Mechanism of BPh3-Catalyzed N-Methylation of Amines with CO2 and Phenylsilane: Cooperative Activation of Hydrosilane

BPh₃ catalyzes the N-methylation of secondary amines and the C-methylenation (methylene-bridge formation between aromatic rings) of N,N-dimethylanilines or 1-methylindoles in the presence of CO₂ and PhSiH₃; these reactions proceed at 30–40 °C under solvent-free conditions. In contrast, B(C₆F₅)₃ shows little or no activity. ¹¹B NMR spectra suggested the generation of [HBPh₃]⁻. The detailed mechanism of the BPh₃-catalyzed N-methylation of N-methylaniline ( 1 ) with CO₂ and PhSiH₃ was studied by using DFT calculations. BPh₃ promotes the conversion of two substrates (N-methylaniline and CO₂) into a zwitterionic carbamate to give three-component species [Ph(Me)(H)N⁺CO₂⁻⋅⋅⋅BPh₃]. The carbamate and BPh₃ act as the nucleophile and Lewis acid, respectively, for the activation of PhSiH₃ to generate [HBPh₃]⁻, which is used to produce key CO₂-derived species, such as silyl formate and bis(silyl)acetal, essential for the N-methylation of 1 . DFT calculations also suggested other mechanisms involving water for the generation of [HBPh₃]⁻ species.     

Hydrophobic Monomers Recognize Microenvironments in Hydrogel Microspheres during Free-Radical-Seeded Emulsion Polymerization

The three-dimensional structure of nanocomposite microgels was precisely determined by cryo-electron micrography. Several nanocomposite microgels that differ with respect to their nanocomposite structure, which were obtained from seeded emulsion polymerization in the presence of microgels, were used as model nanocomposite materials for cryo-electron micrography. The obtained three-dimensional segmentation images of these nanocomposite microgels provide important insights into the interactions between the hydrophobic monomers and the microgels, that is, hydrophobic styrene monomers recognize molecular-scale differences in polarity within the microgels during the emulsion polymerization. This result led to the formation of unprecedented multi-layered nanocomposite microgels, which promise substantial potential in colloidal applications.     

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...     

Intended Treatments of Arithmetic Average in U.S. and Asian School Mathematics Textbooks

This study examined how selected U.S. and Asian mathematics curricula are designed to facilitate students' understanding of the arithmetic average. There is a consistency regarding the learning goals among these curriculum series, but the focuses are different between the Asian series and the U.S. reform series. The Asian series and the U.S. commercial series focus the arithmetic average more on conceptual and procedural understanding of the concept as a computational algorithm than on understanding the concept as a representative of a data set; however, the two U.S. reform series focus the concept more on the latter. Because of the different focuses, the Asian and the U.S. curriculum series treat the concept differently. In the Asian series, the concept is first introduced in the context of “equal‐sharing” or “per‐unit‐quantity,” and the averaging formula is formally introduced at a very early stage. In the U.S. reform series, the concept is discussed as a measure of central tendency, and after students have some intuitive ideas of the statistical aspect of the concept, the averaging algorithm is briefly introduced.     

When does the subadditivity theorem for multiplier ideals hold?

Demailly, Ein and Lazarsfeld proved the subadditivity theorem for multiplier ideals on nonsingular varieties, which states the multiplier ideal of the product of ideals is contained in the product of the individual multiplier ideals. We prove that, in the two-dimensional case, the subadditivity theorem holds on log terminal singularities. However, in the higher dimensional case, we have several counterexamples. We consider the subadditivity theorem for monomial ideals on toric rings and construct a counterexample on a three-dimensional toric ring.

     

Analysis method of the angiotensin-I converting enzyme inhibitory activity based on micellar electrokinetic chromatography.

