Precision synthesis of graft copolymers via living cationic polymerization of p‐acetoxystyrene followed by friedel–crafts‐type termination reaction

This study describes a novel precision synthesis strategy for graft copolymers using Friedel–Crafts‐type termination reaction between a cationically prepared poly(styrene derivative) and the naphthyl side groups from a poly(vinyl ether) main chain. The pendant alkoxynaphthyl groups on the poly(vinyl ether) efficiently terminated the living cationic polymerization of p‐acetoxystyrene (AcOSt) with SnCl₄ in the presence of ethyl acetate as an added base. This research provides the first example of a well‐defined graft copolymer prepared using this method. The resulting polymer contained 40 poly‐(AcOSt) branches, as calculated from the M_w determined via gel permeation chromatography–MALS analysis, which was in good agreement with the estimated number of branches obtained from ¹H NMR analysis. The acetoxy groups in the grafted poly(AcOSt) chains were easily converted into phenolic hydroxy groups under basic conditions. The as‐obtained graft copolymer with poly(p‐hydroxystyrene) side chains exhibited a pH‐sensitive phase separation in water. The synthetic method for preparing the graft copolymers was also effective in the living cationic polymerizations of other styrene derivatives. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4675–4683     

Thermo-responsive polymer brush-grafted porous polystyrene beads for all-aqueous chromatography

Poly(N-isopropylacrylamide) (PIPAAm) brush-grafted porous polystyrene beads with variable grafted polymer densities were prepared using surface-initiated atom transfer radical polymerization (ATRP) for applications in thermo-responsive chromatography. Utilization of these grafted beads as a stationary phase in aqueous chromatographic analysis of insulin provides a graft density-dependent analyte retention behavior. The separations calibration curve on PIPAAm-grafted polystyrene was obtained using pullulan standards and exhibited inflection points attributed to analyte diffusion into bead pores and partitioning into grafted PIPAAm brush surfaces. Presence of these inflection points supports a separation mechanism where insulin penetrates pores in polystyrene beads and hydrophobically interacts with PIPAAm brushes grafted within the pores. Control of PIPAAm brush graft density on polystyrene facilitates effective aqueous phase separation of peptides based on thermally modulated hydrophobic interactions with grafted PIPAAm within stationary phase pores. These results indicated that PIPAAm brush-grafted porous polystyrene beads prepared by surface-initiated ATRP was effective stationary phase of thermo-responsive chromatography for aqueous phase peptide separations.     

Adsorption Equilibrium Equation of Carboxylic Acids on Anion-Exchange Resins in Water

The adsorption of propionic acid and benzoic acid on anion-exchange resins was analyzed, and an adsorption equilibrium equation of carboxylic acids was proposed. The adsorption of carboxylic acids on the anion-exchange resins was considered to be the sum of the physical adsorption of the molecule and the ion-exchange adsorption of the ion, which were independent of each other. For the physical adsorption of carboxylic acids, it was conformed to the Freundlich equation. For the ion-exchange adsorption of carboxylate ions, the equilibrium equation corresponded well with the experimental results for wide ranges of concentration and pH. The equation contains a selectivity coefficient S(A)(Cl) for the chloride ion versus the carboxylate ion, which was considered essentially a constant. The influent of the bicarbonate ion from carbon dioxide in air could also be expressed by the additional equilibrium equation with the selectivity coefficient S(HCO(3))(Cl) for the chloride ion versus the bicarbonate ion. Consequently, an adsorption equilibrium equation can estimate the equilibrium adsorption amounts. Even the effect of a coexisting bicarbonate ion is inconsequential when the parameters of the Freundlich isotherm equation and the selectivity coefficients of the carboxylate ion and the bicarbonate ion in each resin are determined in advance. Copyright 2001 Academic Press.     

