Dispersion and current-voltage characteristics of helical polyacetylene single fibers

To study the transport properties of individual helical polyacetylene (PA) fibers, we developed a method to extract a single fiber from tightly entangled ropes of helical PA bulk film. After a few minutes of sonication of a piece of helical PA bulk film in an organic solution containing surfactant, a droplet of solution is deposited on the pre-pattened electrode under argon atmosphere. AFM images show that extracted helical PA fibers are typically 10 mum in length and 100-200 nm in diameter. We found that the helicity of bulk materials is conserved. We present the temperature dependencies of current-voltage characteristics of individual helical PA fibers doped with iodine.     

Complete 1H and 13C NMR assignments of two phytosterols from roots of Piper nigrum

Using modern NMR techniques, including DQF-COSY, NOESY, HETCOR and HMBC, the full assignments of all 1H and 13C chemical shifts were made for stigmastane-3,6-dione and stigmast-4-ene-3,6-dione, isolated from the roots of Piper nigrum (Piperaceae). Their stereochemistry was resolved by a combination of 2D NOESY data and analysis of coupling constants. The two compounds were isolated from the genus Piper for the first time.     

Melting points and thermal expansivities of proton-disordered hexagonal ice with several model potentials

A method of free energy calculation is proposed, which enables to cover a wide range of pressure and temperature. The free energies of proton-disordered hexagonal ice (ice Ih) and liquid water are calculated for the TIP4P [J. Chem. Phys. 79, 926 (1983)] model and the TIP5P [J. Chem. Phys. 112, 8910 (2000)] model. From the calculated free energy curves, we determine the melting point of the proton-disordered hexagonal ice at 0.1 MPa (atmospheric pressure), 50 MPa, 100 MPa, and 200 MPa. The melting temperatures at atmospheric pressure for the TIP4P ice and the TIP5P ice are found to be about T(m)=229 K and T(m)=268 K, respectively. The melting temperatures decrease as the pressure is increased, a feature consistent with the pressure dependence of the melting point for realistic proton-disordered hexagonal ice. We also calculate the thermal expansivity of the model ices. Negative thermal expansivity is observed at the low temperature region for the TIP4P ice, but not for the TIP5P ice at the ambient pressure.     

Chiral phosphinooxazolidine ligands for palladium- and platinum-catalyzed asymmetric Diels-Alder reactions

Cationic palladium (Pd)- and platinum (Pt)-phosphinooxazolidine catalysts 13a-c, 15a-d, 17a-c, and 19a-c were prepared from phosphinooxazolidine ligands 1-3, MCl(2) (M = Pd and Pt), and counterions, and the activities of the catalysts in the asymmetric Diels-Alder (DA) reactions of cyclic or acyclic dienes with imide dienophiles were investigated. These catalysts demonstrated high levels of catalytic activity. The cationic Pd-POZ complex 13c provided particularly excellent enantioselectivity (98% ee) in the DA reactions of cyclopentadiene with acryloyl-, crotonyl-, and fumaroyl-1,3-oxazolidin-2-ones (20a-c).     

Beta-1,3-glucan polysaccharides as novel one-dimensional hosts for DNA/RNA, conjugated polymers and nanoparticles

Beta-1,3-glucan polysaccharides have triple-stranded helical structures whose sense and pitch are comparable to those of polynucleotides. We recently revealed that the beta-1,3-glucans could interact with certain polynucleotides to form triple-stranded and helical macromolecular complexes consisting of two polysaccharide-strands and one polynucleotide-strand. This unique property of the beta-1,3-glucans has made it possible to utilize these polysaccharides as potential carriers for various functional polynucleotides. In particular, cell-uptake efficiency of the resultant polysaccharide/polynucleotide complexes was remarkably enhanced when functional groups recognized in a biological system were introduced as pendent groups. The beta-1,3-glucans can also interact with various one-dimensional architectures, such as single-walled carbon nanotubes, to produce unique nanocomposites, in which the single-walled carbon nanotubes are entrapped within the helical superstructure of beta-1,3-glucans. Various conductive polymers and gold nanoparticles are also entrapped within the helical superstructure in a similar manner. In addition, diacetylene monomers entrapped within the helical superstructure can be photo-polymerized to afford the corresponding poly(diacetylene)-nanofibers with a uniform diameter. These findings indicate that the beta-1,3-glucans are very attractive and useful materials not only in biotechnology but also in nanotechnology. These unique properties of the beta-1,3-glucans undoubtedly originate from their inherent, very strong helix-forming character which has never been observed for other polysaccharides.     

