Practical synthesis of a 1beta-methylcarbapenem, J-111,225, using 4-mercapto-2-[4-(N-methylaminomethyl)phenyl]pyrrolidine as a precursor

An effective and practical procedure for the synthesis of J-111,225 (1), a new 1beta-methylcarbapenem, was developed using 4-mercapto-2-14-(N-methylaminomethyl)phenyl]pyrrolidine (2a) as a precursor. The coupling reaction of 2a with p-nitrobenzyl (PNB)-protected 1beta-methylcarbapenem enolphosphate 3a and successive removal of PNB group afforded J-111,225 (1) in significantly increased yield compared to the ordinary procedure using a C-2 side-chain thiol with amino-protective groups.     

Hydrobromic acid-dimethyl sulfoxide reagent for dealkylation of 5,10-dialkyl-5,10-dihydrophenazines: Synthesis of 10-alkyl-2(10H)-phenazinones

By the reaction of 5,10-dialkyl-substituted 5,10-dihydrophenazine with hydrobromic acid in dimethyl sulfoxide at 90–110°, 10-alkyl-2(10H)-phenazinone was obtained as a major product. Brominated dihydrophenazine was isolated in the case of 1,6-dichloro-5,10-dimethyl-5,10-dihydrophenazine.     

Laccase‐catalyzed polymerization of lignocatechol and affinity on proteins of resulting polymers

For the synthesis of a new biologically functional polymer from a natural resource by an environment‐friendly method, the laccase‐catalyzed polymerization of a lignin‐based macromonomer, lignocatechol, was carried out for the first time in ethanol–phosphate buffer solvent system to give crosslinked polymers in good yields. Lignocatechol was prepared by the phase separation system of lignin and catechol in aqueous sulfuric acid. The copolymerization was also performed with urushiol to afford the corresponding copolymers in high yields. The polymerization mechanism was estimated by the IR and pyrolysis GC‐MS measurements, suggesting that the polymerization proceeded mainly at the catechol ring through a quinone radical intermediate. The thermal properties were measured by the DSC, TG, and TMA analyses, indicating that the polymers had high thermal stabilities because of the crosslinked structures. In addition, it was found that the resulting polymers had the affinity of bovine serum albumin (BSA) and glucoamylase. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 824–832, 2009     

Localized solutions to the nonlinear wave equation for flexural motions of an elastic beam traveling in an air-filled tube

Steady-progressive-wave solutions are sought to the nonlinear wave equation derived previously [J. Fluids Struct. 16 (2002) 597] for flexural motions of an elastic beam traveling in an air-filled tube along its center axis at a subsonic speed. Fluid-structure interactions are taken into account through aerodynamic loading on the lateral surface of the beam subjected to small but finite deflection but end effects and viscous effects are neglected. Linear dispersion characteristics are first examined by exploiting the small ratio of the induced mass to the mass of the beam per unit length. Centered around the traveling speed of the beam, there exists such a narrow range of propagation velocity that the linear steady propagation is prohibited. In this range, it is revealed that some interesting nonlinear solutions exist. The periodic wavetrain is found to exist as the exact solution. Asymptotic analysis is then made by applying the method of multiple scales and the stationary nonlinear Schrödinger equation is derived for a complex amplitude. A monochromatic solution to this equation corresponds to the exact periodic solution. Imposing undisturbed boundary conditions at infinity, it is revealed that the localized solution exists as a result of balance between the linear instability and the nonlinearity. This solution is checked by solving the nonlinear equation numerically. It is further revealed that the amplitude-modulated wavetrain exists not only in the range of the velocity mentioned above but also outside of it.     

Ion-sensitive field effect transistor as a monovalent cation detector for ion chromatography and its application to the measurement of Na+ and K+ concentrations in serum

An ion-sensitive field effect transistor, which is a small potentiometric ion-sensing probe, was applied as a detector in the ion chromatography of alkali-metal cations. The cation-sensing transistor was prepared by coating the gate part of the probe to form a poly(vinyl chloride) matrix membrane containing tetranactin, which enables detection of alkali-metal ions such as Na+, K+, Rb+, and Cs+. To be able to analyse amounts less than 1 microliter and make full use of the small ion-sensing probe, we constructed a miniature cation-exchange separation column (support 10 microns polystyrene) with a PTFE tube (20 mm x 1.5 mm I.D. x 2.1 mm O.D). As an application of the system, Na+ and K+ concentrations in serum were determined. The analytical results for these two cations were good agreement with those obtained by flame photometry.     

Melt rheology of hyperbranched‐polystyrene synthesized with multisite macromonomer

Melt rheological behaviors of hyperbranched‐polystyrene (PS) copolymerized by dendric macromonomer technique are presented. The time–temperature superposition principle was applicable to the hyperbranched‐PS. The branched‐PS showed slightly lower zero‐shear viscosity in comparison with linear PS regardless of a presence of a number of branches expected from the dendric macromonomer technique. Although the influence of use of multimethacryloyl macromonomer in the polymerization process was marginal for linear viscoelastic regime, nonlinear shear and uniaxial elongational flows showed distinct differences between linear and branched‐PS. The strain dependence of the damping function became weak as increase of macromonomer content. The branched‐PS exhibited the growing elongational viscosity function comparing with linear PS. This prominent effect on the elongational flow behavior can be explained by the molecular architecture of the branched‐PS. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2226–2237, 2009     

Cepaic acid, a novel yellow xanthylium pigment from the dried outer scales of the yellow onion Allium cepa

Cepaic acid was isolated as a novel xanthylium yellow pigment from the dried outer scales of the yellow onion Allium cepa Linne. Its structure was elucidated on the basis of ESI-MS and 2D NMR spectroscopy as a 9-carboxy-1,3,6,8-tetrahydroxyxanthylium, which suggests that cepaic acid and other yellow pigments in the dried outer skin of onion were formed by the nucleophilic reaction of phloroglucinol derived from quercetin, a flavonol in onion scales, by autoxidation to glyoxylic acid. To our knowledge, this is the first report of such a pigment in yellow onion.