New bleeding model of additives in a polypropylene film under atmospheric pressure II

Many additives are commercially used to add more favorable qualities to films. The bleeding process by which the additive in a film comes to the surface is considered. A new bleeding model of additives in a polypropylene film under atmospheric pressure was investigated. Solubility and diffusion are found to be important for explaining this bleeding process. It was found that the experimental results were explained more precisely by assuming a two‐step transport process between the crystalline regions and the amorphous ones. The solubilities and diffusion coefficients of UV‐stabilizers such as 2‐(2H‐benzotriazol‐2‐yl)‐4‐(1,1,3,3‐tetramethylbutyl)phenol and 2‐(2H‐benzotriazol‐2‐yl)‐4‐methylphenol were determined at 40°C. The difference between the saturation solubilities and the diffusion coefficients of UV‐stabilizers was discussed by comparing with the results of molecular dynamics (MD) simulation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Ceramic Dental Molds for the Precision Casting of Titanium and Titanium Alloys: I, Relationship between Particle-Size Distribution of Aggregates and Mold Expansion

A new ceramic dental mold can cast excellent Ti restoratives by controlling expansion due to the oxidation of additive metal particles. The packing structure of the metal and aggregate particles in the mold can be considered a function of the size distribution of the aggregate grains. An investigation of the expansion mechanism reveals three different relationships of void fraction versus linear thermal expansion for the molds at the high temperature under which oxidation of the metal particles occurs. Room-temperature casting, favorable for making high-quality Ti restoratives, can also be achieved by precisely controlling both the amount of additive metal powder and the compositional distribution of aggregate grain sizes in the mold.     

On a fast reactor cycle scheme that incorporates a thoria-based minor actinide-containing cermet fuel

A fast reactor cycle scheme that incorporates a thoria-based minor actinide-containing cermet fuel is given. The present cermet fuel consists of an oxide solid solution of Th and minor actinides and Mo-inert matrix. It has been proposed as a high-performance device that can enhance minor actinide incineration in a fast reactor cycle. It is used in an independent small sub-cycle, whereby dedicated cycle technologies are adopted. Two-step reprocessing process was proposed for the present cermet fuel; it consists of a pre-removal of Mo-inert matrix and an actinide recovery. A preliminary test for the pre-removal of Mo-inert matrix was carried out using a surrogate cermet fuel. Burnup characteristics of a fast reactor core loaded with the cermet fuel were investigated by using neutronic calculation codes. It was revealed that a heterogeneous composition of Mo-inert matrix in inner and outer cores may lead to an effective transmutation of minor actinides and a flattened power density. It was concluded that the present cermet fuel was potentially promising as a high-performance incineration device of minor actinides for fast reactors.     

Optical properties of colloidal crystalline arrays composed of hollow polystyrene spheres

We have evaluated the optical properties of close‐packed and non close‐packed colloidal crystalline arrays made of hollow polystyrene spheres. Close‐packed colloidal crystalline arrays were fabricated by simple evaporation of dispersions, whereas nonclose‐packed colloidal crystalline arrays were fabricated by exploiting electrostatic interactions between the spheres in aqueous dispersion. Optical properties of the arrays were estimated from angle‐resolved reflection spectra. The Bragg diffraction peak of the colloidal crystalline array made of hollow spheres was of shorter wavelength than in the case of solid spheres, not only for the close‐packed array but also for the nonclose‐packed array. These shifts were caused by a decrease in the effective refractive index n_eff with decreasing particle refractive index. We have found that this relationship could be explained by the simple equation n_eff = n_particle?+ n_solvent (1 ? ?), where ? is the volume fraction of the particles, for both close‐packed and non close‐packed arrays. The current work suggests new possibilities for the creation of advanced colloidal crystals. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2364–2368, 2007     

Selective hydrogenation of chloronitrobenzene to chloroaniline in supercritical carbon dioxide over Ni/TiO2: Significance of molecular interactions

