Application of Rh-catalyzed cyclization to the formation of a chiral quaternary carbon

Rh-Catalyzed cyclization was applied to the formation of a chiral quaternary carbon. It has become clear that the Rh-complex can discriminate between isopropenyl and 2-isopentenyl (or isopentyl) substituents, and the cyclization afforded 3,3,4-trisubstituted cyclopentanones with a chiral quaternary carbon in a stereoselective manner. The cyclization of 4-pentenals 6a, b by an achiral neutral Rh(PPh3)3Cl afforded 3,3,4-cis-trisubstituted cyclopentanones (+/-)-7a,b in 86-96%, and the cyclization by a cationic Rh[(R)-BINAP]CIO4 afforded 3,3,4-trans-trisubstituted cyclopentanones (-)-8a, b of 82-86% ee in 88-98% yields. The mechanism of stereoselection by Rh-complexes is also discussed.     

Synthetic Control of the Excited‐State Dynamics and Circularly Polarized Luminescence of Fluorescent “Push–Pull” Tetrathia[9]helicenes

A series of fluorescent “push‐pull” tetrathia[9]helicenes based on quinoxaline (acceptor) fused with tetrathia[9]helicene (donor) derivatives was synthesized for control of the excited‐state dynamics and circularly polarized luminescence (CPL) properties. In this work, introduction of a quinoxaline onto the tetrathia[9]helicene skeleton induced the “push–pull” character, which was enhanced by further introduction of an electron‐releasing Me₂N group or an electron‐withdrawing NC group onto the quinoxaline unit (denoted as Me₂N‐QTTH and NC‐QTTH, respectively). These trends were successfully discussed in terms of by electrochemical measurements and density functional theory (DFT) calculations. As a consequence, significant enhancements in the fluorescence quantum yields (Φ_FL) were achieved. In particular, the maximum Φ_FL of Me₂N‐QTTH was 0.43 in benzene (NC‐QTTH: Φ_FL=0.30), which is more than 20 times larger than that of a pristine tetrathia[9]helicene (denoted as TTH; Φ_FL=0.02). These enhancements were also explained by kinetic discussion of the excited‐state dynamics such as fluorescence and intersystem crossing (ISC) pathways. Such significant enhancements of the Φ_FL values thus enabled us to show the excellent CPL properties. The value of anisotropy factor g_CPL (normalized difference in emission of right‐handed and left‐handed circularly polarized light) was estimated to be 3.0×10^?3 for NC‐QTTH.     

Microdischarge-Induced Decomposition of Ammonia and Reduction of Silver Ions for Formation of Two-Dimensional Network Structure

Microdischarge-induced reaction processes working at atmospheric pressure create fractal-like network structure of metal nano-particles which shows variable electric and optical properties. Due to their smallness, microdischarges or microplasmas can be installed in a gas-tubing system, and they enable us to create a compact chemical reduction reactor which includes decomposers of molecules, gas flows, and aqueous solutions with metallic ions at atmospheric pressure. Ammonia (NH₃) gas is successfully decomposed in this reactor, and its products which include mainly hydrazine (N₂H₄) and flow in the downstream induce reduction reactions for AgNO₃ solution. Various parameters in the reactor trigger formation of functional patterns of silver nano-particles like partially transparent layers whose conductivity is variable. Optical properties of this equivalent films show some absorption spectra coming from structure resonances, which can be an optical metamaterials in this self-assembly process.     

Spin-polarized electronic band structures of the Fe4N-Co4N system

We have calculated spin-polarized electronic band structures of cubic antiperovskite metal nitrides (Fe₄N, Fe₃CoN, FeCo₃N and Co₄N) by the full-potential method with mixed basis augmented plane wave plus local orbitals. It was shown that FeCo₃N has an energy gap of 0.2 eV at the Fermi level in the up-spin band and hence its half-metallic behavior is expected.     

Wavelet‐based data compression for flow simulation on block‐structured Cartesian mesh

A data compression method based on image encoding techniques is presented for a flow simulation data set. An input flow field data set is converted into the octree structure by discrete wavelet transform, and then quantized finely or coarsely depending on its importance in the flow field. Embedded zerotree wavelet encoding as the image encoding technique and entropy encoding reduce the data size by making use of the octree structure created previously. The present compression method is incorporated in a block‐structured Cartesian mesh method called Building‐Cube method. The Building‐Cube method gives not only good performance in the flow simulation but also consistency with the embedded zerotree wavelet encoding in the data compression. Three compression cases for incompressible and compressible flow simulations, including a large‐scale simulation with O(10 ⁸) mesh points, demonstrate that the present compression method gives both high compression ratios and good qualities of compressed data. Copyright © 2013 John Wiley & Sons, Ltd.     

Highly polarized very cold neutrons through a permanent magnet quadrupole

We obtained highly polarized very cold neutrons through a quadrupole magnet with a large aperture. When neutrons go through a quadrupole magnet, parallel-spin neutrons are attracted to the magnet axis and anti-parallel-spin neutrons are repelled off the axis. Therefore, the neutrons through a sufficiently long quadrupole magnet have completely parallel-spin. At the downstream of the quadrupole magnet, we placed another quadrupole magnet to divide neutrons into two regions depending on their spin directions. We obtained the neutron polarization from the integrated count of the two regions and found it was 99.88±0.09 (stat.)±0.05 (syst.)%.     

Monte Carlo Simulation Study on Domain Formation in the Photoinduced Low-Spin High-Spin Transition

The domain formation process of the photo-induced cooperative low-spin (LS) to high-spin (HS) conversion phenomena are studied based on the Monte Carlo simulation method. The existence of the threshold light intensity and the incubation period are demonstrated. It is pointed out that the nucleation barrier of HS domain is surmounted by the fluctuation caused by the repetition of excitation and de-excitation. By defining an effective temperature for this fluctuation, the time scale of incubation period is estimated following the usual domain formation theory. It grossly accounts the Monte Carlo (MC) results in three-dimensional cases. The phase separation of HS and LS domain is reproduced by considering the volume striction effect. The step wise abrupt conversion is ascribed to the de-pinning of the volume striction.