Selective pH gradient formation across a capsule membrane corked with charged synthetic bilayers

Ultrathin, large nylon capsules whose porous membranes were corked with charged, synthetic bilayer-forming amphiphiles (cationic, anionic, zwitterionic bilayers) were prepared. The chemically stable, bilayer-corked capsules can selectively retain 0.1 M aqueous acidic (HCl, HNO₃, H₂SO₄, HClO₄ and p-toluenesulfonic acid) and alkaline solutions (NaOH, Ba(OH)₂, NH₄ OH, and N(Et)₄OH) in the inner aqueous phase depending on the surface charge of corking bilayers: the capsule corked with positively and negatively charged bilayers could selectively store alkalies and acids, respectively, and could keep a selective pH-gradient across the membrane. The zwitterionic bilayer-corking could retain neither acids nor alkalies in the inner aqueous phase. The permeation of these acids and alkalies to the outer phase (pH gradient decreasing across the capsule membrane) could be reversibly controlled by the phase transition of corking bilayers from gel to liquid crystalline state. The selective storage and permeation of acids and alkalies could be explained by the process of permeation of H⁺ or OH^- counter ions across the charged bilayer-corking.     

Efficient heterogeneous catalytic intramolecular Tishchenko reaction of o-phthalaldehyde to phthalide with alkaline earth oxides

The heterogeneous catalytic systems realized by alkaline earth oxides are successfully applicable to the highly efficient intramolecular Tishchenko lactonization of o-phthalaldehyde to phthalide.     

Formation and Characterization of Reversed Micelles Composed of Phospholipids and Fatty Acids

The formation of reversed micellar systems composed of phosphatidylcholine (PC) and fatty acid was newly demonstrated by a significant increase in water content in the organic ethyl oleate phase when the micelles were prepared by the contact method. The solubilized water concentration in the reversed micellar organic phase reached 3 wt%. The new systems are expected to be used as highly biocompatible reversed micellar systems. The structure of the reversed micelles composed of PC and oleic acid was characterized by determining the water concentration and by small-angle X-ray scattering analysis. The reversed micelles composed of PC and oleic acid formed in ethyl oleate were spherical. The radius of gyration was between 30 and 50 Å. The size of the reversed micelles decreased with an increase in the oleic acid concentration and was independent of the PC concentration. Experimental results indicated that the structure of the reversed micellar system was determined by the oleic acid concentration. An increase in the PC concentration caused an increase in the number of reversed micelles of the same size. These reversed micellar systems are expected to be used as solubilization media in pharmaceutical and food industries because they are not toxic.     

Multiple Coulomb excitation of a 70Ge beam and the interpretation of the 02 + state as a deformed intruder

Electromagnetic properties of the low-lying states in a ⁷⁰Ge nucleus were studied through the multiple Coulomb excitation of a ⁷⁰Ge beam with a ^natPb target. Relative γ-ray intensities were measured as a function of emission angle relative to the scattered projectile. Sixteen E2 matrix elements, including diagonal ones, for 6 low-lying states have been determined using the least-squares search code GOSIA. The expectation values 〈Q ²〉 of 0₁ ⁺ and 0₂ ⁺ states in ⁷⁰Ge are compared with those in ^{72, 74, 76}Ge. Simple mixing calculations indicate that the 0₂ ⁺ states in ⁷⁰Ge and ⁷²Se can be treated as deformed intruder states. It is shown that the deformed intruder becomes the ground state in ⁷⁴Kr. These interpretations of the 0₂ ⁺ states in this region are compared with the potential-energy surface calculations by the Nilsson-Strutinsky model, which allow to interpret the experimental results in a qualitative way from the theoretical point of view. Received: 2 September 2002 / Accepted: 5 November 2002 / Published online: 25 February 2003 RID="a" ID="a"e-mail: sugawara@pf.it-chiba.ac.jp Communicated by D. Schwalm     

Reduction of ion thermal diffusivity associated with the transition of the radial electric field in neutral-beam-heated plasmas in the large helical device

Recent large helical device experiments revealed that the transition from ion root to electron root occurred for the first time in neutral-beam-heated discharges, where no nonthermal electrons exist. The measured values of the radial electric field were found to be in qualitative agreement with those estimated by neoclassical theory. A clear reduction of ion thermal diffusivity was observed after the mode transition from ion root to electron root as predicted by neoclassical theory when the neoclassical ion loss is more dominant than the anomalous ion loss.     

