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.     

Tricolor photoviscoelastic technique and its application to moving contact

A new technique for simultaneous determination of both fringe order and principal direction of birefringence in practical photoviscoelastic analysis using white incident light with a set of the primary colors, called tricolor photoviscoelasticity, is described. This method can determine both the fringe order and principal direction of birefringence from a single-color photoviscoelastic image under plane polarization. Then, the authors evaluate time dependent stresses and strains around a contact region in a viscoelastic strip plate under nonproportional loading condition. The variations of the principal stresses and strains are easily obtained over a wide time range by use of the optical constitutive equations of photoviscoelasticity and the characteristic material property functions.     

Synthesis and Magnetic Property of Polyacetylene Bearing πConjugated Bis(Diphenylene)Phenylallyl Radical

Abstract

m- and p Bis(diphenylene)propenylphenylacetylene (m-, p-8) were synthesized and polymerized with WCI₆, MoCl₅, and Rh catalyst, yielding solvent-soluble poly(phenylacetylene)s bearing a π-conjugated bis(di-phenylene)propenyl groups (m-, p-7a). The polymers gave their polyanion derivatives, which were electrolytically and chemically oxidized to yield the corresponding polyradicals (m-, p-7b). The polyradicals were chemically very stable due to the resonance stabilization of an unpaired electron whose spin concentration could be increased up to ca. 2 × 10²³ spins per molar monomer unit. ESR spectroscopy suggested an antiferro-magnetic interaction between unpaired electrons.     

Synthesis and Characterization of the Crystalline Methyl α-Glycoside of the Repeating Unit of the O-Polysaccharide of Vibrio Cholerae O:1

Abstract

There are more than eighty serotypes of Vibrio cholerae, all causing disease with symptoms of Asian cholera. Systematic prevention of cholera by immunization has not yet been achieved because of a lack of a protective vaccine. Vibrio cholerae 0:1 Gramnegative bacteria occur as two immunologically distinct strains: Ogawa and Tnaba. The lipopolysaccharide (LPS) of both strains seem to contain the same 0-polysaccharide antigen consisting^3,4 of (1+2)-a-linked 4-amino-4,6-dideoxy-a-D-mannopyranosyl residues the amino groups of which are acylated with 3-deoxy-L-glycero-tetronic acid. Although the chemical structure of the 0-polysaccharides has been known5 since 1979, the synthesis of its monomeric repeating unit was reported only in 1988.     

Bounding Contingent Claim Prices via Hedging Strategy with Coherent Risk Measures

We generalize the notion of arbitrage based on the coherent risk measure, and investigate a mathematical optimization approach for tightening the lower and upper bounds of the price of contingent claims in incomplete markets. Due to the dual representation of coherent risk measures, the lower and upper bounds of price are located by solving a pair of semi-infinite linear optimization problems, which further reduce to linear optimization when conditional value-at-risk (CVaR) is used as risk measure. We also show that the hedging portfolio problem is viewed as a robust optimization problem. Tuning the parameter of the risk measure, we demonstrate by numerical examples that the two bounds approach to each other and converge to a price that is fair in the sense that seller and buyer face the same amount of risk.     

Space potential particles to enhance the stability of projection-based particle methods

Particle methods have been seldom verified by a Karman vortex simulation, which is commonly performed as a typical benchmark in computational fluid dynamics. This is mainly due to a difficulty in suppression of occurrence of unphysical voids manifested usually in a strong vortex on account of definition of free surface by the Lagrangian tracking framework with inconsistency in volume conservation. This paper presents a simple and effective scheme as a free-surface boundary condition of projection-based particle methods, namely the MPS (moving particle semi-implicit) and Incompressible SPH (ISPH) methods to handle the free surface with consistency in volume conservation. The new scheme is introduced into the Poisson pressure equation (PPE) with consideration of a potential in void space as space potential particle (SPP), to reproduce physical motions of particles around free surface through a particle–void interaction. The enhancing effect of the newly proposed SPP scheme is shown by simulating a few numerical tests, including a whirling water flow, a two-phase surfacing flow, and a set of Karman vortex simulations.     

商业模式创新对财务绩效的影响研究:基于新兴技术企业的实证

研究分析了商业模式创新对财务绩效的影响以及这种影响的环境条件。研究提出了6个理论假设,并采用来自151个新兴技术企业的样本进行了实证检验。研究发现效率型和新颖型商业模式创新都能促进财务绩效。市场不成熟和不正当竞争会加强效率型商业模式创新对财务绩效的促进作用,而不正当竞争会削弱新颖型商业模式创新对财务绩效的促进作用。     

Poly(ethylene terephthalate) Nanofibers Made by Sea–Island‐Type Conjugated Melt Spinning and Laser‐Heated Flow Drawing

Nylon‐6/poly(ethylene terephthalate) (PET) ultra‐multi‐island sea–island conjugated melt‐spun fibers are flow‐drawn at a draw ratio of 174 with heating by CO₂ laser irradiation. Continuous PET nanofibers that have a diameter of 39 nm could be obtained from the flow‐drawn fiber with further drawing and removal of the sea component. In addition, the drawn fiber has a strength of 0.54 GPa. This result shows that a PET nanofiber having a strength almost equal to that of a conventional PET fiber can be obtained by the combination of conjugate‐melt‐spinning and laser‐heated flow‐drawing.