PHOBOS-GRUNT space mission

A near-infrared tunable diode laser spectrometer called TDLAS has been developed that combines telecommunication-type as well as new-generation antimonide laser diodes to measure C₂H₂, H₂O, CO₂ and their isotopologues in the near infrared. This sensor is devoted to the in situ analysis of the soil of the Martian satellite PHOBOS, within the framework of the Russian space mission PHOBOS-GRUNT. In the first part of the paper, we report accurate spectroscopic measurements of C₂H₂ and ¹³C¹²CH₂ near 1.533 μm, of H₂O and CO₂ at 2.682 μm and of the isotopologues ¹³C¹⁶O₂ and ¹⁶O¹²C¹⁸O near 2.041 μm and H₂ ¹⁷O, H₂ ¹⁸O and HDO near 2.642 μm. The achieved line strengths are thoroughly compared to data from molecular databases or from former experimental determinations. In the second part of the paper, we describe the TDLAS spectrometer for the PHOBOS-GRUNT mission.     

Probing electron transfer dynamics at MgO surfaces by Mg-atom desorption

Ultraviolet excitation of high surface area MgO films using 4.7 eV femtosecond pulses results in neutral Mg-atom desorption with hyperthermal kinetic energies in the range 0.1-0.4 eV. The Mg-atom hyperthermal energies and power dependences are similar to those previously observed using nanosecond pulsed excitation. Femtosecond two-pulse correlation measurements reveal the existence of different dynamical paths for Mg-atom desorption. One mechanism displays a sub-150 fs time scale and involves the simultaneous or near-simultaneous transition of two electrons to a 3-coordinated Mg(2+) site. Other paths display picosecond time scales that we associate with dynamics following electron trapping at 3-coordinated Mg(2+) surface sites.     

Competition between planar and central chiral control elements in nucleophilic addition to ferrocenyl imine derivatives

Planar chirality associated with the ferrocene in ferrocenyl oximes and hydrazones bearing chiral auxiliaries effectively competes with or overrides the normally excellent stereocontrol afforded by the auxiliary in determining the diastereoselectivity of addition to the C=N bond.     

The oxidation/reduction kinetics of the plastoquinone pool controls the appearance of the I-peak in the O-J-I-P chlorophyll fluorescence rise: effects of various electron acceptors

Quantitative analysis of the fluorescence induction (FI) rise was used in this study to elucidate the complex effects of N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) on thylakoids. Reduced TMPD molecules, responsible for the ADRY agent effect, caused an increase in the amplitude of the O-J rise. Also, only oxidized TMPD molecules were shown to have the ability to bind the Q(B) pocket of photosystem II (PSII). On the other hand, the I-P rise was slowed in proportion with the oxidized TMPD concentration, inducing the clear appearance of the I-peak. While this property was previously thought to be unique to TMPD, this study shows that some artificial electron acceptors of PSII, silicomolybdate, 2,5-dichloro-p-benzoquinone, and phenyl-p-benzoquinone, have a similar effect. These results demonstrated a major role of the oxido-reduction kinetics of the PQ-pool in the resolution of J-I and I-P phases in the FI of isolated thylakoids.