Highly regio- and stereoselective Michael addition of pseudouridine with propiolates: An efficient method for the synthesis of (E)-pseudouridine-N1-acrylate

The Michael addition of pseudouridine with various propiolates in the presence of DBU as a base and DMF as a solvent is described. It is noteworthy that the reaction is highly regio- and stereoselective and affords (E)-pseudouridine-N1-acrylate in good yields with high purities.     

On the asymptotic behavior of expanding gradient Ricci solitons

Let (M, g, f) be an n-dimensional expanding gradient Ricci soliton with faster-than-quadratic-decay curvature, i.e., ${\lim_{{\rm dist}(O,x)\rightarrow\infty} |{\rm Sect}(x)|\cdot {\rm dist}(O,x)^2=0}$ . When M is simply connected at infinity and n??? 3, we show that its tangent cone at infinity must be a manifold and is isometric to ${\mathbb{R}^n}$ . Here, we also assume that M has only one end for the simplicity of the statement. A crucial step to gain the regularity of the tangent cone at infinity is to prove that the injectivity radius grows linearly. This can be achieved by combining the curvature assumption and a lower bound estimate of volume ratio of all geodesic balls, which is attained as Theorem 3. On the other hand, we also study the asymptotic volume ratio of non-steady gradient Ricci solitons under other weaker conditions.     

Inhibition of O-GlcNAcase by a gluco-configured nagstatin and a PUGNAc-imidazole hybrid inhibitor

Synthesis of a PUGNAc-imidazole hybrid and its characterization as an inhibitor of human O-GlcNAcase through enzyme kinetics and X-ray structural analysis.     

Low-frequency electronic and optical properties of rhombohedral graphite

Low-energy electronic and optical properties of ABC-stacked graphite are respectively studied by the tight-binding model and gradient approximation. The band structures include linear and parabolic bands with and without degeneracy. They show strongly anisotropic dispersions. ABC-stacked graphite is a semimetal due to the slight overlap near the Fermi level between the conduction and valence bands. The interlayer interactions change the energy dispersion, state degeneracy, and the positions of band-crossings and band-edge states. When the state energy is higher than the degenerate energy of the conduction band (E(2d)(c)) or lower than that of the valence bands (E(2d)(v)), a greater number of states might exist. The special band structures would be reflected in the density of states (DOS), the joint density of states (JDOS), and the absorption spectra (A(ω)). For example, the DOS exhibits a cave-like structure at ω = E(2d)(c) and E(2d)(v). Both a special jump in the JDOS and a turning point in the A(ω) occur at ω = E(2d)(c) - E(2d)(v). The DOS and A(ω) could be respectively verified by scanning tunneling spectroscopy and optical absorption spectroscopy.     

Photoswitching tetranuclear rhenium(I) tricarbonyl diimine complexes with a stilbene-like bridging ligand

Highly efficient photoswitching tetranuclear rhenium(I) tricarbonyl diimine complexes with a stilbene-like bridging ligand are reported. The ability to directly populate excited states localized on the bridging ligand is the key for the observed efficient photoisomerization.     

Modal interactions and energy transfers in isotropic turbulence as predicted by local energy transfer theory

Energy transfer processes in decaying, three-dimensional, isotropic turbulence are investigated using numerical results from local energy transfer (LET) theory. The study covers a wide range of evolved, microscale Reynolds numbers (5 < R_λ < 250). It is found that the energy transfer is mainly local (between scales of similar size), but there are also some signs of nonlocal transfer at higher Reynolds number. The nature of the underlying triad-wavenumber interactions, on the other hand, seems to depend on both the Reynolds number and the wavenumber range of interest. In the energy containing and dissipation ranges, both local (all three scales of the triad interaction are of comparable size) and nonlocal (one scale is much larger than the remaining two) interactions are important, with the latter becoming more dominant as the Reynolds number increases. But our nonlocal interactions tend to be less severe than those observed by Domaradzki and Rogallo. More significantly, in the inertial range of high Reynolds number flows, the LET theory predicts dominance of local and near-local interactions. While this is contrary to the result from eddy damped quasi-normal Markovian theory that the important triad interactions are mainly nonlocal, it is closer to the Kolmogorov picture of turbulence. Another interesting result is that, despite their inherent differences, the LET theory and the full simulation of Ohkitani and Kida predict inertial-range values for the energy transfer locality function in fairly good agreement, not only with each other, but also with the analytical closure theory result for infinite Reynolds number, stationary turbulence by Kraichnan. The calculated values reveal that the contributions to the net energy transfer are predominantly from near-local interactions (scale ratios ≈ 4), which is indicative of cancellation of large numbers of highly nonlocal interactions.     

