Concerning the optimum scaling of the inductive substituent constants in substituted benzene reactivities. Aspects from the analysis of quinuclidine basicities

Grob's basicity data sets of 4-substituted quinuclidines are successfully correlated with the LArSR Eq. 1, the correlation parameters of which indicate that the inductive substituent constants involved in δ^o_p just correspond to 0.74°_I.     

Interaction of poly(L-glutamic acid) with cationic surfactants carrying different head groups

Three cationic surfactants carrying a common hydrocarbon tail (dodecyl group) interact differently with fully ionized poly(L-glutamic acid)(PGA), depending on the type of their ionic head groups. Decrease of pH occurred in the order; dodecylammonium chloride (DAC) > dodecyldimethylammonium chloride (DDAC) > dodecyltrimethylammonium chloride (DTAC). The-helix of PGA was strongly induced by the addition of DAC and DDAC but weakly by DTAC. The induction was inhibited when NaCl concentration was greater than 0.05 M. In the solid state, proton transfer through hydrogen bonds from ionic heads of DDAC to carboxylate groups of the polypeptide was observed. Distortion of circular dichroism spectra occurred at high mixing ratios of surfactant to polymer, due to the aggregation of-helices, as confirmed by light scattering measurements and infrared absorption spectra.     

Effect of ionic surfactants on the oscillation frequency of one-electrode-separated piezoelectric quartz crystals modified with chitosan and its derivative

From the pH dependence of oscillation frequencies of one-electrode-separated piezoelectric quartz crystals (ESPQCs) modified with chitosan and N-(1,3-dicarboxypropyl) chitosan (DCPC) in buffer solutions, it was deduced that the chitosan and DCPC films on an ESPQC contained water and that the water content depended on pH. Contrary to the expectation based on the Sauerbrey equation, the binding of ionic surfactants to chitosan and DCPC films increased the frequencies. This apparently abnormal phenomenon was explained by the release of water in swollen films. The frequency of the DCPC-modified ESPQC increased on addition of sodium dodecyl sulfate and hexadecyltrimethylammonium chloride at pH lower and higher, respectively, than 7.8. A linear relationship between surfactant concentration and frequency shift, whose slope depended on only the chain length of the surfactant alkyl group, was obtained in the range 5–50 µmol dm^–3 hexadecyltrimethylammonium chloride. The DCPC-modified ESPQC can be used for a quantitative determination of cationic surfactants in this concentration range.     

Reflection-type hologram for atoms

A cold metastable neon atomic beam was manipulated with a reflective amplitude hologram that was encoded on a silicon surface. A black-and-white pattern of atoms was reconstructed on a microchannel plate detector. The hologram used the enhanced quantum reflection developed by authors and was made of a two-dimensional array of rectangular low and high reflective cells. The surface of the high reflective cell was composed of regularly spaced roof-shaped ridges, while the low reflective cell was simply a flat surface. The hologram was the first demonstration of reflective atom-optical elements that used universal interaction between a neutral atom and solid surface.     

Structure and properties of poly(2,5-dimethylterephthalamides)

Six methyl-substituted wholly aromatic polyamides were synthesized from the reaction of 2,5-dimethylterephthaloyl chloride with p-phenylenediamine, its 2,5-dimethyl and 2-methyl derivatives, m-phenylenediamine, or its 2-methyl and 4-methyl derivatives by solution polycondensation at low temperature. The x-ray diffraction diagrams of the polyamides obtained exhibit crystal patterns. Density values range from 1.26 to 1.37 g/cm³. NMR spectra determined in concentrated H₂SO₄ solution are reported. Poly(2,5-dimethylterephthalamides) have lower thermal stability than the corresponding polyterephthalamides. The increase in solubility of polyamide by the introduction of the 2,5-dimethylterephthaloyl linkage is accompanied by a decrease in thermal stability. The effect of methyl substituents on thermal properties and solubility is discussed in terms of the packing of polymeric molecules and the extent of hydrogen bonding of the amide groups.     

