Mn(III)-initiated facile oxygenation of heterocyclic 1,3-dicarbonyl compounds

The Mn(III)-initiated aerobic oxidation of heterocyclic 1,3-dicarbonyl compounds, such as 4-alkyl-1,2-diphenylpyrazolidine-3,5-diones, 1,3-dialkylpyrrolidine-2,4-diones, 3-alkyl-1,5-dimethylbarbituric acids, and 3-butyl-4-hydroxy-2-quinolinone gave excellent to good yields of the corresponding hydroperoxides, which were gradually degraded by exposure to the metal initiator after the reaction to afford the corresponding alcohols. The synthesis of 30 heterocyclic 1,3-dicarbonyl compounds, the corresponding hydroperoxides and the 10 alcohols, their characterization, and the limitations of the procedure are described. In addition, the mechanism of the hydroperoxidation and the redox decomposition of the hydroperoxides are discussed.     

Weak coupling perturbative calculations of the Wilson loop in lattice gauge theory

Weak coupling perturbative calculations of the Wilson loop in lattice gauge theory are carried out numerically up to order g⁴. Comparison of the results with those of the Monte Carlo calculations shows that there exists a non-perturbative contribution of an essential singularity type which may be identified as the string tension.     

Low temperature fabrication of 5-10 nm SiO2/Si structure using advanced nitric acid oxidation of silicon (NAOS) method

We have developed the advanced nitric acid oxidation of Si (NAOS) method to form relatively thick (5-10 nm) SiO₂/Si structure with good electrical characteristics. This method simply involves immersion of Si in 68 wt% nitric acid aqueous solutions at 120 °C with polysilazane films. Fourier transform infrared absorption (FT-IR) measurements show that the atomic density of the NAOS SiO₂ layer is considerably high even without post-oxidation anneal (POA), i.e., 2.28 × 10²² atoms/cm², and it increases by POA at 400 °C in wet-oxygen (2.32 × 10²² atoms/cm²) or dry-oxygen (2.30 × 10²² atoms/cm²). The leakage current density is considerably low (e.g., 10⁻⁵ A/cm² at 8 MV/cm) and it is greatly decreased (10⁻⁸ A/cm² at 8 MV/cm) by POA at 400 °C in wet-oxygen. POA in wet-oxygen increases the atomic density of the SiO₂ layer, and decreases the density of oxide fixed positive charges.     

Gauss maps of the Ricci-mean curvature flow

In this paper, we investigate the Gauss maps of a Ricci-mean curvature flow. A Ricci-mean curvature flow is a coupled equation of a mean curvature flow and a Ricci flow on the ambient manifold. Ruh and Vilms (Trans Am Math Soc 149: 569–573, 1970) proved that the Gauss map of a minimal submanifold in a Euclidean space is a harmonic map, and Wang (Math Res Lett 10(2–3):287–299, 2003) extended this result to a mean curvature flow in a Euclidean space by proving its Gauss maps satisfy the harmonic map heat flow equation. In this paper, we deduce the evolution equation for the Gauss maps of a Ricci-mean curvature flow, and as a direct corollary we prove that the Gauss maps of a Ricci-mean curvature flow satisfy the vertically harmonic map heat flow equation when the codimension of submanifolds is 1.     

Halichonic acid,a new rearranged bisabolene-type sesquiterpene from a marine sponge Halichondria sp.

A new compound, halichonic acid (1), was isolated from a marine sponge Halichondria sp., together with (6R,7S)-7-amino-7,8-dihydro-α-bisabolene (2). The structure of 1 was elucidated by spectroscopic analysis and ECD spectrum calculation to be a rearranged bisabolene-type sesquiterpene having a 3-azabicyclo[3.3.1]nonene moiety. Compound 2 was cytotoxic against HeLa cells with an IC₅₀ value of 50?μM, whereas 1 did not show cytotoxicity even at 50?μM. It is possible that 1 is biosynthesized from farnesyl pyrophosphate and glycine, with rearrangement.     

Chemical Bonding in Polarised Push–Pull Ethylenes

1,1‐Diamino‐2,2‐bis(triflyl)ethylenes with both twisted and planar structures around the partial “C=C” bond were synthesised. Bonding properties in these compounds were analysed by an experimental approach using high‐resolution X‐ray diffraction data treated with X‐ray wavefunction refinement (XWR). In the twisted compound, a dominant contribution of the charge‐separated resonance structure was revealed. On the contrary, the nearly planar compound still showed π‐bonding character, however, with a considerable contribution of the charge‐separated resonance structure.     

Trifluorosulfonylation Cascade in Allenols: Stereocontrolled Synthesis of Bis(triflyl)enones

Herein, we report investigations embodying the first example of reversal of the native regioselectivity in the reaction of allenols with electrophiles. The effortlessness of C−C bond formation, mild reaction conditions, neither catalysts nor light irradiation, and exquisite selectivity, both in terms of functional-group tolerance and chemo-, site-, and stereo-selectivity, converts this trifluorosulfonylation-rearrangement sequence into an appealing protocol for the preparation of novel functionalized enones. The synthetic utility of this method has been validated by the conversion of the initially prepared bis(triflyl)enones into a variety of bis(triflyl)-functionalized molecules such as 1,3-dienes, allylic alcohols, pyrroles, pyrazoles, and chromenes. Besides, DFT calculations have provided a reliable understanding of observed selectivity.     

Isolation and structure determination of a new thiopeptide globimycin from Streptomyces globisporus subsp. globisporus based on genome mining

Based on genome-mining, a new thiopeptide globimycin was discovered from the extract of Streptomyces globisporus subsp. globisporus, along with known one radamycin. The structure of globimycin was established by a combination of 2D NMR and ESI-MS experiments, and globimycin was identified to be a structural isomer of a known thiopeptide methylsulfomycin. The proposed biosynthetic gene cluster for globimycin and radamycin was found in the genome of S. globisporus subsp. globisporus.