[4+1] Cycloaddition of N-acylimine derivatives with isocyanides: efficient synthesis of 5-aminooxazoles and 5-aminothiazoles

[4+1] Cycloaddition reaction between isocyanides and N-acylimine derivatives generated from N-acyl N,O-acetals acting as isocyanophiles has been developed. These reactions proceeded smoothly and cleanly to afford the corresponding 5-aminooxazoles in high yields. This reaction was extended to the syntheses of 5-aminothiazoles by using N-thioacyl N,O-acetals. A wide range of N-acyl N,O-acetals, N-thioacyl N,O-acetals, and isocyanides were found to be applicable to this reaction.     

Role of Re Species and Acid Cocatalyst on Ir‐ReOx/SiO2 in the C–O Hydrogenolysis of Biomass‐Derived Substrates

The catalytic performance of ReO_x‐modified Ir metal catalyst in the hydrogenolysis of C–O bonds is strongly dependent on the choice of solvent. The acidic property of the Re species becomes obvious in the alkane solvent, and the hydrogenolysis reaction proceeds mainly by acid‐catalyzed dehydration and the subsequent metal‐catalyzed hydrogenation. The acidic property of the Re species is weakened in water; however, the hydrogenolysis reaction proceeds in water via a direct mechanism involving S_N2‐like attack of a hydride species at the interface between Ir and ReO_x on the adsorbed Re alkoxide species. This mechanism enabled the selective dissociation of the C–O bond neighboring the CH₂OH group.     

Solubility of Anthraquinone Derivatives in Supercritical Carbon Dioxide: New Correlations

Solubility of several anthraquinone derivatives in supercritical carbon dioxide was readily available in the literature, but correcting ability of the existing models was poor. Therefore, in this work, two new models have been developed for better correlation based on solid–liquid phase equilibria. The new model has five adjustable parameters correlating the solubility isotherms as a function of temperature. The accuracy of the proposed models was evaluated by correlating 25 binary systems. The proposed models observed provide the best overall correlations. The overall deviation between the experimental and the correlated results was less than 11.46% in averaged absolute relative deviation (AARD). Moreover, exiting solubility models were also evaluated for all the compounds for the comparison purpose.     

Molecularly Designed Nanoparticles by Dispersion of Self‐Assembled Organosiloxane‐Based Mesophases

The design of siloxane‐based nanoparticles is important for many applications. Here we show a novel approach to form core–shell silica nanoparticles of a few nanometers in size through the principle of “dispersion of ordered mesostructures into single nanocomponents”. Self‐assembled siloxane–organic hybrids derived from amphiphilic alkyl‐oligosiloxanes were postsynthetically dispersed in organic solvent to yield uniform nanoparticles consisting of dense lipophilic shells and hydrophilic siloxane cores. In situ encapsulation of fluorescent dyes into the nanoparticles demonstrated their ability to function as nanocarriers.     

Bucillamine Inhibits UVB-Induced MAPK Activation and Apoptosis in Human HaCaT Keratinocytes and SKH-1 Hairless Mouse Skin

Ultraviolet B (UVB) radiation is known as a culprit in skin carcinogenesis. We have previously reported that bucillamine (N-[2-mercapto-2-methylpropionyl]-L-cysteine), a cysteine derivative with antioxidant and anti-inflammatory capacity, protects against UVB-induced p53 activation and inflammatory responses in mouse skin. Since MAPK signaling pathways regulate p53 expression and activation, here we determined bucillamine effect on UVB-mediated MAPK activation in vitro using human skin keratinocyte cell line HaCaT and in vivo using SKH-1 hairless mouse skin. A single low dose of UVB (30 mJ cm⁻²) resulted in increased JNK/MAPK phosphorylation and caspase-3 cleavage in HaCaT cells. However, JNK activation and casaspe-3 cleavage were inhibited by pretreatment of HaCaT cells with physiological doses of bucillamine (25 and 100 µm ). Consistent with these results, bucillamine pretreatment in mice (20 mg kg⁻¹) inhibited JNK/MAPK and ERK/MAPK activation in skin epidermal cells at 6–12 and 24 h, respectively, after UVB exposure. Moreover, bucillamine attenuated UVB-induced Ki-67-positive cells and cleaved caspase-3-positive cells in mouse skin. These findings demonstrate that bucillamine inhibits UVB-induced MAPK signaling, cell proliferation and apoptosis. Together with our previous report, we provide evidence that bucillamine has a photoprotective effect against UV exposure.     