Reverse permeation of sodium ions driven by pH difference across a liquid membrane: time dependencies of membrane resistance and membrane potential in a reverse permeation system

The diffusional flux of sodium ions across a liquid membrane was observed as a reverse permeation phenomenon: sodium ions were transported across the membrane against their own concentration difference. A supported liquid membrane having stearic acid as an ionic carrier was used. The internal aqueous phase contained NaCl and HCl and the external aqueous phase contained NaOH of the same initial concentration as NaCl in the internal aqueous phase. The reverse permeation occurred with a long time delay. During the delay, sodium ions flowed from the acidic to alkaline solution. The diffusion coefficient of sodium ion estimated from the flux equation taking into account the Donnan equilibrium at the interface was found to be much greater than that in the membrane solvent, 1-octanol. In the same membrane system as for the flux measurement, the membrane conductance and the membrane potential were measured as a function of time. The time dependence of the membrane potential in the presteady state showed a biphasic behavior. The initial rapid phase could be attributed to the change in the phase boundary potential and the subsequent slow step to the change in the diffusion potential within the membrane. Before the steady membrane potential had been reached, the reverse permeation of sodium ions against their own concentration difference was not observed. During the slow relaxation process of the membrane potential, the membrane resistance decreased to approach the steady state. Moreover, the oscillation of membrane potential abruptly started at a time in the slow step of the potential change and continued during the steady state. It was suggested that, at the presteady state, the increase in the amount of water in the membrane would drive a drastic change in the state of the liquid membrane in the filter pore, e.g. an inverted micellar structure making.     

Adsorption Isotherm of Water Vapor and Its Large Hysteresis on Highly Ordered Mesoporous Silica

The first and second adsorption–desorption isotherms of water vapor on a new mesoporous material derived from kanemite have been measured. The isotherms show unusual type V isotherms and large hysteresis. The type V isotherms, which have never been observed for the other adsorbates, suggest that the mesoporous material has a hydrophobic surface, although the hydrophobicity decreased after treatment with water vapor because of rehydration of the surface. The significantly large hysteresis could be explained by the difference in contact angle between adsorption and desorption.     

Vinyl Polymerization. 439. Vinyl Polymerization Initiated by Poly(Ethylene Glycol] Diglycolic Acid or its Sodium Salt

Abstract

The polymerization of some kinds of vinyl monomer was found to occur in aqueous solutions of poly(ethylene glycol) diglycolic acid (PEG Acid) or sodium poly(ethylene glycol) diglycolate (PEG Acid Na) through radical mechanisms without any further initiator, as a so-called “uncatalyzed polymerization.” Although the initiating radical species for PEG Acid was determined to be the same as that for PEG Acid Na by means of the spin-trapping technique, the initiating ability of PEG Acid was higher than that of PEG Acid Na. These results are assumed to be attributable to the difference in the initiation mechanisms of the two systems and in the incorporating abilities of monomer into the hydrophobic areas formed by PEG Acid and PEG Acid Na.     

Growth limits in platinum oxides formed on Pt-skin layers on Pt-Co bimetallic nanoparticles

The dynamical oxidation processes of Pt-skin layers on Pt(3)Co were investigated in situ and in real-time by time-resolved X-ray absorption spectroscopy combined with electrochemical measurements. Growth limit behaviors and the suppression of higher-order formation of surface oxides were observed, and these might explain the highly durable nature of Pt-skin layers.