O-Alkylations of pyridoxine and pyridoxamine

O-Alkylations of pyridoxine 1 and pyridoxamine 5 were carried out in acetone in the presence of sodium ethoxide and potassium iodide to give 5-alkoxy-6-methyl-3,4-(bishydroxymethyl)pyridines 2a-j and 5-alkoxy-4-aminomethyl-6-methyl-3-hydroxyrnethylpyridines 6a-e .     

Synthesis of a Stable N‐Hetero‐RhI‐Metallacyclic Silanone

A novel N‐hetero‐Rh^I‐metallacyclic silanone 2 has been synthesized. The silanone 2 , showing an extremely large dimerization energy (ΔG=+86.2 kcal mol^?1), displays considerable stability and persists in solution up to 60 °C. Above 120 °C, an intramolecular C_sp3?H insertion occurs slowly over a period of two weeks leading to the bicyclic silanol 5 . The exceptional stability of 2 , related to the unusual electronic and steric effects of Rh^I‐substituent, should allow for a more profound study and understanding of these new species. Furthermore, the metallacyclic silanone 2 presents two reactive centers (Si=O and Rh), which can be involved depending upon the nature of reagents. Of particular interest, the reaction with H₂ starts with the hydrogenation of Rh^I center leading to the corresponding Rh^III‐dihydride complex 7 and it undergoes a cis/trans‐isomerization via a particular mechanism, demonstrating that addition‐elimination processes can also happen for silanones just like for their carbon analogues!     

Surface Engineering of Titania Boosts Electroassisted Propane Dehydrogenation at Low Temperature

Electric field catalysis using surface proton conduction, in which proton hopping and collision on the reactant are promoted by external electricity, is a promising approach to break the thermodynamic equilibrium limitation in endothermic propane dehydrogenation (PDH). This study proposes a catalyst design concept for more efficient electroassisted PDH at low temperature. Sm was doped into the anatase TiO₂ surface to increase surface proton density by charge compensation. Pt−In alloy was deposited on the Sm-doped TiO₂ for more favorable proton collision and selective propylene formation. The catalytic activity in electroassisted PDH drastically increased by doping an appropriate amount of Sm (1 mol % to Ti) where the highest propylene yield of 19.3 % was obtained at 300 °C where the thermodynamic equilibrium yield was only 0.5 %. Results show that surface proton enrichment boosts alkane dehydrogenation at low temperature.     

Structure in the condensed state and amphiphilic properties of novel copolymers having alkyl chains and phosphatidylcholine analogous groups

N‐Stearylacrylamide (SAAm), N‐oleylacrylamide (OAAm), and N‐laurylacrylamide (LAAm) were synthesized. They were characterized by ¹H‐NMR, ¹³C‐NMR, FT‐IR, melting point measurements, and elemental analysis. The copolymerizations of SAAm, OAAm, and LAAm with 2‐[(3‐(acrylamido)propyl)dimethylammonio]ethyl 2′‐isopropyl phosphate were carried out, and a series of amphiphilic poly(acrylamide)s (1a,b, 2, and 3a,b) were obtained. These copolymers showed polyelectrolyte behavior in their viscous properties in polar solvents. X‐ray diffraction analysis indicated that the copolymers 1a,b formed similar stacked bilayers with hydrophilic groups and hydrophobic parts. The polymorphic phase transition of these copolymers was also observed by DSC. In addition, the monolayers as well as LB films of these amphiphilic copolymers were prepared on the surface of water and their π–A isotherms were investigated at different temperatures. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1293–1302, 1999     

Thermodynamic and Spectroscopic Study of the Adduct Formation of Tris(β-diketonato)lanthanoids with Heteroamines

A remarkable enhancement of the extraction of lanthanoids(Ⅲ)(Ln) with β-diketones in the presence of a Lewis base, so-called synergistic effects, would be caused by the adduct formation of the β-diketonates with the Lewis base. The trend of the variation of the adduct formation constants across the lanthanoid series may be different among β-diketones used. It has also been observed that the trend across lanthanoid series and also the values of the enthalpy change in the adduct formation of the 2-thenoyltrifluoroacetonates(TTA) with 1,10-phenanthroline(phen) are very similar to those with 2,25-bipyridyl(bpy), although the values of the adduct formation constants with the former are larger than those with the latter.     

Experimental investigation of ethylene/air combustion instability in a model scramjet combustor using image-based methods

The combustion instabilities of supersonic combustion were investigated experimentally in a laboratory-scale scramjet combustor with a cavity flame holder. Ethylene was injected transversely from an orifice to the supersonic flow of Mach 2 with a stagnation temperature of 1900 K and a total pressure of 0.37 MPa. The dynamic pressure, CH* chemiluminescence and shadowgraph images were measured with a pressure sensor and a high-speed video camera. Dynamic pressure was analyzed by fast Fourier transform, and time-resolved CH* chemiluminescence images were modally decomposed by the sparsity-promoting dynamic mode decomposition (SP-DMD). The results indicated that two combustion instabilities were observed for cavity shear-layer stabilized combustion and the oscillation between jet-wake stabilized and cavity shear-layer ram combustions for the power spectral density (PSD) of pressure. In the case of the combustion instability of cavity shear-layer stabilized combustion, a dominant peak of approximately 128 Hz was observed for the PSD of pressure. This instability corresponded to an entire flame oscillation of the cavity shear-layer stabilized combustion, which was validated by the SP-DMD and a low rank reproduction with 10 modes. This was driven by a fuel injection oscillation in the injection orifice. In the case of oscillation between the jet-wake stabilized and the cavity shear-layer ram combustions, peaks around 1600 Hz were observed for the PSD of pressure. This mechanism was also explained by the SP-DMD modes and a low rank reproduction using within 10 modes. The DMD and shadowgraph images indicated that the vortex formed by a separation of the boundary layer induced a strong jet-wake flame, resulting in the temporal thermal choke followed by cavity shear-layer stabilized ram combustion. The data-driven approach with SP-DMD clarified the combustion instability mechanisms of the supersonic combustion in detail.     

Elasticity effects on domain coarsening of the lamellar-gyroid transition observed in a nonionic surfactant system

The coarsening process of the gyroid phase of a nonionic surfactant system is investigated by time resolved small angle neutron scattering (SANS) and small angle neutron Laue diffraction techniques. The time evolution of SANS patterns shows anomalous coarsening of the gyroid domains. The observed Laue spot from a gyroid domain becomes elongated along the radial direction with the elapse of time and at a certain time the elongated spot is split into two spots. The results can be interpreted as follows. During the coarsening process, mismatch of the lattice orientation at the domain boundary brings strong stress to the gyroid domain, resulting in the distortion of the domain. The stored stress in the domain finally brings splitting of the gyroid domain. The elastic and fragile nature of the gyroid domains composed of the "soft matter" is responsible for the anomalous coarsening.     

Die Zersetzung von Tetramethyl-2-tetrazen in Gegenwart von Poly(p-vinylbenzyl-bromid)

Ohne Zusammenfassung     

Vinylpolymerisation. 311. Mitt. Synthese und Polymerisation von 2-Brom?thoxyphenoxyphosphorylmethacrylat

Ohne Zusammenfassung     

Synthese und Polymerisation von Benzyl-2-(methacryloyl-oxy)?thylhydrogenphosphat

Ohne Zusammenfassung