Isolation and structure elucidation of genuine oat phytoalexin,avenalumin I

The major phytoalexin from oat leaves has been identified as 2-[2-(4-hydroxyphenyDethenyl] -6-hydroxy-4H-3,1-benzoxazin-4-one ($\text{A}$).     

Ab initio molecular orbital calculations of the cobalt porphine complex. I. LCAO SCF MO calculation of low-spin,high-spin,and π-ionized states of Co-porphine

Ab initio LCAO SCF MO calculations are carried out on planar Co-porphine with a basis set of roughly double zeta quality for Co and N and of single zeta quality for C and H. The net charge on Co and N and the overlap population between them are 1.78, ?0.57, and 0.06, respectively, in the ²A_1g, state, which is known to be the ground state by experiment. The bonding in this complex is thus largely ionic. The first and second calculated ionization potentials are 6.51 and 6.77 eV, respectively, and are in reasonable agreement with the observed ionization potentials of 6.44 and 6.62 eV for Ni-tetraphenylporphine. CI calculations within the framework of the ligand field theory are also performed. The calculated order of the five lowest states is ⁴B_2g ≈ ⁴E_g, ⁴A_2g, ²A_1g, ⁴E_g from below and is not in agreement with the semiempirical order of ²A_1g ≈ ⁴B_2G, ⁴A_2g, ²E_g, ⁴E_g determined by Lin.     

Asymmetric benzoin condensation catalyzed by chiral rotaxanes tethering a thiazolium salt moiety via the cooperation of the component: can rotaxane be an effective reaction field?

Although some reactions on rotaxanes have been reported, the characteristic features of the rotaxanes providing unique reaction fields have hardly been studied, especially as catalyst. In our continuous studies on interlocked molecules such as rotaxanes and catenanes, we have noticed the importance of such interlocked structures with high freedom in functionalized materials such as molecular catalyst. For catalytic asymmetric benzoin condensations, two optically active rotaxanes possessing thiazolium salt moieties were prepared using the binaphthyl group as the chiral auxiliary. The benzoin condensations of aromatic aldehydes catalyzed by the chiral rotaxanes as catalysts gave optically active benzoins with ca. 30% ee in moderate to high chemical yields depending upon the structure of rotaxane and the reaction conditions employed. From the results, two intrarotaxane chirality transfers are confirmed: (i) through-space chirality transfer from wheel to axle and (ii) through-bond chirality transfer controlled with an achiral wheel. Because these asymmetric reaction fields are specific to the rotaxane structure, the importance and possibility of the "rotaxane field" as a particular reaction field is demonstrated in this work.     

Redox behavior of ferrocene-containing rotaxane: transposition of the rotaxane wheel by redox reaction of a ferrocene moiety tethered at the end of the axle

A rotaxane with a ferrocene moiety at the axle terminus was prepared. The redox potential of the ferrocene moiety decreased by ca. 80 mV when the rotaxane had a crown ether wheel capable of moving on the axle. Thus, the stabilization of the oxidized state of the ferrocene moiety is assumed to accompany the transposition of the wheel component on the axle toward the ferrocene moiety. [reaction--see text]     

Direct observations of freeze-etching processes of ice-embedded biomembranes by atomic force microscopy

We have fabricated a cryogenic atomic force microscope that is designed for structural investigation of freeze-fractured biological specimens. The apparatus is operated in liquid nitrogen gas at atmospheric pressure. Freeze-fracturing, freeze-etching and subsequent imaging are carried out in the same chamber, so that the surface topography of a fractured plane is easily visualized without ice contamination. A controlled superficial sublimation of volatile molecules allows us to obtain three-dimensional views of ultrastructures of biological membranes.     

A new ent-clerodane diterpene from the aerial parts of Baccharis gaudichaudiana

A new ent-clerodane diterpene, named bacchariol (1) was isolated from the aerial parts of Baccharis gaudichaudiana DC. (Compositae), together with known ent-clerodane diterpenes (2, 3), eight known flavonoids (4-11) and 3, 5-dicaffeoylquinic acid (12). Their structures were determined by spectroscopic analyses. Flavonoids (7, 8, 11) and 12 showed moderate scavenging activities toward 1, 1-diphenyl-2-picrylhydrazyl (DPPH) radicals.     

Diastereoselective photochromism of a bisbenzothienylethene governed by steric as well as electronic interactions

Introduction of an asymmetric center to C-2 of one of the benzothiophene rings of bisbenzothienylperfluorocyclopentene results in a highly diastereoselective photochromic system. The stereogenic center bears a hydrogen atom, a methyl group, and a methoxymethoxy group. The steric as well as the electronic repulsions gave an 87-88% diastereomer excess in various solvents at room temperature with 80-85% conversion to the colored form. The enantioselective synthesis was also carried out. Upon photoirradiation in hexane, a change in optical rotation at 820 nm, where neither the open form nor the colored form absorbs light, was observed repeatedly.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.