Novel and efficient one‐pot synthesis of azuleno[1,2‐b]‐benzothiophenic enones from the corresponding 2‐cycloheptatrientyl‐3‐(2‐furyl)benzothiophenes

2‐Cycloheptatrienyl‐3‐(2‐furyl)benzothiophenes, which are prepared by Stille coupling reaction of 2‐cyclo‐heptatrienyl‐3‐bromobenzothiophene with the 5‐substituted 2‐trimethylstannylfurans, react with triphenylmethyl tetrafluoroborate to give the corresponding azuleno[1,2‐b]benzothiophenic enones in excellent yields.     

Zirconium-catalyzed chemoselective methylalumination of ethers, amines, and sulfides bearing two terminal alkenyl groups

Chemoselectivity in the methylalumination reaction of unsymmetrical ethers, amines, and sulfides bearing two different terminal alkenyl groups, a 13-tetradecenyl group and an allyl, 4-pentenyl or 6-heptenyl group was examined. The methylalumination of the allyl derivatives proceeded with complete chemoselectivity to afford only the 13-tetradecenyl-monomethylated products. In the methylalumination reactions of the 4-pentenyl and the 6-heptenyl derivatives, in addition to the 13-tetradecenyl-monomethylated products, and dimethylated products were also obtained. However, as in the case of the allyl derivatives, monomethylation to the shorter 4-pentenyl or 6-heptenyl group was not observed, except in the case of 6-heptenyl 13-tetradecenyl amine. The unique selectivity was rationalized upon how readily the intramolecular ligand exchange reaction between intermediate zirconocenium-alkene and zirconocenium-heteroatom complexes could occur.     

A finite element analysis of mach reflection by using the Boussinesq equation

The numerical analysis of ‘Mach reflection’, which is the reflection of an obliquely incident solitary wave by a vertical wall, is presented. For the mathematical model of the analysis, the two-dimensional Boussinesq equation is used. In order to solve the equation in space, the finite element method based on the linear triangular element and the conventional Galerkin method is applied. The combination of explicit and semi-implicit schemes is employed for the time integration. Moreover, one of the treatments for the open boundary condition, in which the analytical solution of the linearized Boussinesq equation in the outside domain is linked to the discrete values of velocity and water elevation in the inside domain, is applied for the modeling of the Mach reflection problem. © 1998 John Wiley & Sons, Ltd.     

Computation of transition to turbulence in the compression stage of a reciprocating engine

The transition to turbulent flow in the compression stage of a reciprocating engine is studied by obtaining the finite-difference numerical solutions to the governing Navier-Stokes equations without using explicit turbulence models. A computational method is developed under the assumption that the flow is in a low-subsonic regime with strong compression. The numerical method is a simple extension of the well known MAC method. Computations were performed for three different chamber geometries at the engine speed of 1400 rpm. The results of the computations clearly demonstrate the transient process in which large tumbling vortices break down into smaller ones near the end of the compression process. The transition process is also caught experimentally by using Mach-Zehnder interferometry.     

Synthesis of carbazole‐based light‐emitting polymers incorporating 2,5‐bis(phenylethenyl)‐4‐decyloxyanisole as collateral fluorophore

The Suzuki coupling polymerization between bis(carbazole) monomer ( CzDB ) and 9,9‐dihexylfluorene‐2,7‐diboronic acid was carried out to obtain PFCz‐PEDA0 having the number‐averaged molecular weight of 7000. The absorption and emission maximum wavelengths were observed at 344 and 408 nm, respectively. The quantum yield (QY) was relatively low (0.12) because of the photo‐induced electron transfer. Subsequently, CzPEDA ‐bearing 2,5‐bis(phenylethenyl)‐4‐decyloxyanisole (PEDA) segment sandwiched with 3‐bromocarbazole units was copolymerized to give PFCz‐PEDAn (n = 05, 10, 20, 35, and 50). The content of PEDA segment in polymer could be controlled by the monomer feed ratio. In CHCl₃ solution, the absorbance at around 400 nm became larger with one isosbestic point at 370 nm, and the emission peak at 448 nm became prominent with increasing the PEDA content. The QY of polymer was increased as the PEDA content, which was a consequence of the fluorescence resonance energy transfer from carbazole‐containing chromophore (energy donor) to PEDA fluorophore (energy acceptor). In spin‐coated film, the maximum QY was obtained in PFCz‐PEDA05 having the most appropriate molar balance of energy donor and acceptor units. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 8141–8148, 2008     

Chelation of cadmium ions by phytochelatin synthase: role of the cysteine-rich C-terminal.

The interactions between Cd(2+) and the C-terminal region of phytochelatin (PC) synthase using recombinant wild-type and mutant PC synthase were studied. We show that site-directed mutagenesis of Cys residues at C(358)C(359)XXXC(363)XXC(366) motif decreases the number of Cd(2+) and other heavy metal ions interacting with the enzyme, and that the motif binds the metals discriminatingly. The optimum binding ratio of PC synthase to Cd(2+) was also determined. The findings indicate that Cys exists as a free SH residue and that it is involved in the regulation of PC enzyme activity by transferring the metals into closer proximity with the catalytic domain. These results are important in understanding heavy metal detoxification mechanisms in higher plants, a step towards phytoremediated-applications.     

Biologically-inspired stochastic vector matching for noise-robust information processing

“End of Moore’s Law” has recently become a topic. Keeping the signal-to-noise ratio (SNR) at the same level in the future will surely increase the energy density of smaller-sized transistors. Lowering the operating voltage will prevent this, but the SNR would inevitably degrade. Meanwhile, biological systems such as cells and brains possess robustness against noise in their information processing in spite of the strong influence of stochastic thermal noise. Inspired by the information processing of organisms, we propose a stochastic computing model to acquire information from noisy signals. Our model is based on vector matching, in which the similarities between the input vector carrying external noisy signals and the reference vectors prepared in advance as memorized templates are evaluated in a stochastic manner. This model exhibited robustness against the noise strength and its performance was improved by addition of noise with an appropriate strength, which is similar to a phenomenon observed in stochastic resonance. Because the stochastic vector matching we propose here has robustness against noise, it is a candidate for noisy information processing that is driven by stochastically-operating devices with low energy consumption in future. Moreover, the stochastic vector matching may be applied to memory-based information processing like that of the brain.     

Generalizations of spectrally multiplicative surjections between uniform algebras

Let $ A $ A and ℬ be unital semisimple commutative Banach algebras. It is shown that if surjections S,T: $ A $ A → ℬ with S(1)=T(1)= 1 and α ∈ ℂ \ {0} satisfy r(S(a)T(b) − α)= r(ab− α) for all a,b ∈ $ A $ A , then S=T and S is a real algebra isomorphism, where r(a) is the spectral radius of a. Let I be a nonempty set, A and B be uniform algebras. Let ρ, τ: I → A and S,T: I → B be maps satisfying σ _π (S(p)T(q)) ⊂ σ _π (ρ(p) τ(q)) for all p,q ∈ I, where σ _π (f) is the peripheral spectrum of f. Suppose that the ranges ρ(I), τ(I) ⊂ A and S(I),T(I) ⊂ B are closed under multiplication in a sense, and contain peaking functions “enough”. There exists a homeomorphism ϕ: Ch(B)→Ch(A) such that S(p)(y)= ρ(p)(ϕ(y)) and T(p)(y)= τ(p)(ϕ(y)) for every p ∈ I and y ∈ Ch(B), where Ch(A) is the Choquet boundary of A.