Almost automorphic solutions for abstract functional differential equations

For abstract linear functional differential equations with an almost automorphic forcing term, we establish a result on the existence of almost automorphic solutions, which extends the classical theorem due to Massera on the existence of periodic solutions for linear periodic ordinary differential equations.     

Ethylene polymerization by chromium complexes with phosphorous‐bridged bisphenoxy ligand

Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl₃(THF)₃, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl₃(THF)₃ in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)^?1 h^?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (M_w = 128,700, M_w/M_n = 1.8) was obtained using a 6 ‐TIBA/B(C₆F₅)₃ system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007     

Hydration Structure Around the Carboxyl Group Studied by Neutron Diffraction with 12C/13C and H/D Isotopic Substitution Methods

Time-of-Flight (TOF) neutron diffraction measurements have been carried out on aqueous 8 mol% sodium acetate solutions in D₂O. Scattering cross sections that were observed for sample solutions involving ¹²C/¹³C and H/D isotopically substituted acetate ions were used to derive the first-order difference functions, Δ_H(Q) and Δ_C(Q), and corresponding distribution functions, G _H(r;r) and G _C(r;r), which describe the environmental structure around the methyl and the carboxyl groups within the acetate ion, respectively. Structural parameters concerning the first hydration shell of the carboxyl group within the acetate ion were obtained through the least squares fit to the observed intermolecular difference function, Δ_C ^inter(Q). The nearest neighbor C _O...D _W1 (C_O: carboxyl carbon atom, D_W1: water deuterium atom) distance, r(C _O...D _W1 ), and the angle, ∠ C _O ...D _W1 -O _W (O _W : water oxygen atom), were determined to be 2.63(1) Å and 120(1)°, respectively. The coordination number, n(C _O ...D _W1 ), was obtained to be 4.0(1). These results are consistent with the hydration structure in which water molecules in the first hydration shell of the carboxyl group are hydrogen-bonded with oxygen atoms of the carboxyl group.     

Studies on analgesic oligopeptides. VI. Further studies of synthesis and biological properties of tripeptide alkylamides, Tyr-D-Arg-Phe-X

Nine analogs based on a structure of Tyr-D-Arg-Phe-X (X = alkylamides or alkylhydrazide containing electron-withdrawing atoms or groups) were newly synthesized and their biological properties were examined by the opioid receptor binding properties of mu-, delta- and kappa-receptors, guinea-pig ileum (GPI) assay and analgesic activity in the tail pinch test after subcutaneous administration in mice. Analogs with X = NHCF2CF3, Sar-ol, or NH(CH2)2CN showed potent activities in the GPI and analgesic assays and high affinity for mu-receptor. An analog with X = taurinamide was found to possess 4-fold higher mu-receptor selectivity than that of [D-Ala2, MePhe4, Gly-ol5]enkephalin (DAGO). The receptor binding properties of previously reported analogs [Chem. Pharm. Bull., 33, 1528 (1985); ibid., 33, 4865 (1985); ibid., 36, 4834 (1988)] were also examined for overall discussion of the structure-activity relationships of this series of tripeptide amides.     

Condensed phase photoelectron asymmetry

Large directional asymmetries were observed in photoelectron distributions from core and valence levels in metals and adsorbate atoms. Intensities varied by factors up to 25 as the angle between A and p was varied. The energy dependence of asymmetry showed atomic behavior similar to that expected for free atoms, modified for the tendency p∥A.     

Complex emulsion inversion pattern associated with the partitioning of nonionic surfactant mixtures in the presence of alcohol cosurfactant

Commercial ethoxylated nonionic surfactant mixtures containing alcohol cosurfactant exhibit a three-phase behavior whose formulation strongly varies with the water/oil ratio. As a consequence, a change in water/oil ratio can result in a sequence of up to three different emulsion inversion processes, through a combination of formulation and composition effects.     

Stereospecific polymerization of isobutyl vinyl ether catalyzed by calcined iron sulfate

The polymerization of isobutyl vinyl ether was studied in a heterogeneous system using iron (II) sulfate calcined in air at various temperatures as a catalyst. The maximum activity was shown by the catalyst calcined at 700°C, which effected the polymerization at room temperature in a few seconds, while the sulfate treated at 750°C was totally inactive. Poly(vinyl ethyl ether) was also obtained by the FeSO₄ (700°C) catalyst at room temperature. This catalyst formed the crystalline polymer (melting temperature 135–138°C) when the reaction was performed in toluene as solvent at room temperature. Poisoning experiments with Hammett indicators were carried out with the FeSO₄ (700°C) catalyst. The treatment with n-butylamine rendered it inactive in the reaction of isobutyl vinyl ether, while its catalytic activity was little affected by dicinnamalacetone. On the basis of the observed results, the nature of active sites of catalyst is discussed.     

Study of the catalytic behavior of montmorillonite/iron(III) and Mn(III) cationic porphyrins

Two samples of montmorillonite (one of Brazilian origin, BNC1 clay, and the other STX-1, supplied by the Clay Mineral Society Repository (University of Missouri, USA) were allowed to react with biomimetic metalloporphyrins of Fe(III) and Mn(III) in cationic form. The compounds were characterized by several techniques, showing that the metalloporphyrins molecules were adsorbed at the surface of the clay platelet crystals. The catalytic activities of the intercalated complexes for the oxidation of alkane were dependent upon the concentration of the porphyrin immobilized in the clay and factors such as the metal ion species in the porphyrins, choice of solvent, and concentration of the iodosylbenzene oxidant. Good selectivity to cyclohexanol instead of cyclohexanone was observed for the catalytic oxidation of cyclohexane by iodosylbenzene.     

Syntheses and configurations of some heterocyclic amidoximes. X-Ray crystal structure of 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime

O-Methyl-α-ketophenylacetohydroximoyl chloride ( 1 ) was prepared by the reaction of O-methyl-α-methoxyphenylacetohydroximoyl chloride ( 5 ) with N-bromosuccinimide and concentrated hydrobromic acid. Reaction of 1 with ethylenediamine gave 3-phenyl-5,6-dihydro-2(1H)-pyrazinone-O-methyloxime ( 6 ). 3-Phenyl-5,6-cyclohexano-5,6-dihydro-2(1H)-pyrazininone-O-methyloxime ( 7 ) was prepared by reaction of 1 with trans-1,2-diaminocyclohexane. The X-ray structure of 6 has been determined. The crystals are orthorhombic, space group Pbca with a = 10.264(3), b = 18.262(4), c = 23.530(4)Å, V = 4411(2)ų, and Z = 16. The structure, which was refined to R = 0.038 using 1652 observed reflections, shows the amidoxime moiety to be the Z configuration. Reaction of benzohydroximoyl chloride with aziridine gave (Z)-aziridinylbenzaldoxime ( 16a ). Ultraviolet irradiation of a benzene solution of 16a gave a mixture of the Z and E isomers 16a and 16b . The E isomer 16b underwent thermal isomerization to 16a at 100°. Reaction of 16a with dimethyl sulfate in sodium hydroxide solution gave (Z)-O-methylaziridinylbenzaldoxime ( 17a ). Photoisomerization of a hexane solution of 17a gave a mixture of the Z and E isomers 17a and 17b which were separated by preparative glc. The isomers 17a and 17b are resistant to thermal Z = E isomerization. The mechanisms of thermal isomerization of benzamidoximes are discussed.