Thermal [2+2] cycloaddition of morpholinoenamines with C60 via a single electron transfer

The thermal reaction of C(60) with five- and six-membered morpholinocycloalkenes in refluxing toluene exclusively gave the [2+2] cycloadducts in high yields. However, a seven-membered homologue sluggishly reacted with C(60) because of the increasing steric hindrance. This cycloaddition reaction is likely to proceed via a single electron transfer (SET), a radical-coupling, and subsequent ion cyclization rather than the prior proton transfer between the radical ions.     

Multiple solutions of semilinear degenerate elliptic boundary value problems

The purpose of this paper is to study a class of semilinear elliptic boundary value problems with degenerate boundary conditions which include as particular cases the Dirichlet problem and the Robin problem. The approach here is based on the super‐sub‐solution method in the degenerate case, and is distinguished by the extensive use of an L^p Schauder theory elaborated for second‐order, elliptic differential operators with discontinuous zero‐th order term. By using Schauder's fixed point theorem, we prove that the existence of an ordered pair of sub‐ and supersolutions of our problem implies the existence of a solution of the problem. The results extend an earlier theorem due to Kazdan and Warner to the degenerate case. © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

Ultrafast excited state dynamics of fucoxanthin: excitation energy dependent intramolecular charge transfer dynamics

Carotenoids containing a carbonyl group in conjugation with their polyene backbone are naturally-occurring pigments in marine organisms and are essential to the photosynthetic light-harvesting function in aquatic algae. These carotenoids exhibit spectral characteristics attributed to an intramolecular charge transfer (ICT) state that arise in polar solvents due to the presence of the carbonyl group. Here, we report the spectroscopic properties of the carbonyl carotenoid fucoxanthin in polar (methanol) and nonpolar (cyclohexane) solvents studied by steady-state absorption and femtosecond pump-probe measurements. Transient absorption associated with the optically forbidden S(1) (2(1)A) state and/or the ICT state were observed following one-photon excitation to the optically allowed S(2) (1(1)B) state in methanol. The transient absorption measurements carried out in methanol showed that the ratio of the ICT-to-S(1) state formation increased with decreasing excitation energy. We also showed that the ICT character was clearly visible in the steady-state absorption in methanol based on a Franck-Condon analysis. The results suggest that two spectroscopic forms of fucoxanthin, blue and red, exist in the polar environment.     

Proposition of Single Molecular Orientation Determination Using polarization Controlled Beam by Liquid Crystal Spatial Light Modulators

We have proposed a method to control the three-dimensional electric field in the focus of an optical microscope using two non-twisted liquid crystal spatial light modulators, and to detect the molecular orientation of a single molecule. The three-dimensional electric field is generated by focusing the beam with two dimensional spatial distribution of polarization. The possibility of detection of three-dimensional single molecular orientation was shown by numerical calculations. © 2005 The Optical Society of Japan     

Birefringent side-hole fiber for use in strain sensor

Novel birefringent single-mode fibers are fabricated with a vacant hole on either side of the central elliptical core, referred to as side-hole fiber, and their intrinsic and tension-induced modal birefringences are measured to know their characteristic properties for the purpose of making a strain sensor. Five sampled side-hole fibers are prepared for measurements. The sensitivity of the strain sensor is primarily determined by two parameters, tension-induced and intrinsic modal birefringences. Tension-induced modal birefringence is controllable by optimal arrangement of the size and location of the side-holes in the cross-section of the fiber. A sensitivity diagram for designating and fabricating side-hole fibers is presented.     

Oxidation behavior of NiAl alloy at low temperatures

Oxidation behavior of NiAl alloy at low temperatures was studied. A NiAl plate was oxidized by exposure to ambient atmosphere at room temperature, heated at 473 K in air, and heated at 773 K in air. The oxide formed on the NiAl surface was investigated by angle‐resolved X‐ray photoelectron spectroscopy (AR‐XPS). Chemical composition and atomic concentration in the oxide layer were analyzed with factor analysis of XPS spectra. Exposure of the NiAl plate to the ambient atmosphere resulted in the formation of an Al₂O₃ layer along with a small amount of NiO. Oxidation of the NiAl plate at 473 K in air formed a film of double‐layered oxide; the top layer consisted of NiAl₂O₄ and a small amount of NiO, and the second layer was Al₂O₃. Successive oxidation at 773 K only changed the oxide‐layer thickness without changing the structure. Formation of oxide observed in the present study corresponds to the thermodynamic prediction for the oxidation behavior of NiAl at 1373 K. Copyright © 2007 John Wiley & Sons, Ltd.     

AC loss of low temperature superconducting AC wire caused by longitudinal and azimuthal AC magnetic field components

We investigated the AC loss characteristics of a low temperature NbTi AC wire by measuring the AC transport current losses in the external AC magnetic field whose components are the longitudinal and transverse ones. The measurement results showed that the AC losses were significantly dependent on the directions and magnitudes of the external longitudinal field component. The AC losses caused by the longitudinal and azimuthal field components were estimated by our previously derived model. The theoretical results well explained the dependence of the AC losses on the longitudinal field components. It was also shown that the AC losses can be substantially reduced by the proper choice of the twisting way.     

Palladium(O)-catalyzed allylic alkylation and amination of allylic phosphates

Allyl diethyl phosphates (1) can be easily substituted with malonates and amines in the presence of palladium(O) catalyst. Synthetic utility of the reaction is demonstrated by the sequential amination-amination and alkylation-amination of (Z)-4-acetoxybut-2-enyl diethyl phosphate (1b) with high regio- and stereoselectivity.     

Structural and conformational studies on citreoviridinol and isocitreoviridinol: syntheses of some 2,6-dioxabicyclo[3.2.1]octanes

Isocitreoviridinol has been newly isolated from the mycelium of $\text{Penicillium citreo-viride}$ B. (IFO 6050) together with citreoviridinol, and their stereostructures have also been elucidated by means of chemical method: the 2,6-dioxabicyclo[3.2.1]octanes have been made, one of which is regarded as a promising synthetic intermediate of citreoviridinol. In addition, isocitreoviridinol diacetate has been derived from citreoviridin in 3 steps.