The hydrogenation of chloronitrobenzene to chloroaniline was investigated over Ni/TiO₂ at 35 °C in supercritical CO₂ (scCO₂), ethanol, and n-hexane. The reaction rate followed the order of scCO₂ > n-hexane > ethanol. In scCO₂, the selectivity to chloroaniline and to aniline over Ni/TiO₂ were 97–99.5% and <1%, respectively, in the conversion range of 9–100%. The high chemoselectivity to chloroaniline cannot be achieved over Ni/TiO₂ in ethanol and n-hexane. In situ high-pressure Fourier transform infrared measurements were made to study the molecular interactions of CO₂ with the following reactant and reaction intermediates: chloronitrobenzene, chloronitrosobenzene, and N-chlorophenylhydroxylamine. The molecular interaction modifies the reactivity of each species and accordingly the reaction rate and the selectivity. The influence of Cl substituent on the interaction modes of CO₂ with these reacting species is discussed. Possible reaction pathways for the hydrogenation of chloronitrobenzene in scCO₂ over Ni/TiO₂ are also proposed.     

Relative reactivity of phenylboronic acid to phenylboronate ion toward L-lactate and mandelate at physiological pH

Kinetic studies were performed on the reactions of phenylboronic acid with L-lactic acid and mandelic acid in acidic aqueous and alkaline solutions in order to specify reactive species in these reactions. It was confirmed that the diprotonated ligand (H₂L: L-lactic acid or mandelic acid) is less reactive than the monoprotonated ligand (HL^?: L-lactate ion or mandelate ion), which made possible direct determination of the rate constants of phenylboronic acid (PhB(OH)₂) and its conjugate base, phenylboronate ion (PhB(OH)₃^?). It was found that PhB(OH)₂ is more reactive than PhB(OH)₃^?. On the basis of kinetic results, it was concluded that the most reactive species are PhB(OH)₂ and HL^? at physiological pH 7.4, so the reaction in the boronic acid-based sensor for L-lactate mainly would occur between these species.     

Chlorine isotope fractionation during reductive dechlorination of chlorinated ethenes by anaerobic bacteria

Chlorine isotope fractionation during reductive dechlorination of trichloroethene (TCE) and tetrachloroethene (PCE) to cis-1,2-dichloroethene (cDCE) by anaerobic bacteria was investigated. The changes in the 37Cl/35Cl ratio observed during the one-step reaction (TCE to cDCE) can be explained by the regioselective elimination of chlorine accompanied by the Rayleigh fractionation. The fractionation factors (alpha) of the TCE dechlorination by three kinds of anaerobic cultures were approximately 0.994-0.995 at 30 degrees C. The enrichment of 37Cl in the organic chlorine during the two-step reaction (PCE to cDCE) can be explained by the random elimination of one chlorine atom in the PCE molecule followed by the regioselective elimination of one chlorine atom in the TCE molecule. The fractionation factors for the first step of the PCE dechlorination with three kinds of anaerobic cultures were estimated to be 0.987-0.991 at 30 degrees C using a mathematical model. Isotope fractionation during the first step would be the primary factor for the chlorine isotope fractionation during the PCE dechorination to cDCE. The developed models can be utilized to evaluate the fractionation factors of regioselective and multistep reactions.     

Four-base codon-mediated incorporation of non-natural amino acids into proteins in a eukaryotic cell-free translation system

Various four-base codons have been shown to work for the introduction of non-natural amino acids into proteins in an Escherichia coli cell-free translation system. Here, a four-base codon-mediated non-natural mutagenesis was applied to a eukaryotic rabbit reticulocyte cell-free translation system. Mutated streptavidin mRNAs containing four-base codons were prepared and added to a rabbit reticulocyte lysate in the presence of tRNAs that were aminoacylated with a non-natural amino acid and had the corresponding four-base anticodons. A Western blot analysis of translation products indicated that the four-base codons CGGU, CGCU, CCCU, CUCU, CUAU, and GGGU were efficiently decoded by the aminoacyl-tRNAs having the corresponding four-base anticodons. In contrast, the four-base codons AGGU, AGAU, CGAU, UUGU, UCGU, and ACGU were not decoded. The stop codon-derived four-base codons UAGU, UAAU, and UGAU were found to be inefficient, whereas the amber codon UAG and opal codon UGA were efficient for the incorporation of non-natural amino acids. The application of the expanded genetic code in a eukaryotic cell-free system opens the possibility of a four-base codon-mediated incorporation of non-natural amino acids into proteins in living eukaryotic cells.