Water‐disintegrative and biodegradable blends containing poly(L‐lactic acid) and poly(butylene adipate‐co‐terephthalate)

In this study, novel biodegradable materials were successfully generated, which have excellent mechanical properties in air during usage and storage, but whose structure easily disintegrates when immersed in water. The materials were prepared by melt blending poly(L ‐lactic acid) (PLLA) and poly(butylene adipate‐co‐terephthalate) (PBAT) with a small amount of oligomeric poly(aspartic acid‐co‐lactide) (PAL) as a degradation accelerator. The degradation behavior of the blends was investigated by immersing the blend films in phosphate‐buffered saline (pH = 7.3) at 40 °C. It was shown that the PAL content and composition significantly affected morphology, mechanical properties, and hydrolysis rate of the blends. It was observed that the blends containing PAL with higher molar ratios of L ‐lactyl [LA]/[Asp] had smaller PBAT domain size, showing better mechanical properties when compared with those containing PAL with lower molar ratios of [LA]/[Asp]. The degradation rates of both PLLA and PBAT components in the ternary blends simultaneously became higher for the blends containing PAL with higher molar ratios of [LA]/[Asp]. It was confirmed that the PLLA component and its decomposed materials efficiently catalyze the hydrolytic degradation of the PBAT component, but by contrast that the PBAT component and its decomposed materials do not catalyze the hydrolytic degradation of the PLLA component in the blends. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Lower closure point of adsorption hysteresis in ordered mesoporous silicas

To examine the nature of the lower closure point of adsorption hysteresis in ordered mesoporous silicas, we measured the temperature dependence of the adsorption-desorption isotherm of nitrogen for three kinds of ordered silicas with cagelike pores and three kinds of ordered silicas with cylindrical pores. The lower closure point pressure of nitrogen in the cagelike pores with sufficiently small necks, that is, the cavitation pressure of a confined liquid, did not depend appreciably on the cage size in the temperature region far away from a hysteresis critical temperature (Tch) but its cage-size dependence was noticeable in the vicinity of Tch. The lower closure point in the cylindrical pores depended on the pore size, and its thermal behavior was totally different from that in the cagelike pores. Nevertheless, the hysteresis critical points of nitrogen in the ordered mesoporous silicas, which are defined as a threshold of temperatures (Tch) and pressure above which reversible capillary condensation takes place in a given size and shape of pores, fell on a common line in a temperature-pressure diagram regardless of the pore geometries. We consider this finding as evidence that capillary evaporation in the cylindrical pores follows a cavitation process in the vicinity of Tch in the same way as that in the cagelike pores and also that the low limit of the hysteresis loop that has been long recognized since 1965 is due to the occurrence of a vapor bubble in a stretched metastable liquid confined to the pores with decreasing pressure (cavitation).     

Freeze-thawing single human embryonic stem cells induce e-cadherin and actin filament network disruption via g13 signaling

Poor adhesion of single human embryonic stem (hES) cells after freeze-thawing causes death. To investigate mechanisms responsible for this, Rho-dependent protein kinase (ROCK) inhibitor Y-27632-treated and untreated single hES cells were analyzed for E-cadherin and F-actin distribution by immunostaining and phalloidin staining respectively and for G13 signaling pathway components by DNA microarray and quantitative polymerase chain reaction (PCR). Y-27632-treated cells clustered rapidly and maintained E-cadherin and F-actin distribution without losing Oct-3/4. Immediately after thawing, E-cadherin in untreated hES cells dotted along the membrane and then displayed eccentric cytoplasmic localization. Bleb formation and early Oct-3/4 loss occurred after F-actin network condensation in the cytoplasm. Microarray analyses and quantitative PCR indicated upregulation of two actin reorganization-associated components of the G13 signaling pathway, Arhgdib and Cdc42, in untreated cells. Considering these findings and that cell death was partly interrupted by Y-27632, E-cadherin and actin cytoskeleton network disruption through the G13 signaling pathway may cause hES cell death after freeze-thawing.     