Separation of neutral and basic enantiomers by cyclodextrin electrokinetic chromatography using anionic cyclodextrin derivatives as chiral pseudo-stationary phases

Separations of neutral and basic racemates were performed using five different anionic cyclodextrin (CD) derivatives as chiral selectors, viz. carboxymethylated β-CD, β-CD phosphate sodium salt, sulfobutyl ether β-CD sodium salt, carboxymethylated γ-CD, and γ-CD phosphate sodium salt. For the separation of neutral racemates, an untreated fused silica capillary was employed and various neutral racemates were successfully separated. Since the pH of the buffer affected the electroosmotic flow (EOF), the resolution was improved by changing the buffer pH. A polyacrylamide coated capillary was employed for the separation of basic racemates to suppress EOF and to prevent adsorption of cationic analyte on the capillary surface. By choosing an appropriate type and concentration of anionic CD, about 40 basic racemates were successfully separated. Some rough binding constants of basic analytes with an anionic β-CD were measured to discuss the optimum concentration of the CD. The migration direction was dependent on the binding constants and the concentration of the CD. The analyte strongly bound to the anionic CD migrated towards the anode but the weakly bound one moved towards the cathode. Anionic γ-CDs were also very useful for the separation of basic enantiomers. Five neutral CDs were employed as chiral selectors to compare selectivity between charged and neutral CDs, and eleven racemates could only be resolved using anionic CDs. The separation of some basic racemates in human plasma was also described. The direct injection of plasma samples was possible for some enantiomers that did not interact strongly with plasma proteins.     

Removal of phosphate by aluminum oxide hydroxide

The development and manufacture of an adsorbent to remove phosphate ion for the prevention of eutrophication in lakes are very important. The characteristics of phosphate adsorption onto aluminum oxide hydroxide were investigated to estimate the adsorption isotherms, the rate of adsorption, and the selectivity of adsorption. Phosphate was easily adsorbed onto aluminum oxide hydroxide, because of the hydroxyl groups. The adsorption of phosphate onto aluminum oxide hydroxide was influenced by pH in solution: the amount adsorbed was greatest at pH 4, ranging with pH from 2 to 9. The optimum pH for phosphate removal by aluminum oxide hydroxide is 4. The selectivity of phosphate adsorption onto aluminum oxide hydroxide was evaluated based on the amount of phosphate ion adsorbed onto aluminum oxide hydroxide from several anion complex solutions. It is phosphate that aluminum oxide hydroxide can selectively adsorb. The selectivity of phosphate onto aluminum oxide hydroxide was about 7000 times that of chloride. This result indicated that the hydroxyl groups on aluminum oxide hydroxide have selective adsorptivity for phosphate and could be used for the removal of phosphate from seawater.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals [Phys. Status Solidi RRL 5, No. 3, R107–R109 (2011)]

In our article, we reported the observation of monoclinic M2 to M1 structural phase transition in VO₂ single crystal near the temperature of ～49 °C. However, the re‐examination of Laue patterns reveals that previously defined monoclinic M1 and M2 phases can be interpreted as monoclinic M2 and triclinic T phases instead. Careful experimental geometry calibration and further refinement of the lattice parameter ratios and angles show that monoclinic M2 and triclinic T phases fit better with the experimental data. On the other hand, our previous misidentification of the insulating phases does NOT affect the conclusions of our article. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)