Asymptotic linear expansion of profile likelihood in the Cox mode

By introducing a new parameterization, Hirose [12] improved on the seminal work of Murphy and van der Vaart [16]: the improvement establishes the efficiency of the estimator through direct quadratic expansion of the profile likelihood, which requires fewer assumptions. This paper aims to demonstrate that the approach in [12] is fully applicable to the Cox proportional hazard model.     

Polymeric Electron Carriers

Polymers containing 1,4-dihydronicotinamide (P-NAH) alloxan (P-A), and viologen (P-V²⁺) moieties were synthesized and characterized. P-NAH reduced various organic substances such as lipoic acid, alloxan, and viologens and also immobilized quinone mediated by alloxan. P-A was reduced to the polymer-bearing alloxan radical and the dialuric acid structure without crosslinks by one- and two-electron reduction, respectively, and P-A also mediated the redox reaction occurring between aqueous and organic (water-immiscible) layers. P-V²⁺ was converted to the stable viologen radical reversibly by one-electron reduction. Electric potentials and currents on photo-reduction of P-V²⁺ and catalytic behavior of P-V²⁺ in the reduction of carbonyl compounds were examined.     

Thermal behavior and dismantlability of adhesives containing various inorganic salts

As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts.     

Novel synthesis of zerumbone-pendant derivatives and their biological activity

Zerumbone 1, having powerful latent reactivity and containing two conjugated double bonds and a double conjugated carbonyl group is the major component of the essential oil of wild ginger, Zingiber zerumbet Smith. The conjugation system plays an important role in the expression of biological activity. N-Bromosuccinimide (NBS) reaction of 1 gave high reactive intermediate 2 with an exo-methylene group, which was obtained from 1 quantitatively. Treatment of 2 with nucleophiles gave various zerumbone-pendant derivatives, including C–H, C–O, C–N, and C–C bond formation, maintaining the conjugation system through S_N2′-type reaction. Almost all zerumbone-pendant derivatives showed a good value of IC₅₀ against the suppressive effect of NO generation. Among them, amine derivative 5, binding with 2 mol of zerumbone, showed the strongest activity (IC₅₀: 0.24 μM).     

Synthesis and spectral properties of ruthenium(II) complexes based on 2,2′-bipyridines modified by a perylene chromophore

Five new 2,2′-bipyridines functionalized with a perylene or a perylenediimide moiety were synthesized and the corresponding heteroleptic ruthenium(II) complexes ([Ru(bpy)₂(L)](PF₆)₂; bpy = 2,2′-bipyridyl, L = perylene-substituted bpy ligand) were prepared. The UV–vis spectra of the ruthenium(II) complexes showed red-shifted and intense absorption bands derived from the conjugated structure of the new ligands.     

Highly Selective Copper‐Catalyzed Hydroboration of Allenes and 1,3‐Dienes

The highly selective copper‐catalyzed hydroboration of allenes has been developed. Allylboranes and alkenylboranes were selectively prepared by the judicious choice of catalytic species (copper hydride and boryl copper). Furthermore, two types of alkenylboranes could be selectively synthesized by the choice of an appropriate ligand. Mechanistic studies confirmed that the protonation of a (Z)‐σ‐allyl copper species, which was isolated and structurally characterized by single‐crystal X‐ray diffraction, was a key step in these reactions. Besides allenes, this method is also applicable to the selective hydroboration of 1,3‐diene derivatives to afford allylboranes and homoallylboranes.     

Direct Synthesis of 1,4‐Diols from Alkenes by Iron‐Catalyzed Aerobic Hydration and C?H Hydroxylation

Various 1,4‐diols are easily accessible from alkenes through iron‐catalyzed aerobic hydration. The reaction system consists of a user‐friendly iron phthalocyanine complex, sodium borohydride, and molecular oxygen. Furthermore, the effect of additional ligands on the iron complex was examined for a model reaction. The second hydroxy group is installed by direct C(sp³) H oxygenation, which is based on a [1,5] hydrogen shift process of a transient alkoxy radical that is formed by formal hydration of the olefin.     

Neomacrophorin I,II, and III,novel drimenyl cyclohexanes with hydroxylated butanoates from Trichoderma sp. 1212-03

Neomacrophorins I (1), II (2), and III (3) were isolated from the culture broth of Trichoderma sp. 1212-03, which was collected at Shirakami Mountainous area in Japan. Structural analyses disclosed that these resemble known macrophorins but possess axial-hydroxy group at C3 as well as different side chains at C7′. These are diastereomeric forms of macrophorins for 5′,6′-epoxide functionality. The NMR analyses suggested their relative configurational relationship between the C1–C15 drimene and C1′–C7′ epoxyquinone moieties. ECD spectral discussions verified them particularly for C5′,C6′-epoxyquinone (1), C5′,C6′-epoxysemiquinone (2 and 3), and 2″,3″-dihydroxybutanoate moiety in 1 and 2. The configuration of C3″-stereocenter of 3 was determined by chiral GC–MS after converting into methyl (S)-3″-hydroxybutanoate by basic of 3 methanolysis. Biological assays disclosed that 1 induces hyphal branching of Cochliobolus miyabeanus as well as cytotoxicity against human colorectal cancer COLO 201.