Composition and plasticizing effect of poly(carboxylic acid) complexes with amino compounds

Poly(carboxylic acid)-dimethylalkylamine complexes were prepared and examined by various methods including infrared spectrometry and chemical titrations. FTIR measurements provided some of the most complete and detailed insights into the type and the stoichiometry of the acid-base complexes. A (1:1) stoichiometric complexation of the poly(carboxylic acid) with tertiary amines was involved in protic solvents. A threshold degree of complexation of 42% was obtained in such a macromolecular system. The equilibrium constant of the proton transfer reaction K was estimated to be independent on the alkyl chain length of the base reagent. Besides the formation of the acid-base complexes, a plasticizing effect of the amine derivatives was demonstrated by differential calorimetry. A T_g depression could be both attributed to the amine molecules linked to the polymer backbone via ionic bonds and to the free molecules dissolved within the free volume of the polymer.     

Hyperfine coupling constants of β-phosphorylated nitroxides: Subtle interplay between steric strain,hyperconjugation, and dipole-dipole interactions

Solvent effects in β-phosphorylated nitroxides show that nitrogen and phosphorus hyperfine coupling constants a_N and a_P, increase and decrease with increasing polarity, polarizity, and Hydrogen Bond Donor effects of solvents, respectively. In a series of articles, it was shown that the driving interaction controlling the change in a_P is the maximization of the N^+?—O^– … ???⁺PO^– dipole – dipole interaction. In this work, we show that the steric strain in spiro β-phosphorylated nitroxides affords the opposite trend for a_P, that is, a_P increases with increasing solvent properties features.     

Quantum repeaters with photon pair sources and multimode memories

We propose a quantum repeater protocol which builds on the well-known Duan-Lukin-Cirac-Zoller (DLCZ) protocol [L. M. Duan, M. D. Lukin, J. I. Cirac, and P. Zoller, Nature (London) 414, 413 (2001)10.1038/35106500], but which uses photon pair sources in combination with memories that allow to store a large number of temporal modes. We suggest to realize such multimode memories based on the principle of photon echo, using solids doped with rare-earth-metal ions. The use of multimode memories promises a speedup in entanglement generation by several orders of magnitude and a significant reduction in stability requirements compared to the DLCZ protocol.     

Slippery or sticky boundary conditions: control of wrinkling in metal-capped thin polymer films by selective adhesion to substrates

Wrinkling patterns at the metallized surface of thin polymer films are shown to be sensitive to the sticky or slippery character of the polymer-substrate interface. Existing theoretical models were expanded to specific boundary conditions (adhesive versus slippery) in order to rationalize these observations. Based on this concept, we were able to propose a new and simple method to orient the wrinkles by chemically patterning the substrate with regions of high and low adhesion.     

Photonic crystal nanocavities in GaAs/AlGaAs with oxidised bottom cladding

We present a solution to the difficult task of removing an oxide-based hard mask from a photonic crystal fabricated in the GaAs/AlGaAs system. We use a polymer backfill technique to seal the AlGaAs layer, thereby making it inaccessible to the wet-etch solution. This allows us to use a GaAs active layer for the photonic crystal placed on an oxidised AlGaAs layer which provides mechanical and thermal support. Using this technique, we fabricated GaAs-based photonic crystal cavities and measured respectable quality factors (Q ≈ 2200) despite the intrinsic asymmetry of the system. The technique presents a viable method for producing electrically injected photonic crystal cavities for operation on a mechanically stable and thermally conducting buffer layer.     

