The first asymmetric total syntheses of both enantiomers of cryptocaryone

The first asymmetric total syntheses of the (+)- and (−)-cryptocaryones are described. Removal of the acetal unit of the enone acetal 5, which was obtained in our previous study from the cyclohexadiene acetal 3, afforded the enone acetal 8 in a one-pot procedure. The acylation of 8 with cinnamoyl chloride and subsequent hydrolysis of the resulting acetal gave the lactol 11. Its oxidation with NIS and tetra-n-butylammonium iodide (TBAI) finally furnished the natural (+)-cryptocaryone 2. The same procedure from ent-3 afforded the unnatural one 1.     

From metal/semiconductor separation to single‐chirality separation of single‐wall carbon nanotubes using gel

In the present work, a review of the metallic (M) and semiconducting (S) separation of single‐wall carbon nanotubes (SWCNTs) using polysaccharide gels is presented. First, the progress of the M/S separation is described, including the following: the discovery of high‐yield separation using agarose gel electrophoresis, the separation of SWCNTs without an electric field, such as through the use of the freeze and squeeze method, the development of continuous separation using column chromatography, and the single‐chirality separation of SWCNTs using a multicolumn with dextran‐based gel. Next, the separation mechanism using gel is discussed, in which separation is achieved by selective adsorption of S‐SWCNTs by gel with a specific combination of surfactant and gel. Lastly, future directions for the separation of SWCNTs and for the use of the separated SWCNTs are discussed.

     

Aragonite twinning in gastropod nacre

Aragonite twinning in gastropod nacre has been investigated using scanning electron microscopy (SEM), electron back-scattered diffraction (EBSD), and transmission electron microscopy (TEM) with the focused ion beam (FIB) sample preparation technique. At the growth front of nacre, Haliotis discus hannai and Omphalius rusticus form a “stack-of-coins” structures, which consist of pseudo-hexagonal and elliptical aragonite tablets, respectively. SEM, EBSD, and TEM analyses revealed that these tablets are monolithic single crystal and almost free of the {1 1 0} twins that are common in aragonite of biotic or abiotic origin. The longest diagonal of the hexagon and the longer axis of the ellipse are parallel to the a-axis of aragonite. The crystal orientation of each tablet in a stack, measured by TEM-Kikuchi pattern analysis, is almost the same but there is occasionally {1 1 0} twin-like relationship between adjacent tablets along the stacking. On the other hand, the fibrous aragonite layer formed prior to the nacreous structure is composed of polycrystalline aragonite with high density of {1 1 0} twins. TEM observation suggests that the interlamellar organic sheet prevents the inheritance of the twins, by selecting only single domain of the twins, through the mineral bridge.     

Intramolecular iodoetherification of ene or diene ketals: facile synthesis of spiroketals

A novel and rapid approach to chiral mono- or di-substituted spiroketals based on remote asymmetric induction by intramolecular iodoetherification of ene or diene ketals has been developed. This strategy concisely offers 5,5- and 5,6-spiroketals including the natural insect pheromone of the wasp.     

Enantiomer separation of pharmaceuticals by capillary gas chromatography with novel chiral stationary phases

New chiral stationary phases of polydimethylsiloxane anchored with (S)-(-)-t-leucine derivatives were provided for use in enantiomer separation of pharmaceuticals by capillary gas chromatography. Fifteen pharmaceuticals were separated into their enantiomeric pairs by converting them into pentafluoropropionyl and heptafluorobutyryl derivatives. The separation factor and resolution obtained from the new phases were superior to those from the conventional Chirasil-Val capillary column.     

Fluorophotometric Determination of Hydrogen Peroxide with Fluorescin in the Presence of Cobalt (II) and Reaction Against Other Reactive Oxygen Species

A fluorophotometric method for the determination of hydrogen peroxide (H₂O₂) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent lactoid fluorescein, by H₂O₂ to give highly fluorescein fluorescence emission. In the determination of H₂O₂, the calibration curve exhibited linearity over the H₂O₂ concentration range of 1.5–310 ng mL⁻¹ at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL⁻¹, 30.8 ng mL⁻¹, and for 308 ng mL⁻¹ of H₂O₂, respectively. The detection limit for H₂O₂ was 1.9 ng mL⁻¹ six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such as singlet oxygen (¹O₂), hydroxyl radical (^•OH), peroxynitrite (ONOO⁻) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery tests of H₂O₂ in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory.     

Approximation of fixed points for amenable semigroups of nonexpansive mappings in Banach spaces

The purpose of this paper is to study iterative schemes of Browder and Halpern types for a semigroup of nonexpansive mappings on a compact convex subset of a smooth (and strictly convex) Banach space with respect to a sequence of strongly asymptotic invariant means defined on an appropriate space of bounded real valued functions of the semigroup. Various applications to the additive semigroup of nonnegative real numbers and commuting pairs of nonexpansive mappings are also presented.     

Photochemical intramolecular nitrene insertion of 6-azidouridine derivatives

A highly efficient intramolecular nitrene insertion was observed upon irradiation of 6-azidouridine derivatives. The N⁶,2′-cyclo structure of the product was determined unequivocally by X-ray crystallography.