Observation of the "self-healing" of an error field island in the large helical device

It was observed that the vacuum magnetic island produced by an external error magnetic field in the large helical device shrank in the presence of plasma. This was evidenced by the disappearance of flat regions in the electron temperature profile obtained by Thomson scattering. This island behavior depended on the magnetic configuration in which the plasmas were produced.     

Synthesis and isomerization of conjugated oligomers containing azoimidazole unit

The Suzuki (for O1 – O3 ) and Stille (for O4 ) coupling polymerization of 2‐(phenylazo)imidazole bearing the benzyl protecting group at the 1‐position gave conjugated oligomers. The transformation from the neutral imidazole in the conjugated oligomer O2 , consisted of the alternating 2,5‐didecyl‐1,4‐phenylene unit, to the cationic imidazolium salt O2S was performed. Depending on the chemical structure of coupling partners, the absorption maximum of conjugated oligomers showed red shift or blue shift from that of the model compound M with the benzene ring at the 4,5‐positions. The absorption maximum wavelength of the cationic conjugated oligomer O2S showed a blue shift from that of the neutral conjugated oligomer O2 . The trans‐to‐cis photoisomerization of the azoimidazole unit in conjugated oligomers was observed by irradiating the light at 436 nm, and the conversion degree to the cis structure had a rough correlation with the maximum absorption wavelength of materials. The trans‐to‐cis photoisomerization in the film state was sluggish. On the other hand, the cis‐to‐trans thermal isomerization of the azoimidazole unit was confirmed and the absorbance returned to the initial state before the photoisomerization. The trans‐to‐cis photoisomerization of the cationic conjugated oligomer O2S required large energy, and the prolonged light irradiation might decompose the azoimidazole unit. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Improvement of pharmaceutical potential of all-trans retinoic acid with hydroxypropyl-��-cyclodextrin

2-Hydroxypropyl-??-cyclodextrin (HP-??-CyD) includes all-trans retinoic acid (RA), covering the double-bond area of RA with substituted hydroxypropyl groups on CyD ring, as proved by the nuclear Overhauser effect (NOE) between methylene protons on the hydroxypropyl groups and the proton on RA. The formation of an inclusion complex results in hydrophilicity and stability. The effect of RA/HP-??-CyD and that of RA without HP-??-CyD on wrinkle scores and skin elasticity during skin treatment were identical, and the cutaneous stimulus was reduced comparing with RA. The results indicated that the RA/HP-??-CyD complex should help to realize new approaches in skin rejuvenation therapy.     

Irreversible helix rearrangement from Cis‐transoid to Cis‐cisoid in poly(p‐n‐hexyloxyphenylacetylene) induced by heat‐treatment in solid phase

Polymerization of p‐n‐hexyloxyphenylacetylene (pHPA) by using a [Rh(norbornadine)Cl]₂‐triethylamine catalyst was carried out at room temperature to afford stereoregular helical poly(p‐n‐hexyloxyphenylacetylene)s (PpHPAs). When ethanol and n‐hexane were used as polymerization solvents, a bright yellow PpHPAs, poly( Y ) with M_n = 8.5 × 10⁴ and its purple red polymer, poly( R ) with M_n = 5.3 × 10⁴ were obtained in 95% yields and 84% yields, respectively. Diffuse reflective UV–vis spectra of poly( Y ) and poly( R ) in solid phase showed different broad absorption peaks at 445 and 575 nm, respectively. X‐Ray diffraction patterns of poly( Y ) and poly( R ) showed typical columnar structures assignable to cis‐transoid and cis‐cisoid structures, respectively, which were also supported by molecule mechanics calculation. Poly( Y ) was irreversibly transformed to a reddish‐black polymer, poly( Y‐B ), which columnar diameter was nearly the same as that of poly( R ). Further, poly( Y ) showed an exothermic peak in the differential scanning calorimetry trace at 80 °C for 1 h in N₂ gas. Thus, these findings suggest a thermally irreversible rearrangement from an unstable cis‐transoid form, poly( Y ) with a stretched cis‐transoid helix to a stable cis‐cisoid form, poly( R ), with a contracted cis‐cisoid helix in the solid phase to give poly( Y → B ) with the cis‐cisoid form. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012