An experimental study of non-isothermal miscible displacements in a Hele-Shaw cell

Non-isothermal miscible displacements in a radial Hele-Shaw cell were experimentally investigated using a scheme in which room temperature liquids of relatively high viscosity were displaced by high-temperature (80 °C), less-viscous liquids. Fundamental characteristics have been presented regarding how the effect of a non-isothermal field on miscible displacement patterns varies in terms of factors such as the viscosity ratio of the more- and less-viscous liquids at 20 °C, M₂₀, the rate of an increase in the pattern’s area, R, and the gap width of the cell, b. The concept of area density was used to quantitatively evaluate the effect of the non-isothermal fields on the patterns. We have found that the effect of the non-isothermal field on the patterns does not monotonically vary with M₂₀ and b. In contrast, it increases with R in the present experimental condition. The experimental results can be explained by introducing an assumption in which heat is transferred mainly to the plates of the cell, in other words, the temperature of the more-viscous liquid remains constant, whereas that of the less-viscous liquid spatiotemporally decreases and the viscosity of it increases along with the temperature decrease. Visualization of non-isothermal field in the cell has been done by means of a thermo sheet and the results support the assumption mentioned above.     

Conversion of MT-sulfone to a trifluoromethyl group by IF5: the application of an MT-sulfone anion as a trifluoromethyl anion equivalent

An MT-sulfone group was converted to a trifluoromethyl group by treatment with IF(5) after an alkylation reaction. Therefore, an MT-sulfone anion can be used as a trifluoromethyl anion equivalent. The formal asymmetric Michael-addition of a trifluoromethyl anion to crotonaldehyde was also performed.     

Chiral ionic liquid-mediated photochirogenesis. Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid

Enantiodifferentiating photocyclodimerization of 2-anthracenecarboxylic acid (AC-H) and its lithium salt (AC-Li) in chiral ionic liquid (CIL), (R)-1-(2,3-dihydroxypropyl)-3-methylimidazolium acetate {[(R)-GLYMI][AcO]}, gave a mixture of two head-to-tail (HT) and two head-to-head (HH) cyclodimers in HT/HH ratios of 1.3-1.7 (for AC-H) and 2.2-4.3 (for AC-Li) with low enantiomeric excesses (ee) of 0-3% for chiral syn-HT and anti-HH dimers. In contrast, irradiation of AC-H in an aqueous solution, containing cucurbit[8]uril (CB[8]) as a host and [(R)-GLYMI][AcO] or [(R)-GLYMI][Tf(2)N] as a modifier of CB portals, afforded the HH dimers in 91-99% selectivity, although the anti-HH dimer was totally racemic. Interestingly, irradiation of AC-H in a dichloromethane solution, containing [(R)-GLYMI][AcO] as a chiral template, led to the formation of the HH-dimers in 98% selectivity with chiral anti-HH dimer in -14% ee, presumably by the dual ligation of two ACs to a CIL through electrostatic and hydrogen-bonding interactions.     

Dual supramolecular photochirogenesis: ultimate stereocontrol of photocyclodimerization by a chiral scaffold and confining host

In contrast to the brilliant success in thermal asymmetric synthesis, precise stereocontrol remains a great challenge in chiral photochemistry because of the lack of effective tools and methodologies for controlling the short-lived, weakly interacting, and highly reactive electronically excited species. In this work, we achieved this goal through the "dual-chiral, dual-supramolecular" photochirogenesis approach, which enabled us to realized dramatic acceleration and perfect stereocontrol in one of the most representative photoreactions. Thus, the [4 + 4] photocyclodimerization of 2-anthracenecarboxylate tethered to an α-cyclodextrin scaffold was accelerated by a γ-cyclodextrin or cucurbit[8]uril host and gave a single enantiomeric cyclodimer (out of four possible chiral and achiral stereoisomers) in up to 98% chemical and 99% optical yield.     

Single-site- and single-atom-resolved measurement of correlation functions

Correlation functions play an important role for the theoretical and experimental characterization of many-body systems. In solid-state systems, they are usually determined through scattering experiments, whereas in cold gases systems, time-of-flight, and in situ absorption imaging are the standard observation techniques. However, none of these methods allow the in situ detection of spatially resolved correlation functions at the single-particle level. Here, we give a more detailed account of recent advances in the detection of correlation functions using in situ fluorescence imaging of ultracold bosonic atoms in an optical lattice. This method yields single-site- and single-atom-resolved images of the lattice gas in a single experimental run, thus gaining direct access to fluctuations in the many-body system. As a consequence, the detection of correlation functions between an arbitrary set of lattice sites is possible. This enables not only the detection of two-site correlation functions but also the evaluation of non-local correlations, which originate from an extended region of the system and are used for the characterization of quantum phases that do not possess (quasi-)long-range order in the traditional sense.     

Recent Progress and Results of LEPS, LEPS2, and ELPH

Hadron photoproduction reactions are complementarily studied at SPring-8/LEPS and ELPH, Tohoku University. Their recent results on hadron structure and interaction are summarized in the present article. On the pentaquark candidate Θ⁺, a clear peak structure is seen in new exclusive analyses using increased statistics data of the γ d→K⁺K^?X reaction. A new project LEPS2 has started at SPring-8 in conjunction with LEPS and ELPH. Recent progress is discussed including a new photon detector system BGO-EGG, which is under construction at ELPH. LEPS2 beam commissioning will start from the end of FY2012.     

Hydrogen Isotope Absorption in Unary Oxides and Nitrides with Anion Vacancies and Substitution

The absorption states of hydrogen isotopes in various ceramic materials were investigated by density functional theory. For pristine ceramic materials, main-group oxides do not form any bond with a hydrogen atom. However, transition metal oxides form hydroxyl groups and absorb hydrogen atoms. Main-group and transition metal nitrides form ionic bonds between a hydrogen atom and the surrounded cation. For anion-deficient ceramic materials, hydrogen atoms are negatively charged because of excess electrons induced by anion vacancies, and ionic bonds form with the surrounded cation, which stabilizes the hydrogen absorption state. N substitutional doping into oxides introduces an electron hole, while O substitutional doping into the nitrides introduces an excess of electrons. Therefore, hydrogen isotopes form covalent bonds in N-substituted oxides, and form hydride ions in O-substituted nitrides. Thus, Al₂O₃, SiO₂, CrN, and TiN are promising materials as hydrogen permeation barriers.     

Hydrostatic Pressure on Toroidal Interaction and Propeller Chirality of Hexaarylbenzenes: Explicit Solvent Effects on Differential Volumes in Methylcyclohexane and Hexane

A unique and effective interaction between the peripheral aromatic blades makes hexaarylbenzenes (HABs) attractive in fundamental research as well as for various applications such as molecular wires, sensors, and supramolecular assemblies. The chiroptical responses of HABs are susceptible to environmental factors such as solvent and temperature owing to the dynamic conformational transitions between the conformers. In this study, pressure dependence on the propeller chiral HABs in two different solvents was studied in detail. The effective differential volumes for two different equilibria were determined by quantitative analyses of CD spectra, affording very large differential volumes from the propeller to toroidal conformer (ΔV_T-C) of +43 and +42 cm³ mol⁻¹, for H2 and H6 , respectively, in methylcyclohexane. The value of H6 was further enhanced to +72 cm³ mol⁻¹ in hexane, the largest value for the typical unimolecular conformational change. Such a response of propeller chirality in HABs is expedient in designing more advanced piezo-sensitive materials.     

Sr substitution effects on atomic and local electronic structure of Ca2AlMnO5+δ

We performed the first-principle calculations based on spin-polarized density functional theory to investigate the Sr substitution effects on the atomic and local electronic structure of Ca₂AlMnO_5+δ. The ionic radius of Sr²⁺ is larger than that of Ca²⁺; thus, the lattice expansion occurs with Sr substitution. From the total energy calculations, we found that Sr substitution makes the oxygen-absorbed phase unstable and realizes the lower operation temperature. From the point of atomic structure, Sr substitution lengthens the bond length between Mn and O atoms connecting Mn and Al atoms in Al tetrahedral (O_Mn-Alt) in oxygen-absorbed phase, because the large Sr²⁺ prevents the release of the Jahn-Teller distortion. We also found that the covalent bonding between Mn and O_Mn-Alt atoms weaken with Sr substitution by the local electronic structure analysis, which results in the unstable oxygen-absorbed phase and weak prepeak and main peak intensity near the onset of O-K edge ELNES of O_Mn-Alt atoms.     

Synthesis and crystallographic studies of garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

High-purity powder specimens of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ have been successfully synthesized by solid-state chemical reaction. The Rietveld refinements from X-ray powder diffraction data verified that these compounds have the garnet-type structure (space group , No. 230) with the lattice constant of a=12.596(2) Å for AgCa₂Mn₂V₃O₁₂ and a=12.876(2) Å for NaPb₂Mn₂V₃O₁₂. Calculation of the bond valence sum supported that Mn is divalent and V is pentavalent in these garnets. Estimation of the quadratic elongation and the bond angle variance showed that the distortions of the MnO₆ octahedra and the VO₄ tetrahedra are significantly suppressed. Our new results of AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ are compared to those of AgCa₂M₂V₃O₁₂ and NaPb₂M₂V₃O₁₂ (M=Mg, Co, Ni, Zn).