Palladium-catalyzed direct N-arylation of nucleosides, nucleotides, and oligonucleotides for efficient preparation of dG-N2 adducts with carcinogenic amino-/nitroarenes

A method for direct palladium-catalyzed N-arylation reaction of nucleobases was developed for the convenient synthesis of DNA adducts with carcinogenic compounds. Using xantphos as the phosphine ligand and tetraethylammonium fluoride as the base in DMSO, several o-iodonitroarenes could be efficiently coupled with 2'-deoxyguanosine, 2'-deoxyadenosine, and 2'-deoxycytidine. The presence of a 3'-phosphate group in the deoxyribose moiety was found to be compatible with this N-arylation reaction; further, oligonucleotides could serve as substrates. The facile nitroreduction of the coupling compounds (12) yielded 2'-deoxyguanosin-N2-ylarylamine adducts, which are known to be biologically important. Compound 12 was easily converted to phosphoramidite derivatives, allowing the preparation of site-specific modified oligonucleotides with arylamine after the nitroreduction.     

Synthesis and fluoride-induced chemiluminescent decomposition of bicyclic dioxetanes substituted with a 2-hydroxynaphthyl group

Five bicyclic dioxetanes bearing a 2-hydroxynaphthyl group, 1aA-1eA, were synthesized and their chemiluminescent decomposition was examined by the use of tetrabutylammonium fluoride (TBAF) as a base in DMSO. It was found that these dioxetanes hold completely the ‘odd/even’ relationship between the substitution pattern of hydroxy as a trigger on the naphthalene ring and their chemiluminescent efficiency, and that dioxetane 1aA exhibited chemiluminescence with the highest efficiency among those for the oxynaphthyl-substituted dioxetanes hitherto known. The significant change in chemiluminescent efficiency depending on the substitution pattern was clarified to be attributed to the marked change in singlet-chemiexcitation efficiency for charge-transfer-induced chemiluminescence (CTICL) of 1aA-1eA. In respect of the rate of CTICL-decomposition, ‘odd/even’ relationship was observed for 1aA-1dA.     

Color modulation for intramolecular charge-transfer-induced chemiluminescence of bicyclic dioxetanes bearing a 3-hydroxy-5-naphthylphenyl moiety in the coordination sphere

Bicyclic dioxetanes 2a, 2b, and 3, bearing a 3-hydroxy-5-naphthylphenyl moiety underwent charge-transfer-induced decomposition with accompanying emission of light, the color of which changed from red to blue responding to a complex of crown ether with potassium t-butoxide used as a base. Furthermore, they afforded unusual chemiluminescence, the spectra of which displayed two peaks in some cases. It was observed for chemiluminescences in the coordination sphere with crown ether that their spectra did not coincide with the spectra of authentic emitters.     

A generalization of Lelieuvre’s formula to equiaffine immersions of general codimension

A non-degenerate equiaffine immersion of codimension one into an equiaffine space is locally expressed in terms of its conormal map and its affine fundamental form. The expression is called the Lelieuvre’s formula. We recently defined the notions of an equiaffine immersion of general codimension and its transversal volume element map. In this paper, we locally express a non-degenerate equiaffine immersion of general codimension into an equiaffine space in terms of its transversal volume element map and its affine fundamental form.     

Evaluating Optical Quality of a Bifocal Soft Contact Lens in Near Vision Using a Shack–Hartmann Wavefront Aberrometer

To assess optical characteristics of bifocal soft contact lenses (BCLs) in use, we measured wavefront aberrations of human eyes, of eyes with a monofocal soft contact lens (MCL), and of eyes with a BCL. Modulation transfer functions (MTFs), Strehl ratios, and simulated images for far and near vision were produced with the measured aberrations. High order aberrations of subject 1 were significantly smaller than those of subject 2 (t-test, P = 0.001). We found that wearing the BCL improved the optical quality of an eye in subject 1, expressed as the horizontal MTF from 2 to 48 cycles per degree (cpd) for near vision and the Strehl ratio (t-test, P = 0.009 for Strehl ratio). But we did not find the same effect in subject 2. This difference may be due to the difference in the aberrations of the eyes of the two subjects.     

Simulation study on microstructure formations in magnetic fluids

We propose the Langevin-type microscopic equations of motion for magnetic fluids. Magnetic fluids are modeled as an ensemble of interacting ferromagnetic nanoparticles suspended in a viscous fluid. The present model is described in terms of position vectors of nanoparticles and orientation vectors of their magnetic dipole moments. In this model, forces and torques arising from the magnetic origin and the surrounding fluid flow are included. Effects of non-spherical particle shape are also taken into account. From the Brownian dynamics simulations of the model, it is found that the present model exhibits various microstructure formation processes in magnetic fluids.     

Effects of encounters on phase separation dynamics from diffusion-controlled growth to coarsening

We investigate the dynamics of phase separations in quenched binary mixtures, such as binary alloys and polymer blends with low mobilities, at higher volume fractions. Computer simulations are performed using simple model equations in the presence of encounters of droplets. Four characteristics stages with three crossovers, including dynamical scaling behavior and temporal power laws, are found beyond a volume fraction of approximately 0.14, where each crossover is attributed to a transition from one growth mechanism to the other. The encounter effect is thus shown to strongly influence a transition from the diffusion-controlled (t^1/2) stage to the coarsening (t^1/3) stage. A simple analytical argument for the simulation results is also presented.     

Investigations of morphology, purity and crystal defects of the InN pillar crystals prepared by means of halide chemical vapor deposition under atmospheric pressure

Indium nitride prepared under atmospheric pressure using a halide chemical vapor deposition method has been examined by means of a variety of analytical techniques. Scanning electron microscopic observations showed that the crystals deposited onto a Si(100) substrate have hexagonal pillar structure. Based on the X-ray diffraction and X-ray pole-figure analyses, it was deduced that each InN pillar crystal grows with a different rotation angle around the 〈001〉 axis. Transmission electron diffraction showed that they are of single-like form. This was also confirmed by the selected area electron diffraction image as well.