Using colloid lithography to fabricate silicon nanopillar arrays on silicon substrates

In this study, we partially grafted geminal silanol groups in the protecting organic shells on the surfaces of gold nanoparticles (AuNPs) and then assembled the alkyl-AuNP-Si(OH)(4) particles onto the surfaces of silicon (Si) wafers. The density of assembled AuNPs on the Si surface was adjusted by varying the geminal silanol group content on the AuNP surface; at its optimal content, it approached the high assembly density (0.0254 particles/nm(2)) of an AuNP assembled monolayer. Using reactive-ion etching (RIE) with the templates as masks, we transferred the patterned AuNP assemblies to form large-area, size-tunable, Si nanopillar arrays, the assembly density of which was controlled by the dimensions of the AuNPs. Using this colloidal lithography (CL) process, we could generate Si nanopillars having sub-10-nm diameters and high aspect ratios. The water contact angles of the high-aspect-ratio Si nanopillars approached 150°. We used another fabrication process, involving electron beam lithography and oxygen plasma treatment, to generate hydrophilic 200-nm-resolution line patterns on a Si surface to assemble the AuNPs into 200-nm-resolution dense lines for use as an etching mask. Subsequent CL provided a patterned Si nanopillar array having a feature size of 200 nm on the Si surface. Using this approach, it was possible to pattern sub-10-nm Si nanopillar arrays having densities as high as 0.0232 nm(-2).     

Radiation induced preparation of new multifunctional nanobiowebs

New poly(vinylidene fluoride) based multi-functional (electroconductive, bioactive and catalytic) nano-biowebs were prepared through gamma radiation induced formation of silica and gold nanoparticles (Au NPs) within electrospun (poly vinylidene fluoride) nanofiberous membranes. The multifunctional membrane is designated as PVdF@silica/Au ESNFM. The morphology of PVdF@silica/Au ESNFM was examined by field emission scanning electron microscopy. The presence of Au particles was confirmed by energy dispersive x-ray analysis. The crystal structure of Au particles and the formation of silica were confirmed by X-ray diffraction analysis. The multi-functionalities (electroconductive, bioactive and catalytic) of the nano-webs were evaluated by cyclic voltammetry. Cytochrome c was immobilized to generate nano-bioweb (PVdF@silica/Au/cyt c ESNFM), which exhibited electrochemical responses to nitrite ions.     

Novel acid-catalyzed rearrangement of methanofullerenes bearing an alpha-ylidic ester to cyclopentanofullerenes: a vinyl cyclopropane-type ring expansion

A novel acid-catalyzed ring expansion of methanofullerenes bearing an alpha-ylidic ester has been investigated. Treatment of dialkyl acetylenedicarboxylate and tricycloalkylphosphine with C(60) led to the isolation of a methanofullerene ylide after passing the reaction mixtures through a basic alumina column. If the reaction mixture was passed through a silica gel column, a cyclopentanofullerene was isolated instead. These new cyclopentanofullerenes consisted of a fused cyclopentanone ring bearing an alpha-hydroxy ester and a phosphonium ylide and were confirmed by their NMR, mass, and X-ray diffraction data. The cyclopentanofullerenes were formed by the ring expansion of the corresponding methanofullerenes in the presence of silica gel. The ring expansion also proceeded by treating methanofullerene with acetic acid in chloroform. On the other hand, the methanofullerenes from RO(2)CCCCO(2)R, PAr(3), and C(60) were stable in silica gel. However, upon heating with acetic acid at 50 degrees C, they underwent ring expansion and dephosphination to give cyclopentenofullerenes. An implicit vinyl cyclopropane ring expansion mechanism was proposed to account for this novel acid-catalyzed rearrangement.