Controlled radical polymerization with polyolefin macroinitiator: a convenient and versatile approach to polyolefin-based block and graft copolymers

This paper introduces the new synthetic methodology of polyolefin-based block and graft copolymers with polar segments [e.g., polystyrene and poly(meth)acrylates]. Various brominated polyolefins were prepared by bromination of polyolefins with N-bromosuccinimide. The resulting brominated polyolefins were able to initiate the controlled radical polymerization of polar monomers, such as methyl methacrylate, ethyl acrylate, t-butyl acrylate, styrene and 2-(dimethylamino)ethyl acrylate, using a CuBr/N,N,N′,N″,N″-pentamethyldiethylenetriamine catalyst system, leading to a variety of polyolefin-based copolymers with a different content of the corresponding polar segment. Because of the accessible synthesis of polyolefin macroinitiators, this synthetic methodology is expected to result in the preparation of a wide range of polyolefin-based block and graft copolymers.     

Recent progress in the preparation,characterization, and applications of nanofibers and nanofiber membranes via electrospinning/interfacial polymerization

Significant progress has been made recently in the fabrication of polymeric nanofibers, their characterization and applications, new polymeric materials, theoretical analysis, and so forth. Hence, in this brief review, we report the progress made in these subjects during the last 5 years. Most of the work concerns nanofibers related to the field of medicine. On the other hand, negligibly few reports have been found on nanofibers related to membrane separation processes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Optical properties of end-sealed hollow fibers

We propose sealing techniques for medical hollow fibers to protect the inner surface of fibers from debris or water that scatters from targets. First, hollow fibers are sealed with a film of polymer that is easily formed by use of a dipping technique. The transmission loss of 20-microm-thick sealing film was 0.2 dB for Er:YAG laser light, and the maximum energy that is available for the film was 180 mJ. Second, a sealed glass cap was applied to the output end of hollow fiber. The silica-glass cap with a wall thickness of 400 microm shows a transmission loss of 0.5 dB and was not damaged by radiation of 400-mJ energy pulses.     

Effect of active oxygen species on the productivity of torularhodin by Rhodotorula glutinis No. 21

The effect of active oxygen species on the productivity of torularhodin, an effective antioxidant, by soil yeast, Rhodotorula glutinis no. 21, was examined. Methylene blue, methyviologen and AAPH [2,2'-azobis(2-amidinopropane) dihydrochloride] were used as generators of singlet oxygen, superoxide anion radicals and peroxy radicals, respectively. All of them indicated effectiveness at a dose of 1.0 x 10(-10) to 3.0 x 10(-6) M. Addition of these generators to the culture medium had almost no influence on the biosynthesis of beta-carotene, whereas it had marked enhancement on those of torulene and torularhodin. Production of uric acid by xanthineoxidase remained unchanged at a torularhodin concentration of up to 100 microM. This result suggests that torularhodin does not directly affect the productivity of superoxide anions. It has been proved that torularhodin has a more potent effect on the scavenging of peroxyl radicals and inhibits substrate degradation by singlet oxygen more effectively than beta-carotene does. Continuous addition of methylene blue enhanced the torularhodin accumulation more markedly than single addition.     

Calculation of phase diagrams for the FeCl2, PbCl2, and ZnCl2 binary systems by using molecular dynamics simulation

Recently, molecular dynamics (MD) simulation has been widely employed as a very useful method for the calculation of various physicochemical properties in the molten slags and fluxes. In this study, MD simulation has been applied to calculate the structural, transport, and thermodynamic properties for the FeCl₂, PbCl₂, and ZnCl₂ systems using the Born—Mayer—Huggins type pairwise potential with partial ionic charges. The interatomic potential parameters were determined by fitting the physicochemical properties of iron chloride, lead chloride, and zinc chloride systems with experimentally measured results. The calculated structural, transport, and thermodynamic properties of pure FeCl₂, PbCl₂, and ZnCl₂ showed the same tendency with observed results. Especially, the calculated structural properties of molten ZnCl₂ and FeCl₂ show the possibility of formation of polymeric network structures based on the ionic complexes of ZnCl ₄ ²⁻ , ZnCl ₃ ⁻ , FeCl ₄ ²⁻ , and FeCl ₃ ⁻ , and these calculations have successfully reproduced the measured results. The enthalpy, entropy, and Gibbs energy of mixing for the PbCl₂-ZnCl₂, FeCl₂-PbCl₂, and FeCl₂-ZnCl₂ systems were calculated based on the thermodynamic and structural parameters of each binary system obtained from MD simulation. The phase diagrams of the PbCl₂-ZnCl₂, FeCl₂-PbCl₂, and FeCl₂-ZnCl₂ systems estimated by using the calculated Gibbs energy of mixing reproduced the experimentally measured ones reasonably well.     

Numerical prediction of fraction of eutectic phase in Sn−Ag−Cu soldring using the phase-field method

A combination of macroscale solidification simulation and phase-field calculation is employed to predict the volume fraction of the eutectic phase in Sn-4.0 mass% Ag-XCu solder alloys (X=0.5–1.1 mass%). The solidification simulation incorporates the cooling rate in the phase-field simulation. We assume the residual liquid solidifies as eutectic phase when the driving force for the nucleation of Cu₆Sn₅ amounts to a critical value, which is determined based on the experimental data. Though the calculation results depend on the experimental data, the obtained fractions are about 40% for 0.5 mass% Cu and more than 90% for 1.1 mass% Cu alloy, which shows good agreement with the experimental data.     

Cloning of a gene for D-sorbitol dehydrogenase from Gluconobacter oxydans G624 and expression of the gene in Pseudomonas putida IFO3738

We have cloned a novel gene for d-sorbitol dehydrogenase (SLDH), which efficiently converted D-sorbitol to L-sorbose, from Gluconobacter oxydans G624 (FERM BP-4415). A cosmid library of the genomic DNA was screened by assaying SLDH activity. The inserted DNA from a positive clone was downsized by subcloning into charomid and pUCP plasmid, successively. Sequencing analysis of the DNA responsible for SLDH activity revealed an open reading frame of 1455 bp coding for 485 amino acid residues with a calculated molecular mass of 53,642 Da. The amino acid sequence showed 42.2% identity with a NAD+-dependent mannitol dehydrogenase (MDH), which catalyzed conversion of d-sorbitol to d-fructose, from Pseudomonas fluorescens DSM50106. Since the intact SLDH was found to be very unstable during isolation and purification, this SLDH fused to 6 x His-tag was expressed in Pseudomonas putida IFO3738 and purified by immobilized metal affinity chromatography using cobalt-based resins. The 6 x His-tag SLDH catalyzed the oxidation of D-sorbitol to L-sorbose and exhibited 15 times higher activity in the presence of NADP+ than that of NAD+. These results indicate that the SLDH is a novel kind of dehydrogenase distinct from MDH previously reported.     

In vitro release kinetics of gentamycin from a sodium hyaluronate gel delivery system suitable for the treatment of peripheral vestibular disease

For certain patients who experience intense vertigo arising from unilateral vestibular lesions, the primary therapy is a vestibular nerve section, an intracranial surgical procedure. One alternative to this treatment is therapeutic ablation of vestibular function on the unaffected side using an ototoxic agent. We prepared a biodegradable sustained-release gel delivery system using sodium hyaluronate that can be administered into the middle ear using only a local anesthetic. The gel contains gentamycin sulfate, the ototoxic agent of choice for treatment of unilateral vestibulopathy, and it exhibits diffusion-controlled release of the drug over a period of hours. The released gentamycin could then diffuse into the inner ear through the round membrane. This represents an important advance over previous formulations, which used only gentamycin sulfate solutions, in that it should allow more careful control of the dose, it should reduce loss of the drug from the middle ear site, and it should maintain intimate contact with the round membrane. By carefully controlling the dose, it should be possible to inhibit vestibular function while minimizing hearing loss. Herein we describe the in vitro release kinetics of gentamycin sulfate from sodium hyaluronate gels and find that the system obeys Fickian behavior.     

Mechanisms of reduction in hole concentration in Al-doped 4H-SiC by electron irradiation

From the temperature dependence of the hole concentration in unirradiated lightly Al-doped 4H-SiC epilayers, an Al acceptor with E_V + 0.2 eV, which is an Al atom (Al_Si) at a Si sublattice site, and an unknown deep acceptor with E_V + 0.35 eV are found, where E_V is the top of the valence band. Both the densities are similar. With irradiation of 0.2 MeV electrons the Al acceptor density is reduced, while the unknown deep acceptor density is increased. Judging from the minimum electron energy required to displace a substitutional C atom (C_s) or the Al_Si, the bond between the Al_Si and its nearest neighbor C_s is broken due to the displacement of the C_s by this irradiation. Moreover, the displacement of the C_s results in the creation of a complex (Al_Si-V_C) of Al_Si and a carbon vacancy (V_C), indicating that the possible origin of the deep acceptor with E_V + 0.35 eV is Al_Si-V_C.