A micellar electrokinetic chromatography (MEKC) method was developed for estimating the angiotensin-I converting enzyme (ACE) inhibitory activity by separating the hippuric acid liberated in the ACE reaction mixture in the presence of an inhibitor, captopril. The hippuric acid was successfully separated and detected by MEKC with a 25 mM sodium dodecyl sulfate solution in a 25 mM phosphate-50 mM borate buffer at pH 7.0; the total analysis took about 5 min. A good linear relationship was observed between the inhibitor and the peak area of hippuric acid release. No significant difference in the ACE inhibitory activity (IC50) of captopril (an antihypertensive medicine) or autolyzed-mushrooms (functional foods) was observed between the conventional method and the MEKC method. The MEKC method was found to be a useful technique for a rapid assay of the ACE inhibitory activity.     

High-quality InAlN/GaN heterostructures grown by metal–organic vapor phase epitaxy

We fabricated high-quality InAlN/GaN heterostructures by metal–organic vapor phase epitaxy (MOVPE). X-ray diffraction measurements revealed that InAlN/GaN heterostructures grown under optimal conditions have flat surfaces and abrupt heterointerfaces. Electron mobility from 1200 to 2000 cm²/V s was obtained at room temperature. To our knowledge, this mobility is the highest ever reported for InAlN/GaN heterostructures. We also investigated the relationship between the Al composition and sheet electron density (N_s) for the first time. N_s increased from 1.0×10¹² to 2.7×10¹³ cm⁻² when the Al composition increased from 0.78 to 0.89.     

Effect of core-shell micelle formation on the redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide)

Redox properties of phenothiazine-labeled poly(ethyl glycidy ether)-block-poly(ethylene oxide) (PT-EGE_n-b-EO_m) are reversibly changed by core-shell micelle formation. In the temperature range higher than the critical micellization temperature (cmt), the anodic potential of PT group positively shifts and concomitantly its anodic current decrease, or levels off compared to those of the reference polymer PT-EO_m without the thermo-responsive EGE_n segment. The former alteration is caused by incorporation of hydrophobic PT groups into a core of the micelle and the latter by the decrease in the diffusion coefficient of PT groups due to formation of the core-shell micelles. The cmt value and the temperature-dependent alteration in the redox properties strongly depend on the polymer structure, especially the length of thermo-responsive EGE_n segment. The electrochemically determined hydrodynamic radii of the polymer aggregates seem to be overestimated, compared to the values reported for the aggregates of other thermo-responsive polymers with similar molecular weights, implying the presence of electrochemically inactive PT groups in the copolymers having longer thermo-responsive segments.     

Discrimination of carbonyl groups of meso-α-diketones with Horner-Wadsworth-Emmons reagent of chiral binaphthyl esters

Asymmetric Horner-Wadsworth-Emmons reactions of selected meso-α-dicarbonyl compounds with chiral phosphonate reagents, which possessed axially dissymmetric 1,1′-bi-2- or 8-naphthol at the carboxylate moiety as a chiral auxiliary, were examined. The reactions proceeded smoothly with good chemical yields as well as with high diastereoselectivities. Z-olefins were preferentially formed, and it was found that the free hydroxy group at the 2′- or 8′-position on the naphthalene ring plays a crucial role in the high diastereoselectivity, probably due to a complex-induced proximity effect. Mechanistic considerations are also described.     

Thermochromic transitions in poly(di-n-hexylsilane) films

The spectra of absorption (77–398 K) and luminescence (5 K) of poly(di-n-hexylsilane) films are studied in relation to the heating of the films above the phase transition temperature. Two new absorption bands in the region of the band of the gauche conformation are found. The position and intensity of these bands depend on the annealing temperature, annealing regime, and sample thickness. These bands are assumed to be associated with the appearance of a liquid crystalline phase in the polymer, which is determined by intermolecular interactions between neighboring polymer chains. The appearance of the liquid crystalline phase in the heat-treated polymer films is confirmed by the increase in their birefringence in comparison with the birefringence of the initial films and by the observation of a stable orientation of an E 7 nematic liquid crystal applied to the surface of an annealed sample. In addition, the absorption spectra of the films cooled after the annealing exhibit many new bands in comparison with the spectra of the initial samples. These bands are associated with the appearance in the polymer of defect states and longer segments as a result of orientation of polymer chains. The appearance of longer segments is consistent with the observation of a long-wavelength band in the luminescence spectra of the annealed samples.