Supramolecular Luminescent Lanthanide Dimers for Fluoride Sequestering and Sensing

Lanthanide complexes (Ln=Eu, Tb, and Yb) that are based on a C₂‐symmetric cyclen scaffold were prepared and characterized. The addition of fluoride anions to aqueous solutions of the complexes resulted in the formation of dinuclear supramolecular compounds in which the anion is confined into the cavity that is formed by the two complexes. The supramolecular assembly process was monitored by UV/Vis absorption, luminescence, and NMR spectroscopy and high‐resolution mass spectrometry. The X‐ray crystal structure of the europium dimer revealed that the architecture of the scaffold is stabilized by synergistic effects of the Eu? F? Eu bridging motive, π stacking interactions, and a four‐component hydrogen‐bonding network, which control the assembly of the two [EuL] entities around the fluoride ion. The strong association in water allowed for the luminescence sensing of fluoride down to a detection limit of 24 nM .     

The adsorption of a substituted benzene,the ethynyl-trifluoro-toluene on Si(100)-2 × 1

The adsorption of 3-ethynyl-trifluoro-toluene (ETFT) on Si(100)-2 × 1 surface in ultra high vacuum is studied in the low coverage regime, through a joint experimental and theoretical approach. The STM images of both filled and empty states revealed few distinct adsorption configurations. On the basis of Density Functional Theory (DFT) calculations the STM images were simulated and three main adsorption configurations were identified, with a predominance of di-sigma bonded species that leave the benzene ring unreacted. A discussion of the reactivity of the reconstructed silicon surface towards benzene derivatives is proposed by comparing the adsorption of ETFT close related molecules, like styrene and phenylacetylene.     

Improved and isotropic resolution in tomographic diffractive microscopy combining sample and illumination rotation

Tomographic Diffractive Microscopy is a technique, which permits to image transparent living specimens in three dimensions without staining. It is commonly implemented in two configurations, by either rotating the sample illumination keeping the specimen fixed, or by rotating the sample using a fixed illumination. Under the first-order Born approximation, the volume of the frequency domain that can be mapped with the rotating illumination method has the shape of a “doughnut”, which exhibits a so-called “missing cone” of non-captured frequencies, responsible for the strong resolution anisotropy characteristic of transmission microscopes. When rotating the sample, the resolution is almost isotropic, but the set of captured frequencies still exhibits a missing part, the shape of which resembles that of an apple core. Furthermore, its maximal extension is reduced compared to tomography with rotating illumination. We propose various configurations for tomographic diffractive microscopy, which combine both approaches, and aim at obtaining a high and isotropic resolution. We illustrate with simulations the expected imaging performances of these configurations.     

Homo- and heteronuclear 2D NMR approaches to analyse a mixture of deuterated unlike/like stereoisomers using weakly ordering chiral liquid crystals

We describe several homo- and heteronuclear 2D NMR strategies dedicated to the analysis of anisotropic (2)H spectra of a mixture of dideuterated unlike/like stereoisomers with two remote stereogenic centers, using weakly orienting chiral liquid crystals. To this end, we propose various 2D correlation experiments, denoted "D(H)(n)D" or "D(H)(n)C" (with n=1, 2), that involve two heteronuclear polarization transfers of INEPT-type with one or two proton relays. The analytical expressions of correlation signals for four pulse sequences reported here were calculated using the product-operators formalism for spin I=1 and S=1/2. The features and advantages of each scheme are presented and discussed. The efficiency of these 2D sequences is illustrated using various deuterated model molecules, dissolved in organic solutions of polypeptides made of poly-gamma-benzyl-L-glutamate (PBLG) or poly-epsilon-carbobenzyloxy-L-lysine (PCBLL) and NMR numerical simulations.     

The ALTO project at IPN-Orsay

The availability of both a tandem deuteron beam and a linac electron beam, the latter converted into Bremsstrahlung, at the new ALTO facility at IPN-Orsay offers a unique opportunity to compare the performance of a laser ion guide under different regimes. The ALTO accelerator has delivered its first electron beam at the end of 2005 and a design for a gas-cell prototype is being studied.     

High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique

We present optical characterization and laser results achieved with single-crystal fibers directly grown by the micro-pulling-down technique. We investigate the spectroscopic and optical quality of the fiber, and we present the first laser results. We achieved a cw laser power of 10 W at 1064 nm for an incident pump power of 60 W at 808 nm and 360 kW peak power for 12 ns pulses at 1 kHz in the Q-switched regime. It is, to the best of our knowledge, the highest laser power ever achieved with directly grown single-crystal fibers.     

High-speed horizontal-path atmospheric turbulence correction with a large-actuator-number microelectromechanical system spatial light modulator in an interferometric phase-conjugation engine

Results of atmospheric propagation for a high-speed, large-actuator-number adaptive optics system are presented. The system uses a microelectromechanical system- (MEMS-) based spatial light modulator correction device with 1024 actuators. Tests over a 1.35-km path achieved correction speeds in excess of 800 Hz and Strehl ratios close to 0.5. The wave-front sensor was based on a quadrature interferometer that directly measures phase. This technique does not require global wave-front reconstruction, making it relatively insensitive to scintillation and phase residues. The results demonstrate the potential of large-actuator-number MEMS-based spatial light modulators to replace conventional deformable mirrors.     

Covalent Grafting of BPin functions on Carbon Nanotubes and Chan–Lam–Evans Post-Functionalization

The chemical functionalization of carbon nanotubes is often a prerequisite prior to their use in various applications. The covalent grafting of 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (BPin) functional groups directly on the surface of multi- and single-walled carbon nanotubes, activated by nucleophilic addition of nBuLi, was carried out. Thermogravimetric analysis (TGA) coupled with mass spectrometry, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ions mass spectrometry (ToF-SIMS) confirmed the efficiency of this methodology and proved the integrity and covalent grafting of the BPin functional groups. These groups were further reacted with various nucleophiles in the presence of a copper(II) source in the conditions of the aerobic Chan–Lam–Evans coupling. The resulting materials were characterized by TGA, XPS and ToF-SIMS. This route is efficient, reliable and among the scarce reactions that enable the direct grafting of heteroatoms at carbonaceous material surfaces.