Stability of naturally occurring pyrazines and construction route of pyrazine rings

Naturally occurring pyrazines fit well the theory that conformity to the TCS rule gives a stable molecular system. Thus, many pyrazines so far synthesized and those in nature which are energetically very stable molecules can be synthetically quite accessible. The TCS rule applies very well to the construction route of pyrazine rings.     

10-Gbit/s Serial Optical Interconnection for an ATM Switch

Serial optical interconnection is proposed for connections in a Torus asynchronous transfer mode switch. A cross-point switch was developed that operates at a bit rate of 20 Gbit/s. The switching operation was successfully performed using cascaded cross-point switches through an optical interconnection configuration consisting of commercial optoelectronics devices. The measured switching rate was 10 Gbit/s, and it was limited by the responses of the optoelectronics devices.     

Synthetic macrocyclic ligands. III. Synthesis of a quinone-hydroquinone redox system incorporated with complexing ability toward cations

Two quinones bridged with a polyether chain and the corresponding hydroquinones were synthesized, and their redox reaction and complexations with sodium and potassium ions were observed.     

A globally convergent Newton method for solving strongly monotone variational inequalities

Variational inequality problems have been used to formulate and study equilibrium problems, which arise in many fields including economics, operations research and regional sciences. For solving variational inequality problems, various iterative methods such as projection methods and the nonlinear Jacobi method have been developed. These methods are convergent to a solution under certain conditions, but their rates of convergence are typically linear. In this paper we propose to modify the Newton method for variational inequality problems by using a certain differentiable merit function to determine a suitable step length. The purpose of introducing this merit function is to provide some measure of the discrepancy between the solution and the current iterate. It is then shown that, under the strong monotonicity assumption, the method is globally convergent and, under some additional assumptions, the rate of convergence is quadratic. Limited computational experience indicates the high efficiency of the proposed method.     

Separation of aromatic substances from aqueous solutions using a reverse osmosis technique with thin,dense cellulose acetate membranes

Investigations were made of the water flux rate and rejection characteristics of aromatic substances in aqueous solutions using a thin, dense cellulose acetate membrane in reverse osmosis experiments. The aromatic substances used were phenol, aniline, hydroquinone and p-chlorophenol. The permeate became more enriched in aromatic compounds as compared to the feed solution as the water content of the membrane increased. By considering both the effects of pressure on the chemical potential of a component and the contribution of viscous flow to the overall transport of that component in the hydrated membrane, a theoretical relationship was developed to predict the negative solute rejection of the membrane. Based on this proposed theory, the permeability coefficients of water and organic solute were estimated from experimental solute rejection data, including negative values. The permeability coefficients of components were in good agreement with previously established correlations in measurements of partition and diffusion coefficients.     

Simple methods for the syntheses of (E)-4- and (E)-5-alkenoic acids by the SN2′ type reactions of γ-vinyl-γ-butyrolactone and δ-vinyl-δ-valerolactone with organocopper reagents

γ-Vinyl-γ-butyrolactone and δ-vinylδ-valerolactone react regio- and stereoselectivity with Grignard reagents in the presence of a copper(I) catalyst or with diorganocuprates to afford (E)-4- and (E)-5-alkenoic acids, respectively, in high yields. Synthetic utility of the former reaction is demonstrated in the simple synthesis of (4E,7Z)-4,7-tridecadienyl acetate.     

Stereochemically controlled asymmetric 1,2-reduction of enones mediated by a chiral sulfoxide moiety and a lanthanum(III) ion

Enantiomerically pure (Z)-β-sulfinyl allylic alcohols of either handedness can be readily prepared from (Z)-β-sulfinyl enones using NaBH(4) or DIBAL reductants in the presence of LaCl(3) as a chelating agent. A chiral sulfoxide auxiliary induces the remote 1,2-asymmetric reduction (1,4-induction) to afford various chiral allylic alcohols in high yields with excellent stereoselectivities (up to 100% de).     

Copper-catalyzed addition reactions of aromatics and ketones to 2-aza-2,4-cyclopentadienone: facile and efficient transformation of carbonyl-ene-nitriles to 1H-pyrrolin-2(5H)-ones

Copper-catalyzed reactions of carbonyl-ene-nitriles with carbon nucleophiles, such as aromatics and ketones, afforded pyrrolin-2-ones (gamma-lactam) in excellent yield. The reaction mechanism involves addition reactions with a ketimine moiety of the 2-aza-2,4-cyclopentadienone intermediate, which is formed via hydration of a nitrile moiety followed by dehydrative cyclization.     

Ladder oligo(m-aniline)s: derivatives of azaacenes with cross-conjugated π-systems

We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. All compounds have planar "azaacene" moieties. The experimental band gaps E(g) ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S(1) state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O(2)). For two oligomers with "tetraazanonacene" moieties, potentials of E(4+/3+) ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations.