Stereospecific Synthesis of Enantiopure [6]Helicene Containing a Seven-Membered Ring and [7]Helicene by Acid-Promoted Stepwise Alkyne Annulations of Doubly Axial-Chiral Precursors**

Enantiopure [6]helicene containing an embedded seven-membered ring and carbo[7]helicene (>99 % ee) with opposite helicity were simultaneously and quantitatively (>99 %) synthesized with a perfect stereospecificity through stepwise acid-promoted intramolecular alkyne annulations of doubly axial-chiral cyclization precursors. The helical handedness of the [6]- and [7]helicenes was fully stereocontrolled by the doubly axial chirality of the precursors as a result of complete axial-to-helical chirality transfer. The cyclizations proceeded in a stepwise manner; the first six-membered ring formation was followed by the kinetically controlled seven- or six-membered ring formation with or without helix-inversion of a [4]helicene intermediate generated during the first cyclization step, thus quantitatively producing enantiopure circularly polarized luminescent [6]- and [7]helicenes with opposite helicity.     

Supported Noble Metal Catalysts and Adsorbents with Soft Lewis Acid Functions

Heterogeneous noble metal catalysts exhibit various functions. Although their redox functions have been extensively studied, we focused on their soft Lewis acid functions. Supported Au, Pt, and Pd catalysts electrophilically attack the π-electrons of soft bases such as alkynes, alkenes, and aromatic compounds to perform addition and substitution reactions. Hydroamination, intramolecular cyclization of alkynyl carboxylic acids, isomerization of allylic esters, vinyl exchange reactions, Wacker oxidation, and oxidative homocoupling of aromatics are introduced based on a discussion of the active species and reaction mechanisms. Furthermore, the adsorption of sulfur compounds, which are soft bases, onto the supported AuNPs is discussed. The adsorption and removal of 1,3-dimethyltrisulfane (DMTS), which is the compound responsible for the stale odor of “hine-ka” in alcoholic beverages, particularly Japanese sake, is described.     

Highly stereoselective approach to chiral building block possessing three contiguous asymmetric centers. Preparation of four possible diastereomers of β,β′-dimethyl-bis-homoallylic alcohol derivative

All four diastereomere of chiral alcohol $\text{2}$ with three contiguous chiral centers were stereoselectively prepared via diastereoselective addition of nucleophiles (crotyl metal or H^-) to α-methyl-β,γ-unsaturated carbonyl compounds $\text{1}$.     

Photoinduced Atom Transfer Radical Addition/Cyclization Reaction between Alkynes or Alkenes with Unsaturated α-Halogenated Carbonyls

We have developed a photochemical ATRA/ATRC reaction that is mediated by halogen bonding interactions. This reaction is caused by the reaction of malonic acid ester derivatives containing bromine or iodine with unsaturated compounds such as alkenes and alkynes in the presence of diisopropylethylamine under visible light irradiation. As a result of various control experiments, it was found that the formation of complexes between amines and halogens by halogen-bonding interaction occurs in the reaction system, followed by the cleavage of the carbon–halogen bonds by visible light, resulting in the formation of carbon radicals. In this reaction, a variety of substrates can be used, and the products, cyclopentenes and cyclopentanes, were obtained by intermolecular addition and intramolecular cyclization.     

Studies of the dynamics of autoignition assisted outwardly propagating spherical cool and double flames under shock-tube conditions

The initiation, propagation, and transition of the autoignition assisted spherical cool flame and double flame are studied numerically and experimentally using n-heptane/air/He mixtures under shock-tube experimental conditions over a wide range of temperatures. The primary goal of the current study is to understand the effects of the ignition Damkohler number, ignition energy, flame curvature, and autoignition-induced flow compression on the propagation of spherical flames to ensure the proper interpretation of shock-tube flame speed measurements at engine-relevant conditions. The results show that at high ignition Damkohler number, there are three different flame regimes, cool flame, double flame, and hot flame. The cool flame speed accelerates dramatically with the increase of ignition Damkohler number. In addition, it is found that the change of flame regime, low-temperature autoignition, flame stretch, and autoignition-induced flow compression result in a complicated non-linear dependence of flame speed on stretch. The results also reveal that the spherical cool flame has much lower Markstein length compared to the hot flame at T > 600 K. Moreover, it is found that both the autoignition assisted cool flame and the trailing hot flame front in the double flame can propagate much faster that the hot flame alone at the same mixture conditions, leading to a nonlinear dependence of flame speed on the mixture initial temperature. The simulated flame trajectories and the flame speed dependence on temperature agree qualitatively well with the shock-tube experiments. A quantitative criterion to ensure the accurate speed measurement of the cool and hot flame is proposed. The present study provides important physical insight and guidance for the flame speed measurement using a shock-tube at engine relevant conditions.     

