Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Improvement in flow-sheet of extraction chromatography for trivalent minor actinides recovery

Journal of Radioanalytical and Nuclear Chemistry - Extraction chromatography flow-sheet employing octyl(phenyl)-N,N-diisobutylcarbonoylmethylphosphine oxide and bis(2-ethylhexyl) hydrogen phosphate...     

Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

Extending the possibility of an N-Troc-protected sialic acid donor toward variant sialo-glycoside synthesis

The potential of an N-Troc-protected sialic acid donor, equipped with phenylsulfenyl functionality as a leaving group, has been explored. As a result, the entitled donor was proven to be highly reactive and to have broad applicability toward the synthesis of variant sialo-glycans, which have N-glycolyl, de-N-acetyl, 1,5-lactam and 8-O-sulfo sialic acid analogs.     

On the Lp–Lq maximal regularity for Stokes equations with Robin boundary condition in a bounded domain

We obtain the L_p–L_q maximal regularity of the Stokes equations with Robin boundary condition in a bounded domain in ?ⁿ (n?2). The Robin condition consists of two conditions: v ? u=0 and αu+β(T(u, p)v – 〈T(u, p)v, v〉v)=h on the boundary of the domain with α, β?0 and α+β=1, where u and p denote a velocity vector and a pressure, T(u, p) the stress tensor for the Stokes flow and v the unit outer normal to the boundary of the domain. It presents the slip condition when β=1 and non‐slip one when α=1, respectively. The slip condition is appropriate for problems that involve free boundaries. Copyright © 2006 John Wiley & Sons, Ltd.     

Phenomenon of labyrinth seal with low static pressure difference and large clearance

This paper discusses the straight-through type labyrinth seal. This labyrinth seal is used for axial flow fans, which h ave an outer ring at the blade tip to seal the clearance between the ring tip and the fan shroud, in order to prevent the reverse flow or leakage. These fans are used for the cooling of automobile radiators . In these cases, the labyrinth seal is used in an extremely low static pressure difference and a large clearance . A significant decrease of the leakage rate was reported even when the labyrinth seal rotated in comparatively low speed in this unique condition according to the authors’ former report. However, this phenomen on is differ ent from past research. Further more the cause of th is phenomenon has not been determined. Therefore, the internal flow was depicted with Computational Fluid Dynamics (CFD) in or der to clarify the ca use of this phenomenon. The results of CFD show that the leakage rate decreases significantly because the carry -over flow is intercepted in the expansion groove. This is the newly discovered phenomenon which occurs under the unique condition of an extremely low differential pressure. It has not been pointed out before as the reason why the rotation decreases the leakage rate.     

Synthesis of a mechanically linked oligo[2]rotaxane

A bifunctional [2]rotaxane, bearing two free functional groups each in the ring and axial parts, was synthesized, followed by its polycondensation with methylene diphenyl diisocyanate leading to a mechanically linked oligo[2]rotaxane.     

Structure and molecular motion of poly(ethylene oxide) chains adsorbed on a silica-tethered poly(methyl methacrylate) by the spin label method

The spin-label method was used to study the structure and molecular motion of poly(ethylene oxide) (PEO) chains adsorbed on a silica-tethered poly(methyl methacrylate) (PMMA). Spin-labelled PEO with a narrow molecular weight distribution, having number averaged molecular weight (M _N)=6.0×10³, was adsorbed on the surface of the silica-tethered PMMA with various grafting ratios in carbon tetrachloride solution at 35?°C. ESR spectra were measured at various temperatures after the samples were completely dried. The ESR spectra are composed of two spectra arising from spin-labels attached to “train” and “tail” segments, which are strongly and weakly interacted with the silica surface, respectively. The fractional amount of the “tail” segments increases extremely with the grafting ratio of PMMA. Molecular mobility of the PEO chains estimated from the temperature dependence of the ESR spectra also decreases significantly with the grafting ratio of PMMA. Structure and molecular motion of the PMMA chains tethered on the silica were also studied using the spin-labelled PMMA. Consequently, parts of the PEO segments penetrate into the PMMA chains and is adsorbed on the silica surface (“train” segments), whereas parts of the PMMA segments protrude from the surface. The other PEO segments are entangled with the tethered PMMA chains (“tail” segments).