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.     

Optimization of the surface texture for silicon carbide sliding in water

Surface texturing has been recognized as an effective means to improve the tribological performances of sliding surfaces. Usually, generation additional hydrodynamic pressure to increase the load carrying capacity is regarded as the most significant effect of surface texture. In the case of silicon carbide sliding against identical material in water, the experimental results indicate that surface texture is also helpful to improve the running-in progress to smooth the contact surfaces, showing another reason to result in low friction. Based on the consideration of enhancing the generation of hydrodynamic pressure and improving running-in progress, a surface texture pattern, which was combined with large (circle, 350 μm in diameter) and small (rectangular, 40 μm in length) dimples, was designed to maximize the texture effect on the load carrying capacity of SiC surfaces sliding in water. The friction coefficient of such textured surface was evaluated and compared with that of untextured and those only with large or small dimples only. The friction reduction mechanisms of the patterns with different dimples in size are discussed.     

Improved detectability with a polymer-based trapping device in rapid HPLC analysis for ultra-low levels of bisphenol A (BPA) in environmental samples.

A new high-performance liquid chromatography (HPLC) method has been developed to detect ultra-low concentrations of bisphenol-A (BPA) (below 1 ng/L (ppt)) using column switching electrochemical detection (ECD). The results were superior to those obtained from manual pretreatment procedure with membrane stationary phase. BPA is inherently ubiquitous in the environment, including tools and solvents used for its analysis; to obtain meaningful results, therefore, the concentration of the overall BPA contamination must be below the detection limit for BPA using the analytical system. Therefore, purified water for preparing the standard BPA solution must be filtered with a hydrophobic membrane to suppress BPA background levels of contamination. In addition, we investigated methods for effectively preserving environmental water containing BPA. The addition of a small amount of ethylenediaminetetraacetic acid (EDTA) provided good recovery even after overnight storage. By employing these precautionary measures and procedures to reduce BPA contamination from the analytical procedure, we could accurately determine l(-10) ppt of BPA in environmental water samples using a column switching HPLC system.     

On the identification of degenerate indices in the nonlinear complementarity problem with the proximal point algorithm

In this paper we focus on the problem of identifying the index sets P(x):=i|x_i>0, N(x):={i|F_i(x)>0 and C(x):=i|x_i=F_i(x)=0} for a solution x of the monotone nonlinear complementarity problem NCP(F). The correct identification of these sets is important from both theoretical and practical points of view. Such an identification enables us to remove complementarity conditions from the NCP and locally reduce the NCP to a system which can be dealt with more easily. We present a new technique that utilizes a sequence generated by the proximal point algorithm (PPA). Using the superlinear convergence property of PPA, we show that the proposed technique can identify the correct index sets without assuming the nondegeneracy and the local uniqueness of the solution.This work was supported in part by a Grant-in-Aid for Scientific Research from the Ministry of Education, Science, Sports and Culture of Japan.Mathematics Subject Classification (2000): 90C33, 65K10     

Development and features of hydro-membrane gas chromatography.

Hydro-membrane gas chromatography (HMGC) is achieved by the annular condensation of water in a capillary column at less than 70 degrees C. The annular membrane of water is formed as a result of the wettability of the stationary phase, which is induced at a water contact angle ranging from 75 degrees to 79 degrees, as derived from a solubility parameter (delta) range of 15.7 +/- 0.3 MPa(1/2) of the coated resin. The range of the liquid to gas volume ratio (beta) required to support the annular membrane should be kept between 0.00005 and 0.0003. In the case of a 0.25-mm i.d. column, the ratio can be set by the combination of a 0.1 to 0.2 microl min(-1) water supply rate and helium gas flow rate. Separation by HMGC develops not only a gas-solid partition but also a focusing effect on the water membrane. One feature of HMGC is that it gives a non-adsorption chromatogram based on the blocking effect of pre-adsorbed water; furthermore, despite the presence of a relatively large quantity of water, the electron impact ionization efficiency is kept the same as in the usual GC/MS condition. The detection limit with the injection of 1 microl of aquatic solution was estimated to be less than 0.1 ppb of low-molecular-weight fatty acids with s/n = 5 on a mass chromatogram at m/z 45. The HMGC/EI-MS system can be applied to the trace analysis of C1 to C3 volatile acids, volatile inorganic acids, and halogenated organic acids in water.     

Quasi-monocyclic near-infrared pulses with a stabilized carrier-envelope phase characterized by noncollinear cross-correlation frequency-resolved optical gating.

Precise characterization of noncollinear optical parametric amplifier idler pulses that have bandwidths of more than an octave with a center wavelength at 990 nm was demonstrated. The method employed was cross-correlation frequency-resolved optical gating with broadband sum-frequency mixing to take advantage of the idler's angular dispersion. Compression to near the transform limit was achieved to produce quasi-monocyclic near-infrared pulses by use of a deformable membrane mirror.     

Alternating copolyfluorenevinyles with polynuclear aromatic moieties: Synthesis,photophysics, and electroluminescence

Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with η_EL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007     

Phase transitions of lanthanide monophosphides with NaCl-type structure at high pressures

Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms.