Preparation and oxidative coupling of bis[o-(hydrosilyl)phenyl]cuprates and bis[o-(fluorosilyl)phenyl]cuprates

Bis[o-(hydrosilyl)phenyl]cuprates and bis[o-(fluorosilyl)phenyl]cuprates were prepared by reacting [o-(hydrosilyl)phenyl]lithiums and [o-(fluorosilyl)phenyl]lithiums, respectively, with copper salts, such as CuCN and Cu(OPiv)₂. The phenylcuprates underwent oxidative coupling to afford 2,2′-bis(hydrosilyl)biphenyls and 2,2′-bis(fluorosilyl)biphenyls.     

Hysteretic behavior of diamagnetic molecular assembly: Magnetic field-induced deformation of tubular self-assemblies composed of amphiphilic molecules

Real-time observation of a morphologies of a multi-component tubular giant vesicle (tGV), which is a self-assembly composed of plural amphiphiles with different packing parameters, was carried out under application of a magnetic field. A tGV, one of the terminals of which was fixed to a bottom of a cell, exhibited the bending deformation under a magnetic field along the perpendicular direction of the long axis. Moreover, the hysteretic behavior in this deformation was observed associated with the increase and decrease of the magnetic fields repeatedly, regardless of the presence or absence of a paramagnetic species. To understand the hysteretic behavior, the molecular cooperative effect, which stabilizes the bending deformation by replacing of the plural kinds of amphiphiles with different packing parameters within a membrane, must be taken into consideration.     

Total Synthesis of (+)‐Dibromophakellin

Two members of a family of pyrrole–imidazole marine alkaloids, (+)‐dibromophakellin and the nonnatural congener (+)‐phakellin, were synthesized enantioselectively from 4‐hydroxy‐L ‐proline. The chiral aminal at C10 was constructed efficiently by means of an Overman‐type [3,3] sigmatropic rearrangement of an enamide (see scheme).

     

Photodynamic Activity of C70 Caged within Surface‐Cross‐Linked Liposomes

[70]Fullerene (C₇₀) encapsulated into a surface‐cross‐linked liposome, a so‐called cerasome, was prepared by an exchange reaction incorporating C₇₀?γ‐cyclodextrin complexes into lipid membranes. Fullerene exchange in a cerasome‐incorporated C₇₀ (CIC₇₀), as well as in a lipid‐membrane‐incorporated C₇₀ (LMIC₇₀), was completed within 1 min with stirring at 25 °C. CIC₇₀ was more resistant to lysis than LMIC₇₀ towards lysing agents such as surfactants. Furthermore, the photodynamic activity of CIC₇₀ in HeLa cells was similar to that of LMIC₇₀, indicating that C₇₀ can act as a photosensitizing drug (PS) without release from cerasome membranes. Thus, in contrast with general drug‐delivery systems (DDSs), which require the drug to be released from the interior of liposomes, carriers for PSs for use in photodynamic therapy (PDT) do not necessarily need to release the drug. These results indicate that DDSs with high morphological stability can increase the residence time in blood and achieves tumor‐selective drug delivery by the enhanced permeability and retention (EPR) effect.     

Another realization of Kerr/CFT correspondence

We study another realization of the Kerr/CFT correspondence. By imposing new asymptotic conditions for the near-horizon geometry of Kerr black hole, an asymptotic symmetry which contains all of the exact isometries can be obtained. In particular, the Virasoro algebra can be realized as an enhancement of symmetry of the AdS geometry. By using this asymptotic symmetry, we discuss finite temperature effects and show the correspondence concretely.     

Realization of a SU(2)×SU(6) system of fermions in a cold atomic gas

We report the realization of a novel degenerate Fermi mixture with an SU(2)×SU(6) symmetry in a cold atomic gas. We successfully cool the mixture of the two fermionic isotopes of ytterbium 171Yb with the nuclear spin I=1/2 and 173Yb with I=5/2 below the Fermi temperature T_{F} as 0.46TF for 171Yb and 0.54TF for 173Yb. The same scattering lengths for different spin components make this mixture featured with the novel SU(2)×SU(6) symmetry. The nuclear spin components are separately imaged by exploiting an optical Stern-Gerlach effect. In addition, the mixture is loaded into a 3D optical lattice to implement the SU(2)×SU(6) Hubbard model. This mixture will open the door to the study of novel quantum phases such as a spinor Bardeen-Cooper-Schrieffer-like fermionic superfluid.     

Chiral vector determination of carbon nanotubes by observation of interference patterns near the end cap

We have observed clear interference images near the end caps of semiconducting carbon nanotubes with quasiarmchair and zigzag chiral vectors, using a scanning tunneling microscope. We performed a simple tight-binding calculation to simulate the interference patterns, in which Bloch states with k and -k wave vectors were superimposed. The calculations were able to reproduce the observed interference patterns. In addition, we demonstrated that the interference patterns can be categorized by the positions of k_{min} in the Brillouin zone that yield minimum energy in the conduction band, and can give information on the chiral vector of a carbon nanotube.     

A Novel Thermosensitive Gel Adsorbent for Phosphate Ions

Summary: A novel thermosensitive gel adsorbent for phosphate ions was developed and its adsorption/desorption properties were investigated. The gel adsorbent was made by the copolymerization of N-isopropylacrylamide (NIPA) and N-[3-(dimethylamino)propyl]acrylamide (DMAPAA). The adsorbent has a volume phase transition temperature (VPTT), below which it becomes hydrophilic. The tertiary amino groups of DMAPAA were ionized and showed a cationic state when the gel swelled. Phosphate ions were adsorbed onto the ionized tertiary amino groups in the gel network below the VPTT and were desorbed above the VPTT because of the suppression of the ionization of the tertiary amino groups of gel and the shrinkage of the gel.     

Regioregulated Syntheses of Poly(aminopyridine)s by Pd‐catalyzed Amination Reaction

Regioregulated poly(aminopyridine)s were synthesized by a Pd‐catalyzed C N coupling reaction. The polymerization using Pd(0) and a bulky monodentate phosphine ligand distinctively produced the para‐linked and meta‐linked poly(aminopyridine)s, without the need for a protection process. The regioregularity of the polymer was confirmed by ¹H NMR spectroscopy. Model reactions were studied to evaluate the possibility of crosslinkage in the polymer. A large difference in reactivity was observed between 5‐amino‐2‐bromopyridine and 2‐amino‐5‐bromopyridine, which should have afforded same product. Density functional theory (DFT) calculations indicated that electron densities of the Br‐bound carbon atom and the pyridine‐nitrogen atom determine the reactivity of the monomers.