Optical Analysis and Qualitative Discrimination of Vortex-Flame Interaction in a Plane Premixed Shear Layer

To obtain practical schemes of vortex–flame interactions, a series of organized eddies formed in the plane premixed shear layer is investigated, instead of a single vortex ring or a single vortex tube. The plane premixed shear layer is first formed between two parallel uniform propane–air mixture streams. For getting clear qualitative pictures of vortex–flame interactions in the plane premixed shear layer, two extreme ignition points are assigned; one is assigned at the center of an organized eddy where the vortex motion plays an important role, the other at the midpoint between two adjacent organized eddies where the rolling-up motion prevails. A premixed flame is initiated by an electric discharge at one of the two assigned points and propagates either in the large scale organized eddy or along the interface between two uniform mixture streams. Propagation and deformation processes of the flame are observed using the simultaneously two-directional and high-speed Schlieren photography. The tangential velocity of organized eddy and the equivalence ratio of premixed shear flow are varied as two main parameters. The outline of propagating flame after the midpoint ignition is numerically analyzed by superposing the flame propagation having a constant burning velocity on the vortex flow field simulated with the discrete vortex method. The results obtained show that there exists another type of vortex–flame interaction in the plane shear layer in addition to the vortex bursting, and that it is caused by the rolling-up motion particular to the coherent structure in the plane shear layer and is simply named the vortex boosting. It is qualitatively concluded therefore that, in the ordinary turbulent premixed flames formed in the plane premixed shear layer, these two fundamental vortex-flame interactions get tangled with each other to augment the propagation velocity. An empirical expression which qualitatively takes into account of the effects of both vortex and chemical properties is finally proposed.     

Hairy particles prepared by living radical graft-polymerization

Novel particles having designed hairs were prepared by living radical graft-polymerization on core particles. The living radical species used in this study was a kind of photo-iniferter, N, N-diethyl-thiocarbamate. Main component of hair was poly(N-isopropylacrylamide) (PNIPAM) which was a representative thermo-sensitive polymer. The polymerization was carried out by UV irradiation at room temperature that was lower than the transition temperature of PNIPAM. Incorporation of a small amount of acrylic acid into the hair caused significant change in the properties of hairy particles. The mode of comonomer charge also enabled to design the hair structure on the particles.     

Effects of the number of fatty acid residues on the phase behaviors of decaglycerol fatty acid esters

The effects of the number of fatty acid residues (n) in decaglycerol fatty acid esters, i.e., decaglycerol laurates (abbreviated to (C11)nG10), on the phase behaviors of three laurate esters, (C11)1.9G10, (C11)2.7G10, and (C11)3.4G10, were investigated. The unreacted decaglycerol remaining in each ester was removed by liquid extraction before use. (C11)1.9G10 formed hexagonal liquid crystals in aqueous solutions, while (C11)2.7G10 and (C11)3.4G10, which are more hydrophobic than (C11)1.9G10, formed lamellar liquid crystals. The cloud point in aqueous solution was measured for mixtures of these three esters. The cloud phenomenon was observed when the weight ratio of hydrophilic groups to the total surfactant (WH/WS) was around 0.6. The cloud point shifted to a markedly higher temperature, even with a slight increase in the WH/WS ratio. The solubilization abilities of (C11)nG10 for the oils m-xylene and (R)-(+)-limonene were also examined. When the WH/WS ratio was between 0.60 and 0.64, (C11)nG10 formed microemulsions and lyotropic liquid crystals in the presence of water and the oils. These self-organized structures were stable, even above 90 degrees C. It is concluded that the phase behavior of (C11)nG10 are insensitive to temperature, but strongly dependent on both the WH/WS ratio and the number of fatty acid residues (n).     

3D-CT(Computer Tomography) Measurement of an Instantaneous Density Distribution of Turbulent Flames with a Multi-Directional Quantitative Schlieren Camera (Reconstructions of High-Speed Premixed Burner Flames with Different Flow Velocities)

In order to provide a suitable technique for 3D observation of high speed turbulent flames, non-scanning 3D-CT(Computer Tomography) technique using a multi-directional quantitative schlieren system with flash light source, is proposed for instantaneous density distribution of unsteady premixed flames. This “schlieren 3D-CT” is based on (i)simultaneous acquisition of flash-light schlieren images taken from numerous directions, and (ii) 3D-CT reconstruction of the images by an appropriate CT algorithm. In this paper, first, as a preliminary research, 3D-CT reconstruction of non-axisymmetric steady flame is made with a single-directional quantitative schlieren system. Next, with custom-made 20 directional schlieren camera, instantaneous density distributions of a high-speed turbulent flames of nozzle exit velocities of 8.0 and 10.0 m/s has been CT-reconstructed. The 3D-views of the reconstructed flame front shape clearly give the information of the flame structure with fine scale corrugations. Based on the distributions, area-enlargement rates of the flame front area are derived, and investigated.     

Reversible helix-random coil transition of poly(m-phenylenediethynylene) by a rotaxane switch

Pendant rotaxane switch-tethering poly(m-phenylene diethynylene) was synthesized by the polyoxidative coupling of a rotaxane containing an axle-terminal m-diethynylbenzene group and an optically active crown ether. The reversible helix-random coil transition of the polymer was successfully performed by the positional switching of the rotaxane wheel.