Optical properties of donor-acceptor phenylene-ethynylene systems containing the 6-methylpyran-2-one group as an acceptor

Donor-acceptor phenylene ethynylene systems containing the 6-methylpyran-2-one group, synthesized via classic or microwave-assisted Sonogashira cross-coupling, exhibit pronounced solvatochromism in fluorescence suggesting a highly polar excited state; 4-[4-(4-N,N-dihexylaminophenylethynyl)phenylethynyl]-6-methylpyran-2-one has a fluorescence quantum yield >0.9 in cyclohexane.     

Electrochemistry, spectroelectrochemistry, chloride binding, and O2 catalytic reactions of free-base porphyrin-cobalt corrole dyads

Three face-to-face linked porphyrin-corrole dyads were investigated as to their electrochemistry, spectroelectrochemistry, and chloride-binding properties in dichloromethane or benzonitrile. The same three compounds were also investigated as to their ability to catalyze the electroreduction of dioxygen in aqueous 1 M HClO4 or HCl when adsorbed on a graphite electrode. The characterized compounds are represented as (PCY)H2Co, where P = a porphyrin dianion; C = a corrole trianion; and Y = a biphenylenyl, 9,9-dimethylxanthenyl, or anthracenyl spacer, which links the two macrocycles in a face-to-face arrangement. An axial binding of one or two Cl- ligands to the cobalt center of the corrole is observed for singly and doubly oxidized (PCY)H2Co, with the exact stoichiometry of the reaction depending upon the spacer size and the concentration of Cl- added to solution. No Cl- binding occurs for the neutral or reduced forms of the dyad, which contrasts with what is seen for the monocorrole, (Me4Ph5Cor)Co, where a single Cl- ligand is added to the Co(III) corrole in PhCN. The Co(III) form of the corrole in (PCY)H2Co also appears to be the catalytically active species in the electroreduction of dioxygen, which occurs at potentials associated with the Co(IV)/Co(III) reaction, that is, 0.35 V in 1 M HClO4 as compared to 0.31-0.42 V for the same three dyads in PhCN and 0.1 M TBAP. The potential for the catalytic electroreduction of O2 in HCl shifts negatively by 60 to 70 mV as compared to E(1/2) values in 1 M HClO4, consistent with the binding of Cl- to the Co(IV) form of the corrole and its rapid dissociation after electroreduction to Co(III) at the electrode surface.     

Analysis of carbohydrates in plants by high-performance anion-exchange chromatography coupled with electrospray mass spectrometry

A mass spectrometer was coupled to high-performance anion-exchange chromatography (HPAEC) with the help of electrochemical neutralization of the eluent and post-column addition of lithium chloride for carbohydrate analysis. Parallel selective channels (single ion monitoring) were used to decrease the detection limits and separate unresolved peaks. The mass specific detection allowed the simultaneous analysis of a wide range of sugar alcohols, mono-, di- and oligosaccharides. Carbohydrates extracted from leaves of poplar submitted to drought stress were analyzed using pulsed amperometric detection (PAD), then mass spectrometry. It allowed the confirmation of peak attribution and the identification of salicin as a major compound in the extracts. Different responses to water deficit and re-hydration were obtained for several carbohydrates, suggesting different roles in osmoprotection processes.     

Synthesis and characterization of Co/CdSe core/shell nanocomposites: bifunctional magnetic-optical nanocrystals

Nanocomposite materials provide the possibility for multifunctional properties in contrast with their more-limited single-component counterparts. Here, we report the synthesis and characterization of the first all-inorganic core/shell hybrid magnetic-optical nanoparticle, cobalt/cadmium selenide. The core/shell nanocrystals are prepared in a facile one-pot reaction, and their microstructure is analyzed using low- and high-resolution transmission electron microscopy. Using magnetic and optical characterization, we demonstrate bifunctional behavior, whereby the core retains the magnetic properties of the starting Co nanoparticle, and the shell emits similarly to a single-component CdSe nanoparticle. Interestingly, while the coercivity was found to be unchanged by shell formation, the blocking temperature for the composite structure was observed to be substantially lower (Co: >350 K; Co/CdSe: 240 K). In addition, we observed that at low temperatures (20 K) shell CdSe photoluminescence (PL) decay was very rapid (<1 ns). In contrast, nanocrystalline CdSe PL decay is typically much slower at such temperatures (>50 ns). Finally, we propose possible explanations for the unusual magnetic and optical behavior of the core/shell hybrid nanostructures.     