Challenge in the speciation of nitrogen-containing compounds in heavy petroleum fractions by high temperature comprehensive two-dimensional gas chromatography

Extending the knowledge related to nitrogen-containing compounds presents an important interest for the petroleum industry due to their implication in atmosphere pollution as well as their inhibitive or refractive behaviour towards hydroprocessing. Most of the nitrogenated species are concentrated in heavy petroleum cuts. As no analytical method is resolutive enough for these heavy cuts, particularly regarding nitrogen-containing compounds, a new approach is needed. For this reason, this study focuses on the development of a GC×GC technique, through the hyphenation of a specific NCD detector with a GC×GC system at high temperature. The performances of highly polar thermally stable stationary phases, in particular those composed of promising ionic liquids, were monitored in normal and reversed configurations. Subsequently, after the extraction of neutral or basic compounds by adsorption on an ion-exchange resin, a first quantitative determination was attempted for a straight-run and a direct coal liquefaction vacuum gas oils. This study led to a better understanding of the behaviour of highly aromatic N-compounds by 2D-GC including an ionic liquid phase as well as a deeper N-characterization of heavy petroleum fractions.     

Fluorescence photobleaching to evaluate flow velocity and hydrodynamic dispersion in nanoslits

Velocity measurement is a key issue when studying flows below the micron scale, due to the lack of sensitivity of conventional detection techniques. We present an approach based on fluorescence photobleaching to evaluate flow velocity at the nanoscale by direct visualization. Solutions containing a fluorescent dye are injected into nanoslits. A photobleached line, created through laser beam illumination, moves through the channel due to the fluid flow. The velocity and effective diffusion coefficient are calculated from the temporal data of the line position and width respectively. The measurable velocity range is only limited by the diffusion rate of the fluorescent dye for low velocities and by the apparition of Taylor dispersion for high velocities. By controlling the pressure drop and measuring the velocity, we determine the fluid viscosity. The photobleached line spreads in time due to molecular diffusion and Taylor hydrodynamic dispersion. By taking into account the finite spatial and temporal extensions of the bleaching under flow, we determine the effective diffusion coefficient, which we find to be in good agreement with the expression of the two dimensional Taylor-Aris dispersion coefficient. Finally we analyze and discuss the role of the finite width of the rectangular slit on hydrodynamic dispersion.     

Triaryl-1,3,5-triazinane-2,4,6-triones (Isocyanurates) Peripherally Functionalized by Donor Groups: Synthesis and Study of Their Linear and Nonlinear Optical Properties

The linear optical (LO) and nonlinear optical (NLO) properties of a series of isocyanurates functionalized by donor arms at the periphery are reported herein. These octupolar derivatives were obtained in a straightforward way from commercial isocyanate derivatives and were fully characterized. Although several of these compounds are known, those that exhibited the largest NLO activities are all new compounds. In terms of second-order activity, several of these derivatives exhibit remarkable activity/transparency tradeoffs. In terms of third-order activity, the longer derivatives with the stronger donor groups (X=NH(2) , NMe(2) , or NPh(2) ) were shown to possess significant two-photon absorption cross sections. These strongly luminescent derivatives exhibit two-photon absorption cross sections up to 410?GM. DFT computations were also conducted to unravel their electronic structures and to rationalize their NLO properties. To our knowledge, the present study is the first concerned with the nonlinear optical properties of these original cyclotrimers.     

Fabrication of highly homogeneous As2Se3 glass under argon flow

The present study relates to a new method for the synthesis of As₂Se₃ glass in a controlled atmosphere. The advantage of this technique is that it does not require sealing of the silica reaction container and therefore makes it likely to substitute the current industrial batch by batch synthesis which actually needs very expensive single-use sealed silica vessels.An experimental device has been developed for these purposes. It is equipped with a stirring mechanism to homogenize the molten bath. In order to avoid contamination by oxygen and moisture, the synthesis is carried out under argon flow (pressure of 1 bar). Material losses during synthesis can be reduced to less than 2% when temperature is progressively increased up to 430 °C. Bulk glass ingots are finally obtained according to a two-step annealing process. Their chemical composition is analyzed by EDS and shows a variation range of less than 0.2%. The excellent reproducibility of the given method is also confirmed by the refractive indexes, that do not differ for more than 1 · 10⁻³ from one another.Adverse absorption bands due to oxygen do not occur in the 8-12 μm spectral region when 1000 ppm of Mg is added. As no distilling operation has been carried out until now, the magnesium oxide partially keeps staying in the glass and leads to scattering losses at short wavelengths.