The conformational and binding properties of ethylbipyridinio-modifiedβ-Cyclodextrin using induced circular dichroism

The conformational and binding properties of mono-6-deoxy-6[4-(1-ethyl-4-pyridinio)-1-pyridinio]--cyclodextrin (1) in complex formation with some guest compounds were examined by induced circular dichroism (ICD) spectra in aqueous solution. Compound 1 showed much stronger binding ability for some guest compounds (1: 1 complexes), compared with-cyclodextrin (-CDx) and a positively charged -CDx [C-6-mono-pyridino--CDx (2)]. Marked conformational changes of1 (the spatial position of the ethyl viologen (C₂V²⁺) group relative to the cavity in 1) were observed upon complex formation with some guests like 1-adamantanecarboxylic acid (ACA) and sodium cholate (SC).     

Control of structure and particle size of iron oxide on carrier oxide by the sol-gel method using organic polydentate ligands

It was tried to control the structure and particle size of iron oxide supported on a carrier by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands. The iron oxide/carrier composites were prepared by calcining carrier oxides impregnated with organic ligands and Fe(NO₃)₃·9H₂O. When ligands were diacetone alcohol and ethanol, the structure of the iron oxide was exclusively corundum. But, with ligands such as ethylene glycol, citric acid and galacturonic acid, the structure of the iron oxide changed from corundum to spinel as the amount of ligands used increased. With both series of ring and straight chain saccharides, size of the iron oxide particles changed depending on saccharides used. It was thus concluded that the structure and particle size of iron oxide supported on a carrier can be regulated by using organic polydentate ligands.     

Enantioselective hydrogenation of α,β-unsaturated carboxylic acids over cinchonidine-modified Pd catalysts: effect of substrate structure on the adsorption mode

Systematic variation of the substrate structure in the enantioselective hydrogenation of α,β-unsaturated carboxylic acids over cinchonidine-modified Pd catalysts indicated that aryl substituents in β position changed the adsorption mode of the substrates on the metal surface and eventually the configuration of the products formed in excess as compared to aliphatic substrates. The configuration of the products formed in excess by hydrogenation of eight α,β-unsaturated carboxylic acids, of which two have not been described yet, indicated that the substrates bearing aromatic ring in β position were adsorbed on the opposite face of the CC group compared to acids having aliphatic group in β position.     

Copolymerization of isopropenyl and isopropylidene oxazolones with styrene

2-Isopropenyl-4-isopropyl-2-oxazolin-5-one (M₂), was copolymerized with styrene (M₁), and the monomer reactivity ratios were determined to be r₁ = 0.31 ± 0.03, r₂ = 1.12 ± 0.10. New isomerized oxazolones (M₂), 2-isopropylidene-4-methyl-3-oxazolin-5-one, 2-isopropylidene-4-isopropyl-3-oxazolin-5-one, and 2-isopropylidene-4-isobutyl-3-oxazolin-5-one were prepared and copolymerized with styrene. The monomer reactivity ratios were: r₁ = 0.36 = 0.07, r₂ = 0.0; r₁ = 0.39 ± 0.06, r₂ = 0.00 ± 0.10; r₁ = 0.39 ± 0.10, r₂ = 0.0, respectively. The isomerized oxazolones showed no tendency towards homopolymerization by radical initiator. From the results of infrared and NMR spectra and hydrolysis of the copolymer, it was indicated that the isomerized oxazolones participated in copolymerization in the form of 1–4 polymerization of the conjugated dienes (exo double bond at C₂ and the C?N in the ring). Copolymers reacted with nucleophilic reagents such as amines and alcohols.     

Research On a Ceramics Membrane Reactor for Natural Gas Conversion

We explore the new concept for a ceramics membrane reactor including the investigation of the nickel-based catalysts for methane conversion into synthesis gas and the exploitation of an oxide ionic and electronic mixed conductor. When Ca_0.8Sr_0.2Ti_1−xFe_xO_3−α exhibiting the ionic and electronic mixed conduction was used as a support material of Ni based catalyst, coke formation over the catalyst under the methane conversion with air or carbon dioxide was strongly depended on the iron (III) ion contents, x. From the relationship between the amount of carbon deposited on the catalyst and the mixed conduction in support oxide materials, it was suggested that the self-migration of lattice oxygen inside the support regulated by the balance between the oxide ionic and electronic conductivities played an important role to prevent from accumulating the deposited carbon over the catalysts. In addition, we demonstrated the methane conversion into synthesis gas at 1173 K with one component ceramics membrane reactor constructed with the same type of perovskite-type oxide for both the catalyst supported and mixed conductor.