L'électron habillé non relativiste dans un champ magnétique

We consider a nonrelativistic electron interacting with a classical magnetic field pointing along the $x_3$-axis and with a quantized electromagnetic field. Because of the translation invariance along the $x_3$-axis, we consider the reduced Hamiltonian associated with the total momentum along the $x_3$-axis and, after introducing an ultraviolet cutoff and an infrared regularization, we prove that the reduced Hamiltonian has a ground state if the coupling constant and the total momentum along the $x_3$-axis are sufficiently small. Finally, we determine the absolutely continuous spectrum of the reduced Hamiltonian and we prove that the renormalized mass of the electron is greater than its bare one. To cite this article: L. Amour et al., C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

On the binding of successive sounds: perceiving shifts in nonperceived pitches

It is difficult to hear out individually the components of a "chord" of equal-amplitude pure tones with synchronous onsets and offsets. In the present study, this was confirmed using 300-ms random (inharmonic) chords with components at least 1/2 octave apart. Following each chord, after a variable silent delay, listeners were presented with a single pure tone which was either identical to one component of the chord or halfway in frequency between two components. These two types of sequence could not be reliably discriminated from each other. However, it was also found that if the single tone following the chord was instead slightly (e.g., 1/12 octave) lower or higher in frequency than one of its components, the same listeners were sensitive to this relation. They could perceive a pitch shift in the corresponding direction. Thus, it is possible to perceive a shift in a nonperceived frequency/pitch. This paradoxical phenomenon provides psychophysical evidence for the existence of automatic "frequency-shift detectors" in the human auditory system. The data reported here suggest that such detectors operate at an early stage of auditory scene analysis but can be activated by a pair of sounds separated by a few seconds.     

Consequences of cochlear damage for the detection of interaural phase differences

Thresholds for detecting interaural phase differences (IPDs) in sinusoidally amplitude-modulated pure tones were measured in seven normal-hearing listeners and nine listeners with bilaterally symmetric hearing losses of cochlear origin. The IPDs were imposed either on the carrier signal alone-not the amplitude modulation-or vice versa. The carrier frequency was 250, 500, or 1000 Hz, the modulation frequency 20 or 50 Hz, and the sound pressure level was fixed at 75 dB. A three-interval two-alternative forced choice paradigm was used. For each type of IPD (carrier or modulation), thresholds were on average higher for the hearing-impaired than for the normal listeners. However, the impaired listeners' detection deficit was markedly larger for carrier IPDs than for modulation IPDs. This was not predictable from the effect of hearing loss on the sensation level of the stimuli since, for normal listeners, large reductions of sensation level appeared to be more deleterious to the detection of modulation IPDs than to the detection of carrier IPDs. The results support the idea that one consequence of cochlear damage is a deterioration in the perceptual sensitivity to the temporal fine structure of sounds.     

Experimental investigation of amplitude and phase quantum correlations in a type II optical parametric oscillator above threshold: from nondegenerate to degenerate operation

We describe a stable type II optical parametric oscillator operated above threshold that provides 9.7 +/- 0.5 dB (89%) of quantum noise reduction on the intensity difference of the signal and idler modes. We also report the first experimental study, to our knowledge, by homodyne detection of the generated bright two-mode state in the case of frequency-degenerate operation obtained by the introduction of a birefringent plate inside an optical cavity.