Molecular rheology of concentrated polymer systems. I

The primitive chain model of Doi and Edwards is generalized to include the short-time relaxation process. Stress relaxation after a sudden imposition of strain is studied in detail. It is shown that in the linear region (small strain) stress relaxation occurs in two steps, the relaxation of chain segments between the fixed entanglement points, and the relaxation of the entanglement points, in accordance with the conventional picture, whereas in the nonlinear region (large strain) there appears a new relaxation process between the above two. The characteristic time of this process is the Rouse relaxation time which the entire chain would have if there were no entanglements, and increases with the square of the molecular weight. This result is consistent with experimental observations.     

Synthesis and reactivity of β-cyclodextrin-histamine as enzyme model

Cyclodextrin (CD) has a hydrophobic cavity which acts like a binding site of an actual enzyme. But enzymatic turnover reaction did not occur in CD-catalyzed reactions. -CD was modified by a histamine group to attach a reactive functional group. -CD-histamine accelerates the hydrolysis of p-nitrophenyl acetate. Catalytic rate constant of this reaction is close to an actual enzyme, -chymotrypsin. Enzymatic turnover reaction is realized with this compound at around neutral pH value.     

Organometallic compounds : XII. stereochemical interconversion reactions between 1,1′−bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes

Meso and racemic isomers of 1,1′-bis(α-hydroxyalkyl)ferrocene derivatives, and trans and cis isomers of 7-oxa[3]ferrocenophanes have been isolated. The configurations of these isomers have been determined both by spectroscopy and from their reaction behavior. It has been found that the ring-closure and ring-opening interconversion reactions between 1,1′-bis(α-hydroxyalkyl)ferrocenes and 7-oxa[3]ferrocenophanes are stereospecific. PMR spectra of the diols and ethers have been examined at 100 MHz in CF₃COOH, and the existence of α-[1′-(α-hydroxyalkyl)ferrocenyl]carbonium ions has been demonstrated in this acid. A mechanism for the various interconversion reactions is proposed on the basis of their stereospecific reactivity and from the PMR spectra of the carbonium ions.     

Liquid crystalline polyfluorenes for blue polarized electroluminescence

A series of 9,9‐dialkyl‐poly(fluorene‐2,7‐diyl)s containing linear and branched alkyl substituents with a M_n of up to 200000 g/mol has been synthesized. Moreover, some of the polymers were end capped with a suitable hole transport functionality, such as a triphenylamine derivative, to improve their charge transport properties and to control the molecular weight. The thermal alignment of these novel polymers on a rubbed polyimide layer led to highly anisotropic film formation with dichroic ratios (absorption parallel and perpendicular to the rubbing direction) of up to 26 in absorption and 21 in emission.     

CXCR4 Stimulates Macropinocytosis: Implications for Cellular Uptake of Arginine-Rich Cell-Penetrating Peptides and HIV

1. Download : Download high-res image (261KB)
2. Download : Download full-size image

Highlights? CXCR4 was identified as a receptor to stimulate cellular uptake of R12 peptide ? Interaction with R12 stimulates internalization of CXCR4 via macropinocytosis ? SDF-1α and HIV-1 gp120 protein also induce macropinocytosis ? Macropinocytic uptake of HIV-1 diminished the infection of host cells     

Switchable antenna: a star-shaped ruthenium/osmium tetranuclear complex with azobis(bipyridine) bridging ligands

A star-shaped Ru/Os tetranuclear complex, in which a central Os unit is linked to three peripheral Ru units by 4,4'-azobis(2,2'-bipyridine) (azobpy) bridging ligands, was prepared to examine the unique photodynamics regulated by its redox state. The Ru/Os tetranuclear complex exhibits Ru-based luminescence at 77 K, whereas the three-electron reduction (one for each azobpy) of the Ru/Os complex results in luminescence from the Os unit. The photoexcited state of the Ru/Os complex rapidly decays into low energy metal-to-ligand charge-transfer states, in which the excited electron is localized in the azobpy ligand in the form of azobpy(.-). Upon the one-electron reduction of the azobpy ligands, the above-mentioned low-energy states become unavailable to the photoexcited complex. As a result, an energy transfer from the Ru-based excited state to the Os-based excited state becomes possible. Ultrafast transient absorption measurements revealed that the energy transfer process consists of two steps; intramolecular electron transfer from the terminal bipyridine ligand (bpy(.-)) to form azobpy(2-) followed by a metal-to-metal electron transfer. Thus, the Ru/Os tetranuclear complex collects light energy into the central Os unit depending on the redox state of the bridging ligands, qualifying as a switchable antenna.     

Photoemission study on the valence band of a β-FeSi2 thin film using synchrotron radiation

Resonant and constant-initial state photoemission spectroscopies using synchrotron radiation were applied to investigate the valence-band electronic structure of a semi-conducting β-type iron-disilicide (β-FeSi(2)) thin film. The results clearly indicated that the component elements, iron (Fe) and silicon (Si), contribute differently to the valence band features; the Fe 3d orbitals mainly concentrate in the top region of the valence band while the Si 3s and 3p orbitals spread over the wide region of the valence band. The β-FeSi(2) thin film showed a typical p-type semi-conducting nature with a work function of 4.78 eV. The β-FeSi(2) film showed the Fe M(1)VV Auger lines around the kinetic energy of 88 eV. It would be expected from these observations that there exist strong interactions between iron and silicon atoms in the β-FeSi(2) film resulting in orbital mixing and band formation.     

Palladium-catalyzed denitrogenation reaction of 1,2,3-benzotriazin-4(3H)-ones incorporating isocyanides

1,2,3-Benzotriazin-4(3H)-ones and 1,2,3,4-benzothiatriazine 1,1(2H)-dioxide reacted with isocyanides in the presence of a palladium catalyst to give 3-(imino)isoindolin-1-ones and 3-(imino)thiaisoindoline 1,1-dioxides, respectively, in high yield. An intermediate azapalladacycle was generated through denitrogenation of the triazine moiety, and an isocyanide was incorporated therein.