Charge-transfer interaction in liquid-crystalline materials and their application to photonics

Photochemical phase transition of push-pull type azobenzene liquid crystal (LC), which contains both an electron donor and an acceptor in both ends of the azobenzene moiety, has been explored. Polymer azobenzene LCs were prepared, which show nematic (N) LC behavior in the trans form while no LC phase in the cis isomer. Photoirradiation of a very thin film of the azobenzene LCs (∼ 200 nm) in the trans form resulted in disappearance of the N phase due to transcis photoisomerization of each mesogen, and the N phase recovered quickly when the irradiated sample was kept in the dark because of cis-trans thermal isomerization and reorientation of trans-azobenzenes. Time-resolved measurements by the use of a laser pulse (355 nm; 10 ns FWHM) revealed that the N to isotropic (I) phase transition took place in 200 μs. The thermal I-N phase transition of the push-pull type azobenzene LC occurred in 800 ms at 135 °C. This response is faster by one order of magnitude than the response of azobenzene LCs without charge-transfer interaction.     

Behavior of adsorbed hydrogen on Ni(1 1 1) surface with reemitted slow-positron spectroscopy

We have measured reemitted slow-positrons from hydrogen-adsorbed Ni(1 1 1) surface on different adsorbing conditions. It is seem that the reemitted slow-positron yield is maximum in the (2 × 2)-2H superstructure on Ni(1 1 1) surface. The origin of the change in reemitted slow-positron due to different adsorbing conditions will be discussed.     

On the minimal volume of simplices enclosing a convex body

Let \({C \subset \mathbb{R}^n}\) be a compact convex body. We prove that there exists an n-simplex \({S\subset \mathbb{R}^n}\) enclosing C such that \({{\rm Vol}(S) \leq n^{n-1} {\rm Vol}(C)}\) .     

Permittivity enhancement of transparent poly(vinylidene fluoride) nanocomposite films by loading titania-coated barium titanate nanoparticles

Barium titanate (BT) nanoparticles are coated by titania and modified by fluoroalkylsilane. The BT nanoparticles are incorporated into polyvinylidene fluoride (PVDF) films to obtain highly dielectric and transparent nanocomposite films at low filler loadings. Incorporation of BT nanoparticles having average sizes of 12 and 22 nm is performed. Incorporation of BT nanoparticles enhances the permittivity of PVDF films. Higher transparency of nanocomposite films is achieved by incorporating 12-nm nanoparticles compared to that by 22-nm nanoparticles. The polarisation mechanism in the nanocomposite films is examined using the Vo–Shi model. The result indicates that even a slight increase in the thickness of titania-coating layer on the BT nanoparticles increase the permittivity of the nanocomposite films. Comparison of the measured and calculated permittivities showed that the incorporation of BT nanoparticles coated with titania provides a practical approach to create transparent nanocomposite films having high permittivity.

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The formation of large scale reconstructed images through the use of holograms

We propose and demonstrate a method which constructs large size multicolor images using a holographic technique in limited spaces, i.e., tunnels. A traffic sign image of the same size and color as an actual traffic sign board is displayed using many comparative small holograms. Each hologram is composed of a single computer generated hologram (CGH). Though it was necessary to make many CGHs, we have shortened the hologram production time by putting a reconstructed image on long distance, and using many reconstruction sources. Moreover, though cross-talk images are caused in a color reconstruction, by adjusting the optical system it is possible to make sure that drivers see only the appropriate image. Many holograms function as one big hologram, and it has been confirmed that a large reconstructed image can be displayed in a limited space.     

Positron diffusion in the liquid phase

We introduce effective Lagrangian with spontaneously broken density and the massive internal gauge fields based on the Sethna–Sachdev–Nelson formula, and propose an explanation for the increase of the positron diffusion length in the liquid metal phase with temperature. It is shown that the effective mass of the positron in the liquid phase decreases with temperature due to restoration of the spontaneously broken density and the massive gauge fields around the positron.     

Quadrupole Moments of Na Isotopes

The electric quadrupole coupling constants eqQ/h of ²⁰Na (I ^π = 2⁺, T _1/2 = 449.7 ms), ²¹Na (I ^π = 3/2, T _1/2 = 22.49 s) and ²⁵Na (I ^π = 5/2, T _1/2 = 59.6 s) in single crystal ZnO and TiO₂ were precisely measured by applying the β-NMR technique. The ratio of the quadrupole moments between ²⁰Na (²⁵Na) and ²¹Na was determined to be 0.728 ± 0.023 (0.011 ± 0.002).