Density-fluctuation-induced swelling of polymer thin films in carbon dioxide

We report an anomalous swelling of polymer thin films in carbon dioxide (CO(2)) which is associated (in both locus and form) with the density fluctuation ridge that forms along the extension of the coexistence curve of gas and liquid in the P-T phase diagram. Neutron reflectivity results showed that CO(2) could be sorbed to a large extent ( approximately 60%) in thin polymer films even when the bulk miscibility of the polymer with CO(2) is very poor. The anomalous swelling is found to scale with the polymer radius of gyration (R(g)) and extends to a distance approximately 10 R(g).     

Structural study of self-assembled monolayers of ferrocenylalkanethiols on gold by angleresolved X-ray photoelectron spectroscopy

An angle-resolved X-ray photoelectron spectroscopic study has been performed on structures of self-assembling systems, viz ferrocenylthiols on a gold (111) crystal. The angular dependence of the intensities of photoemission reveals that ferrocenyl groups are on the outermost layer, separated from the gold substrate by hydrocarbon chains of the thiol groups.     

A time-decomposition algorithm for a stiff linear two-point boundary-value problem and its application to a nonlinear optimal control problem

An algorithm is proposed to solve a stiff linear two-point boundary-value problem (TPBVP). In a stiff problem, since some particular solutions of the system equation increase and others decrease rapidly as the independent variable changes, the integration of the system equation suffers from numerical errors. In the proposed algorithm, first, the overall interval of integration is divided into several subintervals; then, in each subinterval a sub-TPBVP with arbitrarily chosen boundary values is solved. Second, the exact boundary values which guarantee the continuity of the solution are determined algebraically. Owing to the division of the integration interval, the numerical error is effectively reduced in spite of the stiffness of the system equation. It is also shown that the algorithm is successfully imbedded into an interaction-coordination algorithm for solving a nonlinear optimal control problem.The authors would like to thank Mr. T. Sera and Mr. H. Miyake for their help with the calculations.     

Propagation of solitary ion acoustic waves in inhomogeneous plasmas

A WKB solution for the propagation of a solitary ion acoustic wave in a plasma with a density gradient is obtained.     

Electrochemical assembly and potential-dependent plasmon absorption of au nanoclusters covered with a 4-aminothiophenol self-assembled monolayer

Gold nanoclusters covered with 4-aminothiophenol (4-ATP) self-assembled monolayers (SAMs) were electrochemically assembled on an Au or ITO electrode. The assembly mechanism is discussed on the basis of results of electrochemical, FT-IR, and XPS measurements. The intensity of plasmon absorption of the gold nanocluster assembly was shown to be dependent on applied potential as a result of electrochemical doping/undoping of a counteranion in the polyaniline film.     

Enzymatic transformation of bacterial polyhydroxyalkanoates into repolymerizable oligomers directed towards chemical recycling

The enzymatic transformation into an oligomer was carried out with the objective of developing the chemical recycling of bacterial polyesters. Poly(R-3-hydroxyalkanoate)s (PHAs), such as poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyhexanoate)] and poly[(R-3-hydroxybutyrate)-co-12%(R-3-hydroxyvalerate)], were degraded by granulated Candida antarctica lipase B immobilized on hydrophilic silica (lipase GCA) in a diluted organic solvent at 70 degrees C. The degradation products were cyclic oligomers having a molecular weight of a few hundreds. The obtained cyclic oligomer was readily repolymerized by the same lipase (lipase GCA) to produce the corresponding polyester in a concentrated solution. The cyclic oligomer was copolymerized with epsilon-caprolactone using lipase to produce the corresponding terpolymers having an Mw of 21,000. This is the first example of the enzymatic chemical recycling of bacterial PHAs using lipase. Poly(R-3-hydroxybutyrate) [P(3HB)] was also degraded into the linear-type R-3HB monomer to trimer by P(3HB)-depolymerase (PHBDP) in phosphate buffer at 37 degrees C. The degradation using PHBDP required a longer reaction time compared with the lipase-catalyzed degradation in organic solvent. The monomer composition of the oligomer depended on the origin of the PHBDP. The R-3HB monomer was predominately produced by PHBDP from Pseudomonas stutzeri, while the R-3HB dimer was produced by PHBDP from Alcaligenes faecalis T1. Repolymerization of these oligomers by lipase in concentrated organic solvent produced a relatively low-molecular-weight P(3HB) (e.g., Mw=2,000). Degradation of P(3HB) by lipase in organic solvent into repolymerizable cyclic oligomer and degradation of P(3HB) by PHBDP in buffer into hydroxy acid type R-3HB dimer.     

Heterogeneity in oscillator networks: are smaller worlds easier to synchronize?

Small-world and scale-free networks are known to be more easily synchronized than regular lattices, which is usually attributed to the smaller network distance between oscillators. Surprisingly, we find that networks with a homogeneous distribution of connectivity are more synchronizable than heterogeneous ones, even though the average network distance is larger. We present numerical computations and analytical estimates on synchronizability of the network in terms of its heterogeneity parameters. Our results suggest that some degree of homogeneity is expected in naturally evolved structures, such as neural networks, where synchronizability is desirable.     

Studies on the chemical constituents of stem bark of Millettia leucantha: isolation of new chalcones with cytotoxic,anti-herpes simplex virus and anti-inflammatory activities

Four new chalcone derivatives (1, 4, 7, 10) were isolated from the stem bark of Millettia leucantha KURZ (Leguminosae) along with two known ones (2, 6) and five known flavones (3, 5, 8, 9, 11). Structure elucidation and unambiguous assignment of the isolates were achieved with the aid of 1D and 2D NMR extensive studies. Correlation of 10 to 4 was successfully done by reduction with Et(3)SiH/CF(3)CO(2)H. Moderate cytotoxic activity was observed in chalcones (1, 10), whereas dihydrochalcones (4, 6) showed moderate anti-Herpes Simplex Virus (HSV) activity. Interestingly, flavone 8 showed significant anti-inflammatory effects inhibiting both cyclooxygenase (COX)-1 and -2.     

Sigmasigma* transition in anti,cisoid alternating oligosilanes: clear-cut evidence for suppression of conjugation effect by a cisoid turn

On the basis of the UV absorption spectra of the anti,cisoid alternating oligosilanes, the first experimental clear-cut evidence was presented for the generally accepted idea that the sigma conjugation in polysilanes does not effectively extend through a tetrasilane fragment with a small dihedral angle such as a cisoid turn.