Reaction potential map analysis of site selectivity of acrylic acid and acrylonitrile

The reaction potential map (RPM) method has been extended so that the molecular reactivity towards nucleophiles can be analyzed. An anion consisting of the nucleus with + 1 charge and a pair of electrons was adopted as the model nucleophile. From the interaction energy between a substrate and this model particle, RPM and its component maps were obtained. With respect to practical applications, the reactivities of acrylic acid and acrylonitrile towards nucleophiles were examined. In these molecules, the exchange interaction as well as the charge-transfer interaction were found to be very important in the elucidation of the observed site selectivity.     

Correlation between oxygen consumption and photobleaching during in vitro photodynamic treatment with ATX-S10.Na(II) using pulsed light excitation: dependence of pulse repetition rate and irradiation time

We revealed that in ATX-S10.Na(II)(13,17-bis (1-carboxypropionyl) carbamoylethyl-8-etheny-2-hydroxy-3-hydroxyiminoethylidene-2,7,12,18-tetraethyl porphyrin sodium)-mediated photodynamic therapy using 667 nm nanosecond-pulsed light excitation at a peak intensity of 2.0 MW/cm(2), phototoxicity increased with decreasing pulse repetition rate in the range of 5-30 Hz for A549 cell cultures. To examine the relation between the reaction mechanism and measured phototoxicity, we carefully measured the kinetics of photochemical oxygen consumption and photobleaching during irradiation of ATX-S10.Na(II)-sensitized A549 monolayer cultures. Measurements of oxygen consumption with a microelectrode, which was performed just above the cells, showed that there was no significant difference between the magnitudes of decrease in oxygen at the three repetition rates at the same cumulative fluence. Loss of ATX-S10.Na(II) fluorescence intensity also exhibited little repetition rate dependence when compared at the same cumulative fluence. We investigated the correlation between oxygen consumption and photobleaching during irradiation and obtained "fluorescence-oxygen diagrams." The diagrams showed dynamic changes between oxygen-dependent and oxygen-independent photobleaching at the higher repetition rates of 10 and 30 Hz, whereas such change was not clearly seen over the whole irradiation time at 5 Hz. These results suggest that the reduced phototoxicity at high repetition rates might be due to an oxygen-independent reaction. We presumed that the change in the reaction mechanism was associated with the local concentrations of the photosensitizer and oxygen in cells during irradiation.     

Kinetic pathway to double-gyroid structure

We have investigated the structural development during order-order transitions to the double-gyroid (DG) phase of nonionic surfactant/water systems based on two-dimensional small-angle x-ray scattering patterns from highly oriented ordered mesophases. The lamellar (L) to DG transition proceeds through two intermediate structures, a fluctuating perforated layer structure having ABAB stacking and a hexagonal perforated lamellar structure with ABCABC stacking (HPLABC). For a hexagonally packed cylinder (H) to DG transition, we also observed the HPLABC structure as the intermediate phase, thus the HPLABC is an entrance structure for the DG phase. The hexagonal perforated lamellar (HPL) structure consists of hexagonally packed holes surrounded by the planar tripods, and the transition from HPL structure to the DG phase proceeds by rotation of the dihedral angle of connected tripods. A geometrical consideration shows that large deformations of HPL planes are necessary to form the DG structure from the HPLABC structure, whereas the transition from a HPL structure with ABAB stacking (HPLAB) to the DG structure is straightforward. In spite of the topological constraints, the HPLABC structure is observed in the kinetic pathway to the DG structure.     

Studies on the constituents of Lonicera species. XVII. New iridoid glycosides of the stems and leaves of Lonicera japonica THUNB

Four new iridoid glycosides, named L-phenylalaninosecologanin (1), 7-O-(4-beta-D-glucopyranosyloxy-3-methoxybenzoyl)secologanolic acid (2), 6'-O-(7alpha-hydroxyswerosyloxy)loganin (3) and (Z)-aldosecologanin (5), were isolated, together with a known one, newly named (E)-aldosecologanin (4), from the stems and leaves of Lonicera japonica. Their structures were established on the basis of chemical and spectral data.     

Five new sesquiterpenoids and a new diterpenoid from Erigeron annuus (L.) PERS., Erigeron philadelphicus L. and Erigeron sumatrensis RETZ

The aerial parts of Erigeron annuus (L.) PERS., E. philadelphicus L. and E. sumatrensis RETZ. (Compositae) have been investigated chemically. A new sesquiterpenoid, 6beta,14-epoxyeudesm-4(15)-en-1beta-ol (1), and a new diterpenoid, philadelphinone (6), have been isolated from E. philadelphicus. Four new sesquiterpenoids, (7R*)-opposit-4(15)-ene-1beta,7-diol (2), 11-methoxyopposit-4(15)-en-1beta-ol (3), 15-methoxyisodauc-3-ene-1beta,5alpha-diol (4) and 10alpha-hydroxycadin-4-en-15-al (5), have been isolated from E. annuus. Compounds 2 and 4 were also isolated from E. sumatrensis. The structures of the new compounds were elucidated on the basis of their spectral data.     

Biomimetic formation of gramicidin S by dimerization-cyclization of pentapeptide precursor on solid support

The biomimetic formation of gramicidin S, cyclo(-d-Phe-Pro-Val-Orn-Leu-)₂, by the dimerization and cyclization of pentapeptide precursor without the protection of δ-amino group of the Orn residue was examined on a solid support. The cyclization of H-d-Phe-Pro-Val-Orn-Leu-oxime on a resin with an oxime group of 0.62 mmol/g in 1,4-dioxane directly gave gramicidin S in a 50% yield. The dimerization-cyclization mode on the solid support was similar to that of the biosynthesis of gramicidin S on an enzyme.