Pockels effect of water in the electric double layer at the interface between water and transparent electrode

We have obtained the first experimental evidence for the Pockels effect of water, which is induced by a high electric field in the electric double layer (EDL) on the water-transparent electrode interface. The electric-field induced energy shift of the visible interference fringes of a 300 nm indium-tin-oxide (ITO) electrode layer is observed, indicating a negative refractive index change at the interface. Numerical calculation reproduces well the experimental observation, showing that the signal mainly originates from water in the EDL. The Pockels constants of water are estimated to be r₃₃ = 5.1 × 100 pm/V and r₁₃ = 1.7 × 100 pm/V. The large anisotropy of the Pockels effect of water is deduced from the incidence angle dependence of the p-polarization signal. At the same time, the ITO shows a blue shift of the band gap in the UV due to the band population effect in the space charge layer. The plasma frequency in the near IR is also expected to increase due to the band population effect, since the ITO has a high doped carrier population close to metal. A negative refractive index change in the ITO space charge layer is induced from both effects, but its effect on the signal is estimated to be much smaller than that of the negative refractive index change of water in the EDL.     

Transient stability of AC multi-strand superconducting cables

AC application, it is necessary to estimate the stability of multi-strand superconducting cable. Therefore, we have been studying the transient stability of non-insulated multi-strand cable when one strand in a cable turns into the normal state locally. In the quench process, local temperature rise produced by current redistribution among strands is not desirable for stability. In a previous work, we discussed the effect of Cu matrix allocated to each strand on the transient stability and showed that the Cu matrix allocation can improve the stability of non-insulated multi-strand cable through mainly numerical simulations. In this paper, we carried out experiments on three kinds of non-insulated three-strand cables; one consists of NbTi/CuNi strands and the others consist of NbTi/Cu/CuNi strands having different cross-sectional arrangement. These sample strands have almost the same diameter, the same matrix to superconductor ratio and the same B–J characteristics to evaluate the effect of Cu allocation quantitatively. We choose to define the transient stability in terms of the minimum quench energy (MQE) at each DC transport current. We also investigated the transient stability of sample cables when quench is initiated in two or three (all) strands simultaneously.     

Preparation of polysaccharide derivatives and their chiral recognition mechanism

Several new phenylcarbamate derivatives of cellulose and amylose having fluoro and methyl groups or 4-trimethylsilyl substituent on the phenyl groups were prepared and their chiral recognition abilities as chiral stationary phases for HPLC were evaluated. These derivatives are soluble in chloroform and exhibit chiral discrimination in ¹H NMR spectroscopy. Based on the above results and molecular mechanics calculation of interaction energies between the derivatives and enantiomers, the mechanism of chiral discrimination is discussed.     

Peculiar ‘Reptational’ Movements of Single Synthetic Polymer Chains on Substrate Observed by AFM

Peculiar ‘reptational’ movements of isotactic PMMA chains on mica are observed by in situ AFM. The polymer molecules comprise long flexible chains that exhibit reptative, or snake‐like, motion on the substrate along the direction of the polymer chain. Intriguingly, some chains underwent forward then backward motion in which the head of the chain moved in a curvilinear manner along the previous contours of the polymer chain. No limitation in the direction of movement for the ends of the polymer chain was anticipated based on an assumed reptational mechanism. As a result, the chains recovered a conformation that had been adopted prior to the initial movement. Several factors that may affect the movement are discussed.