Utilisation of CO2 as “Structure Modifier” of Inorganic Solids

Utilisation of CO₂ as a chemical reagent is challenging, due to the molecule's inherent chemical stability. However, CO₂ reacts promptly at high temperature (∼1000 °C) with alkaline-earth oxides to form carbonates and such reactions are used towards capture and re-utilisation. In this work, this concept is extended and CO₂ is utilised as a reagent to modify the crystal structure of mixed-metal inorganic solids. Modification of the crystal structure is a “tool” used by materials scientists to tailor the physical property of solids. CO₂ gas was reacted with several isostructural mixed-metal oxides Sr₂CuO₃, Sr_1.8Ba_0.2CuO₃ and Ba₂PdO₃. These oxides are carefully selected to show anion vacancies in their crystal structure, to act as host sites for CO₂ molecules, leading to the formation of carbonate anions, (CO₃)²⁻. The corresponding oxide carbonates were formed successfully and the favourable formation of SrCO₃ as secondary phase was minimised via an innovative, yet simple synthetic procedure involving alternating of CO₂ and air. We also derived a simple model to predict the kinetics of the reactions for the cuprates, using first-principles density functional theory and assimilating the reaction to a gas-surface process.     

Theoretical study of the second-order nonlinear optical properties of [N]helicenes and [N]phenylenes

The second-order nonlinear optical properties of helicenes and phenylenes have been theoretically investigated at the time-dependent Hartree-Fock level using the Austin model 1 semiempirical Hamiltonian. Both the antisymmetric isotropic component of the first hyperpolarizability (beta) and its projection on the dipole moment (beta(parallel)) have been determined for increasingly large helical systems as well as for their analogs substituted by donor/acceptor pairs. It is found that (i) in nonsubstituted helicenes and phenylenes, beta increases monotonically with the size of the system and slightly depends on the nature of the helix; (ii) the corresponding beta(parallel) is mostly determined by the radial component of the first hyperpolarizability vector; (iii) in helicenes, beta(parallel) is positive and presents quasiperiodic oscillations with the helix; (iv) in phenylenes, beta(parallel) depends upon the size of the helix and it can be either positive or negative as a result of the differences in evolution with N of the radial components of the dipole moment and first hyperpolarizability. Substituting the helicenes and phenylenes by the prototypical NH2/NO2 donor/acceptor pair provides a diversity of effects on beta and beta(parallel) that encompasses decrease, increase, and change in sign.     

Tunable single-mode fiber-VCSEL using an intracavity polymer microlens

We report a tunable, single-mode vertical cavity surface-emitting laser (VCSEL) format suitable for array operation, power scaling, fiber coupling, and operation in isolated environments such as those required by atom optics. The devices are fiber VCSELs, consisting of a semiconductor gain and mirror structure separated from a mirror-coated optical fiber by an air (or vacuum) gap. The gain structure has polymer microlenses fabricated on its surface, of characteristics suitable to focus the oscillating mode on both cavity mirrors, ensuring stable fundamental mode emission and high fiber coupling efficiency. We demonstrate such devices in continuous-wave operation at 1.03 microm at room temperature, with a single-mode tuning range of 13 nm, laser threshold as low as 2.5 mW, and a maximum fiber-coupled output power of 10 mW.     

Multi-grams scale purification of xanthanolides from Xanthium macrocarpum. Centrifugal partition chromatography versus silica gel chromatography

Plants of the Asteraceae family are known as a source of sesquiterpene lactones with interesting biological activities. The purification of several xanthanolides (xanthathin, 4-epi-xanthanol and 4-epi-isoxanthanol) was realized in one step, directly from the crude chloroformic extract of the leaves of X. macrocarpum by silica gel chromatography and for the first time by liquid/liquid chromatography (counter-current chromatography/centrifugal partition chromatography), using a FCPC 5L (Fast centrifugal partition chromatograph, Kromaton Technologies, Angers, France). Recovery, purity of xanthathin and solvent consumption were improved with the liquid/liquid chromatography compared to solid/liquid chromatography.     

Salting-out effect induced by temperature cycling on a water/nonionic surfactant/oil system

This paper presents original effects induced by temperature cycling on the transitional phase inversion of emulsions, stabilized by a nonionic polyethoxylated C18E6 surfactant model. The phase inversion follow-up is performed by electrical conductivity measurements, which involves focusing the study on the shape and location of the emulsion inversion region. In that way, new observations are brought out as a gradual evolution of the emulsion inversion along the cycling process. Two alternative approaches are considered for tackling these results: (i) first, a molecular approach regarding the particular organization and rearrangement of water clusters surrounding the surfactant polymer polar head, and (ii) second, a thermodynamic approach only considering the whole Gibbs free energy of the system. The volumic approaches are transposed, here, to the water/oil interface, and disclose that the phase inversion zone is included in a metastable region, able to stabilize for a given temperature, either metastable O/W emulsions or stable W/O ones. In that way, this study proposes novel and complementary insights into the phenomena governing the emulsion phase inversion.     

Asymmetric amplification in catalysis by trans-1,2-diaminocyclohexane bistriflamide

A strong asymmetric amplification is observed in the addition of diethylzinc on aromatic aldehydes in the presence of the bistriflamide of trans-1,2-diaminocyclohexane 3a. The asymmetric amplification originates from the insolubility of the catalyst precursor 3a of low enantiomeric excess (ee), with a concomitant large increase of ee for the minor soluble part of 3a. Controlled mono-N-acetylation of 3a (20% ee) at -78 degrees C allowed isolation of 4 possessing 90% ee. [reaction: see text].