Drop Size Distribution Bimodality and Its Effect on O/W Emulsion Viscosity

The research work on why and how distribution bimodality tends to reduce the viscosity of a particulate suspension is reviewed. The transfer of the corresponding concepts to emulsions requires some statistical tools, and becomes particularly easy with probability scale plotting which is reviewed. Viscosity reduction can be attained for different kinds of fine and coarse emulsion associations. The results are shown to depend on the characteristics of the base emulsions as well as on the way they are mixed.     

Chiral Fluorinated α‐Sulfonyl Carbanions: Enantioselective Synthesis and Electrophilic Capture,Racemization Dynamics,and Structure

Enantiomerically pure triflones R¹CH(R²)SO₂CF₃ have been synthesized starting from the corresponding chiral alcohols via thiols and trifluoromethylsulfanes. Key steps of the syntheses of the sulfanes are the photochemical trifluoromethylation of the thiols with CF₃Hal (Hal=halide) or substitution of alkoxyphosphinediamines with CF₃SSCF₃. The deprotonation of RCH(Me)SO₂CF₃ (R=CH₂Ph, iHex) with nBuLi with the formation of salts [RC(Me)? SO₂CF₃]Li and their electrophilic capture both occurred with high enantioselectivities. Displacement of the SO₂CF₃ group of (S)‐MeOCH₂C(Me)(CH₂Ph)SO₂CF₃ (95 % ee) by an ethyl group through the reaction with AlEt₃ gave alkane MeOCH₂C(Me)(CH₂Ph)Et of 96 % ee. Racemization of salts [R¹C(R²)SO₂CF₃]Li follows first‐order kinetics and is mainly an enthalpic process with small negative activation entropy as revealed by polarimetry and dynamic NMR (DNMR) spectroscopy. This is in accordance with a C_α? S bond rotation as the rate‐determining step. Lithium α‐(S)‐trifluoromethyl‐ and α‐(S)‐nonafluorobutylsulfonyl carbanion salts have a much higher racemization barrier than the corresponding α‐(S)‐tert‐butylsulfonyl carbanion salts. Whereas [PhCH₂C(Me)SO₂tBu]Li/DMPU (DMPU = dimethylpropylurea) has a half‐life of racemization at ?105 °C of 2.4 h, that of [PhCH₂C(Me)SO₂CF₃]Li at ?78 °C is 30 d. DNMR spectroscopy of amides (PhCH₂)₂NSO₂CF₃ and (PhCH₂)N(Ph)SO₂CF₃ gave N? S rotational barriers that seem to be distinctly higher than those of nonfluorinated sulfonamides. NMR spectroscopy of [PhCH₂C(Ph)SO₂R]M (M=Li, K, NBu₄; R=CF₃, tBu) shows for both salts a confinement of the negative charge mainly to the C_α atom and a significant benzylic stabilization that is weaker in the trifluoromethylsulfonyl carbanion. According to crystal structure analyses, the carbanions of salts {[PhCH₂C(Ph)SO₂CF₃]Li? L }₂ ( L =2 THF, tetramethylethylenediamine (TMEDA)) and [PhCH₂C(Ph)SO₂CF₃]NBu₄ have the typical chiral C_α? S conformation of α‐sulfonyl carbanions, planar C_α atoms, and short C_α? S bonds. Ab initio calculations of [MeC(Ph)SO₂tBu]^? and [MeC(Ph)SO₂CF₃]^? showed for the fluorinated carbanion stronger n_C→σ* and n_O→σ* interactions and a weaker benzylic stabilization. According to natural bond orbital (NBO) calculations of [R¹C(R²)SO₂R]^? (R=tBu, CF₃) the n_C→σ*_{S? R} interaction is much stronger for R=CF₃. Ab initio calculations gave for [MeC(Ph)SO₂tBu]Li ? 2 Me₂O an O,Li,C_α contact ion pair (CIP) and for [MeC(Ph)SO₂CF₃]Li ? 2 Me₂O an O,Li,O CIP. According to cryoscopy, [PhCH₂C(Ph)SO₂CF₃]Li, [iHexC(Me)SO₂CF₃]Li, and [PhCH₂C(Ph)SO₂CF₃]NBu₄ predominantly form monomers in tetrahydrofuran (THF) at ?108 °C. The NMR spectroscopic data of salts [R¹(R²)SO₂R³]Li (R³=tBu, CF₃) indicate that the dominating monomeric CIPs are devoid of C_α? Li bonds.     

