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.     

Synthesis and refractive‐index control of fluoropolymers by the polyaddition of bis(epoxide)s and triazine di(aryl ether)s

The polyaddition of fluorine‐containing bis(epoxide)s and fluorine‐containing triazine di(aryl ether)s were examined to give the corresponding fluorine‐containing poly(cyanurate)s. It was observed that the synthesized fluoropolymers had good thermal stabilities and good film‐forming properties. The glass transition temperatures (T_g's) and refractive‐indices (n_D's) of synthesized polymers were determined by differential scanning calorimetry and ellipsometry, respectively, and it was found that the values of T_g's and n_D's were supported by their fluorine containing ratios and skeletons. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4421–4429, 2007     

Infrared Features of Unquenched Lattice Landau Gauge QCD

The running coupling and the Kugo-Ojima parameter of unquenched lattice Landau gauge are simulated and compared with the continuum theory. Although the running coupling measured by the ghost and gluon dressing function is infrared suppressed, the running coupling has a maximum of α₀ ∼ 2 − 2.5 at around q = 0.5 GeV irrespective of the fermion actions (Wilson fermions and Kogut-Susskind (KS) fermions). The Kugo-Ojima parameter c which saturated to about 0.8 in quenched simulations becomes consistent with 1 in the MILC configurations produced with the use of the Asqtad action, after averaging the dependence on polarization directions caused by the asymmetry of the lattice. The presence of the correction factor 1 + c ₁/q ² in the running coupling depends on the lattice size and the sea quark mass. In the large lattice size and small sea quark mass, c ₁ is confirmed of the order of a few GeV. The MILC configuration of a = 0.09 fm suggests also the presence of dimension-4 condensates with a sign opposite to the dimension-2 condensates. The gluon propagator, the ghost propagator, and the running coupling are compared with recent pQCD results including an anomalous dimension of fields up to the four-loop level.     

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.     

Introduction of several trifluoromethyl groups onto the activated aromatic materials with CF3TMS-CuI-KF system

Trifluoromethylation onto the tetrafluorophthalonitrile and tetrafluoroisophthalonitrile has been carried out using CF₃TMS-CuI-KF system, and it was demonstrated that these trifluoromethylation enabled us to successfully construct di- and/or tri-trifluoromethylated benzonitriles via the decyanotrifluoromethylation.     

Photoluminescence properties of trace amounts of Pr and Tb in yttria-stabilized zirconia

We have investigated the photoluminescence (PL) properties of trace amounts of Pr and Tb in single-crystal samples of yttria-stabilized zironia (YSZ), and found that Pr of the order of 10⁻⁶ mass% and Tb of the order of 10⁻⁵ mass% in YSZ can be detected by the PL spectroscopy. The PL spectra of the YSZ samples for the 280 nm excitation were comprised of several peaks and a broad emission. The peaks were attributed to transitions of Pr³⁺ and Tb³⁺ in the YSZ samples, whereas the broad emission seemed to be attributed to the yttria-associated oxygen vacancies. The peak intensities corresponded to the amounts of Pr and Tb in the YSZ samples, the amounts of which were analyzed by glow discharge mass spectrometry. In the PL excitation spectra, but not in the photoabsorption spectra, small peaks at 376 and 381 nm were observed, and were attributed to the transitions of Tb³⁺ in the YSZ samples. The results of the PL excitation spectra corresponding to the Pr³⁺ line emissions suggest that the charge transfer occurs between the YSZ and Pr ion in it. The trace amounts of these lanthanoids in YSZ would disturb the decay process of the photoinduced electrons to the yttria-associated oxygen vacancies.     

A New Method for Rotation and Brightness Invariant Pattern Recognition Based on Modified Multiple Circular Harmonic Expansions

A new method for rotation and brightness invariant pattern recognition was proposed by applying multiple circular harmonic expansions to the joint transform correlator. The amplitudes of the multiple orders of circular harmonic expansions made from a detecting image were synthetically modified to respond to the same auto-correlation peaks. These modified circular harmonic expansions were arranged in the input plane as reference patterns together with an arbitrary target pattern, and the correlation signals between them were calculated in the subtracted joint transform correlator. The fraction of the correlation-peak intensities between the target and the references were extracted as a new discrimination parameter. This new parameter performs pattern recognition under rotation and brightness invariance with good discriminability. Its high discriminability has been proved in computer simulations using the face image patterns of many individuals.     

SILEX-1装置上等离子体尾场加速电子初步实验

激光等离子体加速电子机制可以产生准单能的高能电子束, 近年来成为国际上的研究热点. 中国工程物理研究院激光装置已经能够达到286TW的输出功率, 为国内在该领域的研究提供了实验条件. 文章介绍了在SILEX-1装置上开展的激光等离子体加速电子的初步实验, 并对测得结果进行讨论, 为下一步实验的进行提供了准备条件.