New 1,3-dioxane type ionic liquid crystal materials having a terminal double bond

New 1,3-dioxane type ionic liquid crystal materials having a terminal double bond were synthesized. The mesomorphic behaviour of these compounds was measured. The principal features of these compounds are a smectic A phase over a very wide range including room temperature, and a low isotropic to mesophase transition temperature (for example, compound 6-1: Cr-22 SmA 25 I).     

Aerobic oxidative kinetic resolution of secondary alcohols with naphthoxide-bound iron(salan) complex

The first general method for iron-catalyzed aerobic oxidative kinetic resolution of secondary alcohols was achieved with good to high enantiomeric differentiation (k(rel) = 7-50). Although iron(salan) complex 1 does not catalyze alcohol oxidation, the naphthoxide-bound iron(salan) complex does.     

Catalytic asymmetric oxidation of cyclic dithioacetals: highly diastereo- and enantioselective synthesis of the S-oxides by a chiral aluminum(salalen) complex

Aluminum(salalen) complex 1 [salalen = half-reduced salen, salen = N,N'-ethylenebis(salicylideneiminato)] was found to be a highly efficient catalyst for asymmetric oxidation of cyclic dithioacetals in the presence of 30% hydrogen peroxide as an oxidant. In the reaction of a series of 2-substituted 1,3-dithianes bearing alkyl, alkenyl, alkynyl, and aryl groups as the substituent, the trans-monoxides were obtained in high yields with 19:1 → >20:1 dr (diastereomeric ratio) and 98-99% ee (enamtiomeric excess). The reaction of nonsubstituted 1,3-dithiane also proceeded in a highly enantioselective manner to give the monoxide with a small formation of the trans-1,3-dioxide, an overoxidation product. Five-membered 1,3-dithiolanes and seven-membered 1,3-dithiepanes also underwent oxidation to give monoxides with high diastereo- and enantioselectivity. It was found that the equilibrium between the two chairlike conformers of dithianes has relevance to the observed diastereoselectivity in the first oxidation process, and the dioxide formation in the oxidation of 1,3-dithiane and its stereochemistry also can be explained by the conformational equilibrium of the product monoxide.     

Electronic band structure of partially inverse spinel MgIn2S4 as calculated by the semiempirical pseudopotential method

The electronic band structure of the partially inverse spinel MgIn₂S₄ has been calculated on the symmetry lines ΓΛL, ΓΔX and ΓΣK by the semiempirical pseudopotential method. The general features of the band structure of MgIn₂S₄ are quite similar to those of the normal spinel CdIn₂S₄. The conduction band minimum is located at Γ and the valence band maximum is along the Σ line. The indirect energy gap (Γ_1cΣ_4v) is 2.50 eV. The effects of magnesium vacancy and variations in the cation distribution and in the parameter u are examined and shown to be small.     

Variational calculation of second-order reduced density matrices by strong N-representability conditions and an accurate semidefinite programming solver

The reduced density matrix (RDM) method, which is a variational calculation based on the second-order reduced density matrix, is applied to the ground state energies and the dipole moments for 57 different states of atoms, molecules, and to the ground state energies and the elements of 2-RDM for the Hubbard model. We explore the well-known N-representability conditions (P, Q, and G) together with the more recent and much stronger T1 and T2(') conditions. T2(') condition was recently rederived and it implies T2 condition. Using these N-representability conditions, we can usually calculate correlation energies in percentage ranging from 100% to 101%, whose accuracy is similar to CCSD(T) and even better for high spin states or anion systems where CCSD(T) fails. Highly accurate calculations are carried out by handling equality constraints and/or developing multiple precision arithmetic in the semidefinite programming (SDP) solver. Results show that handling equality constraints correctly improves the accuracy from 0.1 to 0.6 mhartree. Additionally, improvements by replacing T2 condition with T2(') condition are typically of 0.1-0.5 mhartree. The newly developed multiple precision arithmetic version of SDP solver calculates extraordinary accurate energies for the one dimensional Hubbard model and Be atom. It gives at least 16 significant digits for energies, where double precision calculations gives only two to eight digits. It also provides physically meaningful results for the Hubbard model in the high correlation limit.     

Soot particles in piston-top pool fires and exhaust at 5 and 15 MPa injection pressure in a gasoline direct-injection engine

This study shows the structure of soot particles sampled directly from wall wetting-induced pool fires formed on the piston top in a spark-ignition direct-injection (SIDI) engine. Of particular interest is its variation with injection pressure considering the current trend of high-pressure DI system development to reduce engine-out particulate emissions. Thermophoretic particle sampling was performed for transmission electron microscope (TEM) imaging, which was post-processed for statistical analysis of key morphology and internal structure parameters. These include the size distribution of soot aggregates and primary particles as well as carbon-layer fringe-to-fringe gap and concentricity. With the fixed engine speed and load conditions, in-flame soot particles are compared to the exhaust particles sampled simultaneously at selected 5 and 15 MPa injection pressures corresponding to low-speed/low-load and high-speed/high-load in practical engine operation. From the TEM images and statistical analysis, it was found that more concentrated and taller pool fire developed for 5-MPa injection leads to smaller soot aggregates composed of smaller soot primary particles due to suppressed soot growth in fuel-rich flames. However, the soot particles formed in 15-MPa injection-induced pool fires are at a more reactive status evidenced by less defined core-shell boundaries and higher fringe separation. The higher soot reactivity results in enhanced soot oxidation, which explains smaller soot aggregates and primary particles found for the 15-MPa injection in the exhaust sample.     

Isomerization of spirobenzopyrans bearing electron-donating and electron-withdrawing groups in acidic aqueous solutions

Spirobenzopyrans, which are well known as photochromic compounds, exist as thermodynamically stable protonated ring-opened isomers (protonated merocyanine form, McH) in an acidic aqueous solution in the dark. In the present study, we investigated effects of substitution of the spirobenzopyrans on a ring-opening behavior in an aqueous system. We prepared five polymerizable spirobenzopyrans that are substituted with a methoxy group or a nitro group at the 6'- or 8'-positions and without a substituent. These monomers were copolymerized with N,N-dimethylacrylamide to evaluate the spirobenzopyrans in aqueous solution. Correlation between ring-opening rates and the kind and position of the substitution can be summarized as follows: the substitution of an electron-donating methoxy group and the substitution at the 8'-position increased the ring-opening rate, whereas the substitution of an electron-withdrawing nitro group decreased the rate. The effects of the substitution can be explained by changes in the electron density of the oxygen atom of the spirobenzopyrans.     

Asymmetric olefin aziridination using a newly designed Ru(CO)(salen) complex as the catalyst

Highly enantioselective and good to high-yielding aziridination of conjugated and non-conjugated terminal olefins and cyclic olefins was achieved using a newly designed Ru(CO)(salen) complex as the catalyst in the presence of SESN(3) under mild conditions.