Highly dispersive large mode area photonic bandgap fiber

An all-silica photonic bandgap fiber composed of a low-index core surrounded by alternating high- and low-index rings allows us to achieve a large mode area (500 microm(2)) and large chromatic dispersion. Sharp resonances from the even Bragg mode to odd ring modes theoretically lead to 20,000 ps/(nm km) chromatic dispersion when large bends are applied. By nature, sharp resonances are sensitive to inhomogeneities along the fiber length. Under experimental conditions, the resonances are broadened and the dispersion coefficient is decreased to 1000 ps/(nm km). However, to the best of our knowledge, this is the largest dispersion coefficient reported using a large mode area fiber.     

Q-switched Yb-doped nonlinear microstructured fiber laser for the emission of broadband spectrum

We report on an innovative configuration of a supercontinuum laser based on an Yb-doped nonlinear microstructured fiber. Due to this particular fiber design combining amplification and nonlinear properties, a wideband output spectrum is generated in the fiber under the Q-switched regime. By exploiting stimulated Brillouin scattering, high peak power pulses are achieved and contribute to a spectral broadening due to a nonlinear wavelength conversion process. Both infrared (1000-1200 nm) and visible (650-750 nm) spectra are generated with an average power of 200 mW.     

Evidence of wave front folding of sonic booms by a laboratory-scale deterministic experiment of shock waves in a heterogeneous medium

The influence of the planetary boundary layer on the sonic boom received at the ground level is known since the 1960s to be of major importance. Sonic boom propagation in a turbulent medium is characterized by an increase of the mean rise time and a huge variability. An experiment is conducted at a 1:100,000 scale in water to investigate ultrasonic shock wave interaction with a single heterogeneity. The experiment shows a very good scaling with sonic boom, concerning the size of the heterogeneities, the wave amplitude, and the rise time of the incident wave. The wave front folding associated with local focusing, and its link to the increase of the rise time, are evidenced by the experiment. The observed amplification of the peak pressure (by a factor up to 2), and increase of the rise time (by up to about one magnitude order), are in qualitative agreement with sonic boom observations. A nonlinear parabolic model is compared favorably to the experiment on axis, though the paraxial approximation turns out less precise off axis. Simulations are finally used to discriminate between nonlinear and linear propagations, showing nonlinearities affect mostly the higher harmonics that are in the audible range for sonic booms.     

SURFACTANT-OIL-WATER SYSTEMS NEAR THE AFFINITY INVERSION. PART X: EMULSIONS MADE WITH ANIONIC-NONIONIC SURFACTANT MIXTURES.

Anionic and nonionic surfactants exhibit opposite changes in hydrophilicity with a change of temperature. This antagonism can be harnessed by the use of mixtures. The phase behavior and emulsion type are mapped on a temperature water-oil/ratio diagram for different anionic-nonionic mixtures. It is shown that the mixing can result in insensitivity to temperature of different kinds of emulsions.     

Shearing a glassy material: numerical tests of nonequilibrium mode-coupling approaches and experimental proposals

The predictions of a nonequilibrium schematic mode-coupling theory developed to describe the nonlinear rheology of soft glassy materials have been numerically tested in a sheared binary Lennard-Jones mixture. In this Letter, we focus on the existence, behavior, and properties of an effective temperature T(eff) for the slow modes of the fluid, as defined from a generalized fluctuation-dissipation theorem. New, simple experimental protocols to access T(eff) are proposed, and one such experiment is numerically performed. Our results give strong support to the thermodynamic interpretation of T(eff) and make it experimentally accessible in a very direct way.     

NMR studies of the chalcogen analogues of benzofuran. IV—Proton,carbon-13 and selenium-77 magnetic resonance in nitrobenzo[b]selenophenes

The ¹H, ¹³C and ⁷⁷Se chemical shifts have been measured for mononitrobenzo[ b ]selenophenes. For the homocyclic nuclei, the observed ¹H- and ¹³C-values calculated from the empirical increments of nitrobenzene. Anomalous effects are observed in the 2- and 3-substituted derivatives and the nature of the Se? NO₂ interactions in the former is discussed. ⁷⁷Se chemical shifts of the 4-, 5- and 7-nitro derivatives are approximately correlated with the CNDO calculated electron densities; they also compare well with those of selenoanisoles and other phenyl alkyl selenides. The chemical shifts are also compared with the corresponding values in other heterocycles containing a selenophene moiety.