A new triterpene synthase from Arabidopsis thaliana produces a tricyclic triterpene with two hydroxyl groups

[structure: see text] Thirteen oxidosqualene cyclase homologues exist in the genome of Arabidopsis thaliana. One of these genes, At4g15340, was amplified by PCR and expressed in yeast. The yeast transformant accumulated tricyclic triterpene, (3S,13R)-malabarica-17,21-dien-3,14-diol (arabidiol), whose structure was determined by NMR and MS analyses. Its epoxide analogue, (3S,13R,21S)-malabarica-17-en-20,21-epoxy-3,14-diol (arabidiol 20,21-epoxide), was also isolated from the transformed yeast. This is the first example of a triterpene synthase that yields a tricyclic triterpene with two hydroxyl groups.     

Stereochemical course in water addition during LUP1-catalyzed triterpene cyclization

Arabidopsis thaliana LUP1 (At1g78970) catalyzes the cyclization of oxidosqualene into lupeol and 3beta,20-dihydroxylupane (lupanediol). The stereochemical course of water addition to the lupanyl cation was studied. The X-ray crystal structure of lupanylepoxide 3,5-dinitrobenzoate established the configuration of epoxide as 20S. LiAlD4 reduction of the epoxide enabled the chemical shift assignment of prochiral methyl groups at C20 of lupanediol. Correlation of these methyl groups with biosynthetic lupanediol from [1,2-(13)C(2)] acetate established the stereochemical course of water addition. [reaction: see text].     

Quadrature phase-shifting interferometer with a polarization imaging camera

We present a new high-speed phase distribution measurement, in which a polarization imaging camera is applied to a quadrature phase-shifting interferometer. The polarization imaging camera composed of a polarizer-mask on a detector array can provide simultaneously two phase-shifted data in quadrature. Two sets of two phase-shifted data in quadrature are obtained before and after a change of the interferometer such as object displacement or environmental disturbances. Phase sum and difference distributions of the interferograms between two states with arbitrary phase-shift in the interferometer are calculated with the two sets of two phase-shifted data in quadrature. This phase calculation method in the pixel displaced phase-shift method has such advantage that phase-shifted data required for the calculation of phase distributions can be obtained by only two pixels in the polarizer-mask detector array, which means no reduction of the image resolution in the other direction. The principle of this technique and experimental results are presented.     

Resolution enhancement techniques for optical lithography and optical imaging theory

Production of a fine pattern is necessary to get a high integration degree of integrated circuits. The conventional methods which utilize high numerical aperture and short wavelength exposure are limited by designing and manufacturing of a practical lens and make the focus depth narrow. Resolution enhancement techniques (RETs) have, therefore, been required and proposed. This paper introduces a phase-shifting mask, a typical RET, points out the problems and inconsistencies of conventional optical imaging theory and explains the image formation concept of expansion of plane waves. Essentially using this concept, an attempt is also made to describe some other typical RETs with potential.     

Experimental wavelet analysis of flexural waves in beams

The wavelet transform (WT) is applied to the time-frequency analysis of flexural waves in beams. The WT with the Gabor wavelet decomposes a dispersive wave into each frequency component in the time domain, which enables one to determine the traveling time of a wave along the beam at each frequency. By utilizing this fact, a method is developed to identify the dispersion relation and impact site of beams.     

Synthesis, reactions and DNA damaging abilities of 10-membered enediyne-sulfone and related compounds

The synthesis and Myers-Saito type cycloaromatization reactions of 10-membered enediynes containing a sulfone or a sulfoxide moiety are described. These enediynes cycloaromatized smoothly under physiological conditions to generate bioactive α,3-didehydrotoluene biradicals, that showed potent DNA damaging abilities. Further, in the presence of a nucleophile such as amine or sulfide, cycloaromatization did not occur following the radical reaction pathway but ionically induced cycloaromatization took place.     

Effect of aspirin on chromosome aberration and DNA damage induced by X-rays in mice

In order to reveal the anticlastogenic potency of aspirin, we evaluated the suppressive ability of aspirin on chromosome aberrations induced by X-ray. Aspirin at doses of 0.5, 5 and 50 mg/kg was administrated intraperitoneally or orally at 0.5 h after or before the X-ray irradiation. The anticlastogenic activity of aspirin on chromosome aberrations induced by X-ray was determined in the mouse micronucleus test and alkaline single cell gel electrophoresis (SCG) assay in vivo. The frequency by polychromatic erythrocytes with micronuclei (MNPCEs) was decreased by about 19–61% at 0.5 h after and about 23–62% at 0.5 h before the X-ray irradiation. DNA damage by X-ray was significantly decreased by oral administration of aspirin at 0.5 h after or before the X-ray irradiation for the SCG assay. We consider aspirin can be used as preventive agents against exposure of X-ray.     

1,2-Carbopentafluorophenylation of Alkynes: The Metallomimetic Pull-Push Reactivity of Tris(pentafluorophenyl)borane

We report the novel single-step 1,2-dicarbofunctionalization of an arylacetylene with an allylsilane and tris(pentafluorophenyl)borane [B(C₆F₅)₃] involving C−C bond formation with C−H bond scission at the β-position to the silicon atom of an allylsilane and B→C migration of a C₆F₅ group. The 1,2-carbopentafluorophenylation occurs smoothly without the requirement for a catalyst or heating. Mechanistic studies suggest that the metallomimetic “pull-push” reactivity of B(C₆F₅)₃ imparts consecutive electrophilic and nucleophilic characteristics to the benzylic carbon of the arylacetylene. Subsequent photochemical 6π-electrocyclization affords tetrafluoronaphthalenes, which are important in the pharmaceutical and materials sciences. Owing to the unique reactivity of B(C₆F₅)₃, the 1,2-carbopentafluorophenylation using 2-substituted furan proceeded with ring opening, and the reaction using silyl enolates formed a C−C bond with C−O bond scission at the silyloxy-substituted carbon.