Anionic fullerenes, calixarenes, coronenes, and pyrenes as activators of oligo/polyarginines in model membranes and live cells

We report that the efflux of 5(6)-carboxyfluorescein anions from neutral egg yolk phosphatidylcholine vesicles is mediated by oligo/polyarginines only in the presence of activating amphiphilic anions. Screening of anion activators reveals best synergism for amphiphilic carboxylates (fullerene > calix[4]arene approximately coronene > pyrene > calix[6]arene > alkyl), whereas amphiphilic sulfates show less satisfactory activation despite often lower effective concentrations. The analogous alcohols and one calix[4]arene diphosphate were inactive. These results are discussed in the context of a tentative anion carrier mechanism, where interactions with bilayer (interface-directed translocation) and carrier (arene-templated carboxylate-guanidinium pairing) contribute to activator efficiencies. Applied to HeLa cells, pyrenebutyrate is shown to significantly increase the uptake of a fluorescently labeled octaarginine in a concentration-dependent manner.     

Oxygen dissolution and transport in cobaltporphyrin-bound organophosphazene membranes

Rubbery poly(organophosphazene)s were synthesized, and were combined with cobaltporphyrin (CoP) which binds molecular oxygen rapidly and reversibly. The apparent oxygen-binding equilibrium constant (K_app) is in proportion to the physical solubility coefficient of oxygen in the polymer, although the reduced equilibrium and thermodynamic parameters are not dependent on the polymer matrix species. Diffusivity of oxygen via the fixed CoP(D_C) is enhanced for poly(organophosphazene) membranes with a larger oxygen diffusion constant. Poly(organophosphazene) membranes with both a large K_app and D_C yield high oxygen permeability.     

Mechanism of two-dimensional chiral growth of 6,13-pentacenequinone thin films on Si(1 1 1)

Thin film growth of 6,13-pentacenequinone (C₂₄H₁₂O₂, PnQ) on Si(1 1 1)-7 × 7 at room temperature (RT) was studied by low-energy electron microscopy (LEEM) and ab initio density functional theory (DFT) calculations. Our experiments yielded direct microscopic observation of enantiomorphic evolution mechanism in the initial stage of the chiral-like growth of PnQ islands, under kinetic growth conditions. We observed that the faster growth direction aligns with the direction of easier molecule incorporation, or lowest kink formation energy, rather than along the lowest energy step. Real time observation of the growth and subsequent relaxation of island shape revealed that kinetically stiff direction differs from the thermodynamic one. This feature together with anisotropic mass incorporation determines the enantiomorphic evolution and rotational arrangement of crystallites during the growth of elongated organic molecules, like PnQ.     

Ta 5d band symmetry of 1T-TaS1.2Se0.8 in the commensurate charge-density-wave phase

We present a detailed angle-resolved photoemission study on the layered transition-metal dichalcogenide 1T-TaS1.2Se0.8 in the commensurate charge-density-wave (CDW) phase. A drastic reduction in the spectral weight along the high symmetry line GammaM, particularly around the point M, is observed when s-polarized light was used. This implies that the initial state must be symmetric with respect to a mirror plane perpendicular to the line GammaK, which is consistent with conventional band calculations in the absence of the CDW. We conclude that there is only a limited amount of modification of the electronic structure of 1T-TaS1.2Se0.8 in the commensurate CDW phase due to the CDW-related potential.     

Reversible photoelectronic signal conversion based on photoisomerization-controlled coordination change of azobenzene-bipyridine ligands to copper

A new "molecular photoelectronic transducer", working in a cyclic manner totally powered with light irradiation, has been constructed. The UV/blue-controlled repetitive motion of azobenzene moieties in 6,6'-bis(4' '-tolylazo)-4,4'-bis(4-tertbutylphenyl)-2,2'-bipyridine causes reciprocal CuI translocation between two coordination environments, resulting in pumping of the redox potential of CuI. Therefore, UV/blue light information can be successfully transformed into an electrode potential change and positive/negative current response, which is closely related to natural visual transduction both functionally and mechanically. This result demonstrates a new strategy for artificial molecular machine assembly, i.e. forming a path with multistep chemical reactions between input/output couples at choice.     

Palladium-catalyzed cyanoesterification of norbornenes with cyanoformates via the NC-Pd-COOR (R = Me and Et) intermediate

[reaction: see text] Palladium-catalyzed cyanoesterification of norbornenes proceeds stereoselectively via NC-Pd-COOR (R = Me and Et) complexes as intermediates.     

A new 19-metal-atom cluster [(Me2PhP)10Au12Ag7(NO3)9] with a nearly staggered-staggered M5 ring configuration

New mixed metal clusters with M19 metal frameworks have been synthesized by NaBH4 reduction of Au(NO3)(PMe2Ph) together with AgNO3 in ethanol. Single crystal X-ray diffraction has revealed Au12Ag7 and Au17Ag2 metal skeletons for these clusters, which are best described in terms of bicapped pentagonal antiprismatic cages with a staggered-staggered M(5) ring configuration. These clusters connect the missing link between M13 icosahedral and M25 biicosahedral clusters providing a view of the cluster growth process. A TEM image of this cluster has been observed, which has clearly demonstrated single-sized nano-particles of less than 1.0 nm.     

Asymptotics toward the planar rarefaction wave for viscous conservation law in two space dimensions

This paper is concerned with the asymptotic behavior of the solution toward the planar rarefaction wave connecting and for the scalar viscous conservation law in two space dimensions. We assume that the initial data tends to constant states as , respectively. Then, the convergence rate to of the solution is investigated without the smallness conditions of and the initial disturbance. The proof is given by elementary -energy method.

     

Powder spectra of 181Ta NMR in 2HTaS2

Powder spectra of ¹⁸¹Ta NMR in a swept field for the transitions between degenerate PQR states are discussed. Spin-echo signals of ¹⁸¹Ta in 2HTaS₂ powder have been observed at 4.2 K with line shapes that can clearly be associated with two inequivalent Ta sites, having well-defined asymmetry parameter (η) with values of 0.00 and 0.52 (± 0.02), one of which has the local charge density deviating strongly from the axial symmetry.