Alkali metal salt‐catalyzed aldol addition of dimethylsilyl enolate on a polyether structure

The aldol addition of dimethylsilyl enolates to aldehydes with alkali metal salt catalysts was examined. Several kinds of polyether derivatives were employed as solid solvents without a liquid one. In the presence of the polymer (Gr) obtained from poly(ethylene glycol) methyl ether methacrylate (PEGMA) or the crosslinked derivatives (GLs) from PEGMA, the aldol addition proceeded efficiently and yielded the product. The effective catalyst was lithium bromide for Gr and potassium bromide for GLs. The crosslinked polyether GLs were easily separated from the reaction mixture by simple filtration, which was preferable to simplifying the treatments of the reaction. The results demonstrated that the presence of polyether structures provided a favorable reaction environment and enabled the reaction under solvent‐free conditions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2075–2084, 2005     

Lewis base catalyzed Mannich-type reactions between trimethylsilyl enol ethers and aldimines

Lewis base catalyzed Mannich-type reaction between trimethylsilyl enol ethers and N-tosylaldimines is described. Nitrogen anions generated from amides or imides such as lithium benzamide or potassium phthalimide are found to be effective Lewis base catalysts in DMF at room temperature to afford the corresponding beta-amino carbonyl compounds in good to high yields; the oxygen anion generated from carboxylic acids such as lithium acetate was also found to be effective in dry DMF. The above-mentioned lithium acetate-catalyzed Mannich-type reaction between aldimines and various trimethylsilyl (TMS) enol ethers such as silyl ketene acetal proceeded smoothly even in water-containing DMF. Then, Lewis base catalyzed three-component Mannich-type reactions of TMS enol ether, tosylamide, and aromatic aldehyde having electron-withdrawing group such as p-nitrobenzaldehyde were investigated. The reaction proceeded smoothly to afford the corresponding beta-amino ester in good yield. Further, ammonium carboxylates such as tetrabutyl ammonium acetate or tetrabutyl ammonium benzoate were found to be more effective Lewis base catalysts in the above-mentioned Mannich-type reaction. The synthesis proceeded in various solvents at lower temperatures. The reaction between aldimines and TMS enol ethers generated from thioester and various ketones such as propiophenone or cyclohexanone also proceeded smoothly to afford the corresponding beta-amino carbonyl compounds in high yields with good to high anti-selectivities.     

Noncommutative Riemann Surfaces by Embeddings in $${\mathbb{R}^{3}}$$

We introduce C-Algebras of compact Riemann surfaces as non-commutative analogues of the Poisson algebra of smooth functions on . Representations of these algebras give rise to sequences of matrix-algebras for which matrix-commutators converge to Poisson-brackets as N → ∞. For a particular class of surfaces, interpolating between spheres and tori, we completely characterize (even for the intermediate singular surface) all finite dimensional representations of the corresponding C-algebras.     

Immobilization of a Bacterial Cytochrome P450 Monooxygenase System on a Solid Support

Bacterial cytochrome P450s (P450s), which catalyze regio‐ and stereoselective oxidations of hydrocarbons with high turnover rates, are attractive biocatalysts for fine chemical production. Enzyme immobilization is needed for cost‐effective industrial manufacturing. However, immobilization of P450s is difficult because electron‐transfer proteins are involved in catalysis and anchoring these can prevent them from functioning as shuttle molecules for carrying electrons. We studied a heterotrimeric protein‐mediated co‐immobilization of a bacterial P450, and its electron‐transfer protein and reductase. Fusion with subunits of a heterotrimeric Sulfolobus solfataricus proliferating cell nuclear antigen (PCNA) enabled immobilization of the three proteins on a solid support. The co‐immobilized enzymes catalyzed monooxygenation because the electron‐transfer protein fused to PCNA via a single peptide linker retained its electron‐transport function.     

Multi-sideband Generation in a Femtosecond Cr4+:YAG Laser

We describe the behavior of multi-sidebands in a self-mode-locked femtosecond Cr⁴⁺:YAG laser operating near 1.54 μm. Stokes and anti-Stokes sideband components are extended over 20 THz around the center frequency. An interesting feature here is that when the spectral width of the mode-locked pulse is increased, the specific Stokes sideband near 1.65 μm (a shift of 13.5 THz) is strongly enhanced due to an induced-Raman process in the laser rod. The measured frequency shifts for all sidebands are well explained by four-wave-mixing processes in the laser rod, accompanied by the resonance effect of the soliton and dispersive wave, both of which are affected mainly by cavity dispersions.     

Modulation of auditory evoked responses to spectral and temporal changes by behavioral discrimination training

Background  

Due to auditory experience, musicians have better auditory expertise than non-musicians. An increased neocortical activity during auditory oddball stimulation was observed in different studies for musicians and for non-musicians after discrimination training. This suggests a modification of synaptic strength among simultaneously active neurons due to the training. We used amplitude-modulated tones (AM) presented in an oddball sequence and manipulated their carrier or modulation frequencies. We investigated non-musicians in order to see if behavioral discrimination training could modify the neocortical activity generated by change detection of AM tone attributes (carrier or modulation frequency). Cortical evoked responses like N1 and mismatch negativity (MMN) triggered by sound changes were recorded by a whole head magnetoencephalographic system (MEG). We investigated (i) how the auditory cortex reacts to pitch difference (in carrier frequency) and changes in temporal features (modulation frequency) of AM tones and (ii) how discrimination training modulates the neuronal activity reflecting the transient auditory responses generated in the auditory cortex.     

Two-phase coexisting state of n-hexatriacontane in the first-order phase transition

The small crystal of n-hexatriacontane was observed by a polarizing microscope in the rotator phase transition temperature region. In the temperature region, the rotator phase coexists with the solid phase (low-temperature ordered phase). The boundaries of two phases move reversibly with the temperature change. The area fractional change of the rotator phase can be described by the Debye relaxation. The relaxation time decreases and the relaxation strength increases as the sample temperature is raised. The relaxation time agrees well with that of the dynamic specific heat, which was measured in the frequency range of 0.0003≤f/Hz≤0.05.