Enantioselective synthesis of C2-functionalized, N-protected morpholines and orthogonally N,N'-protected piperazines via organocatalysis

In this Letter, we describe a novel three-step, one-pot procedure for the enantioselective synthesis of N-benzyl protected morpholines and orthogonally N,N'-protected piperazines with chiral alkyl groups installed at the C2 position of each heterocyclic core via organocatalysis. This methodology allows for the rapid preparation of functionalized morpholines and piperazines that are not readily accessible through any other chemistry in good to excellent % ee (55-98% ee).     

Noninvasive measurement of scattering anisotropy in turbid materials by nonnormal incident illumination

Many existing methods for the recovery of optical parameters from turbid materials rely on the diffusion approximation, which does not permit the recovery of the degree of anisotropy in the scattering phase function. These methods also make the explicit assumption that light is normally incident at the top surface of the material. We demonstrate a steady-state imaging technique that uses nonnormally incident light to determine anisotropy parameter g by fitting Monte Carlo simulation results to high dynamic range images of the intensity profiles of samples. The proposed method is simpler than existing methods and does not rely on thin samples to produce reasonable results.     

High-temperature measurements of the rates of the reactions CH2O + Ar → Products and CH2O + O2 → Products

The two-channel thermal decomposition of formaldehyde [CH₂O], (1a) CH₂O + Ar → HCO + H + Ar, and (1b) CH₂O + Ar → H₂ + CO + Ar, was studied in shock tube experiments in the 2258-2687 K temperature range, at an average total pressure of 1.6 atm. OH radicals, generated on shock heating trioxane-O₂-Ar mixtures, were monitored behind the reflected shock front using narrow-linewidth laser absorption. 1,3,5 trioxane [C₃H₆O₃] was used as the CH₂O precursor in the current experiments. H-atoms formed upon CH₂O and HCO decomposition rapidly react with O₂ to produce OH via H + O₂ → O + OH. The recorded OH time-histories show dominant sensitivity to the formaldehyde decomposition pathways. The second-order reaction rate coefficients were inferred by matching measured and modeled OH profiles behind the reflected shock. Two-parameter fits for k_1a and k_1b, applicable in this temperature range, are:

     

Hybrid improper ferroelectricity: a mechanism for controllable polarization-magnetization coupling

First-principles calculations are presented for the layered perovskite Ca3Mn2O7. The results reveal a rich set of coupled structural, magnetic, and polar domains in which oxygen octahedron rotations induce ferroelectricity, magnetoelectricity, and weak ferromagnetism. The key point is that the rotation distortion is a combination of two nonpolar modes with different symmetries. We use the term "hybrid" improper ferroelectricity to describe this phenomenon and discuss how control over magnetism is achieved through these functional antiferrodistortive octahedron rotations.     

Thermal diffusion shock waves

The Ludwig-Soret effect or thermal diffusion, which refers to the separation of liquid mixtures in a temperature gradient, is governed by a nonlinear, partial differential equation in space and time. It is shown here that the solution to the nonlinear differential equation for a binary mixture predicts the existence of shock waves completely analogous to fluid shocks and obeys an expression for the shock velocity that is an exact analogue of the Rankine-Hugoniot relations. Direct measurements of the time dependent, spatial absorption profile of a suspension of nanometer sized particles subjected to a sinusoidal temperature field generated by a pair of continuous laser beams, as well as self-diffraction experiments, show motion of the particles in agreement with the predictions of nonlinear theory.     

Enhanced infrared transmission through subwavelength coaxial metallic arrays

We report the observation of enhanced near-infrared transmission through arrays of subwavelength coaxial metallic structures compared with that through comparable diameter hole arrays as a result of localized electromagnetic modes supported by the complex coaxial unit cell. Polarization and angle-dependent transmission measurements clearly demonstrate the coupling between this localized mode and delocalized surface plasmon modes. A generalized, multiple discrete states Fano line shape provides a good fit to the experimental results.     

The ν4 fundamental of three isotopic species of CF4

The vibration-rotation spectra of the ν₄ fundamental of ¹²CF₄, ¹³CF₄, and ¹⁴CF₄ have been observed with 0.06 cm^?1 resolution. A least squares fit of the data has been used to evaluate the pertinent molecular constants. The band centers are 631.199, 629.285, and 627.348 cm^?1 for ¹²CF₄, ¹³CF₄, and ¹⁴CF₄, respectively. The Coriolis constant ζ₄ has been estimated for the three isotopes.