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.     

Functional binders for reversible lithium intercalation into graphite in propylene carbonate and ionic liquid media

Poly(acrylic acid) (PAA), poly(methacrylic acid) (PMA), and poly(vinyl alcohol) (PVA), which have oxygen species as functional groups, were utilized as a binder for graphite electrodes, and the electrochemical reversibility of lithium intercalation was examined in PC medium and ionic liquid electrolyte, lithium bis(trifluoromethanesulfonyl)amide dissolved in 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)amide (BMP-TFSA). Columbic efficiency of 75–80% with more than 300 mAh g^?1 was achieved upon first reduction/oxidation cycle in both electrolytes using these binding polymers, which were significantly improved in comparison to a conventional PVdF binder (less than 45% of columbic efficiency for the first cycle). For the graphite-PVdF electrode, co-intercalation and/or decomposition of PC molecules solvating to Li ions were observed by the electrochemical reduction, resulting in the cracking of graphite particles. In contrast, the co-intercalation and decomposition of PC molecules and BMP cations for the first reduction process were completely suppressed for the graphite electrodes prepared with the polymers containing oxygen atoms. It was proposed that the selective permeability of lithium ions was attained by the uniform coating of the graphite particles with PAA, PMA, and PVA polymers, because the electrostatic interaction between the positively charged lithium ions and negatively charged oxygen atom in the polymer should modulate the desolvation process of lithium ions during the lithium intercalation into graphite, showing the similar functions like artificial solid-electrolyte interphase.     

Modification of cleanup methods for dioxin analysis in green leafy vegetables and comparison of packing methods for a multi-layer silica gel column

To determine polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and coplanar polychlorinated biphenyls (Co-PCBs) in green leafy vegetables, the cleanup method was modified, and packing methods for a multi-layer silica gel column were compared in food samples. First, the additional cleanup was examined for a mono-ortho PCBs fraction obtained by alumina column chromatography from spinach extract. Small solids such as rough crystals that remained after concentration of the mono-ortho PCBs fraction were identified as long-chain hydrocarbons from leaf epicuticular wax by GC/MS. Cleanup using an activated carbon silica gel column with n-hexane as the washing solvent was effective. Next, multi-layer silica gel columns packed by wet packing and dry packing were compared using komatsuna, salmon and butter as samples. The columns prepared by both methods gave similar values at each isomeric concentration level and showed similar efficiency with favorable recoveries.     

ZnO nanostructured film deposition using the separated pulsed laser deposition (SPLD) assisted by electric and magnetic drift motion

We have developed the separated pulsed laser deposition (SPLD) technique to prepare high quality ZnO based films exhibiting uniform and droplet-free properties. This SPLD consists of an ablation chamber and a deposition chamber which can be independently evacuated under different ambient gases.The gas species and the pressures in both chambers can be arbitrarily chosen for the specific deposition such as nanostructured films and nanoparticles. The ablation chamber is a stainless steel globe and the deposition chamber is a quartz tube connected to a metallic conic wall with an orifice. We used a KrF excimer laser with λ = 248 nm and 25 ns pulse duration. The different gas conditions in two chambers allow us to realize optimal control of the plasma plume, the gas phase reaction and the film growth by applying the bias voltage between the conic wall and the substrate under the magnetic field. We can expect that at appropriate pressures the electric and magnetic field motion (E × B azimuthal drift velocity) gives significant influences on film growth.We have deposited ZnO thin films at various pressures of ablation chamber (Pab) and deposition chamber (Pd). The deposition conditions used here were laser fluence of 3 J/cm², laser shot number of 30,000, Pab of 0.67-2.67 Pa (O₂ or Ar), Pd of 0.399-2.67 Pa (O₂), and substrate temperature of 400 °C. Particle-free and uniform ZnO films were obtained at Pab of 0.67 Pa (Ar) and Pd of 1.33 Pa (O₂). The ZnO film showed high preferential orientation of (002) plane, optical band gap of 2.7 eV, grain size of 42 nm and surface roughness of 1.2 nm.     

Synthesis and hydrophilic property of polypropylene-graft-poly(polyethylene glycol-methacrylate) (PP-g-P(PEGMA))

Polypropylene-graft-poly(polyethylene glycol-methacrylate) (PP-g-P(PEGMA)), which is a hydrophobic-hydrophilic graft copolymer, was synthesized by a combination of an atom transfer radical polymerization (ATRP) of PEGMA with brominated polypropylene (PP-Br), which was synthesized from PP-OH prepared by metallocene-catalyzed copolymerization. Its structure was confirmed by ¹H NMR and GPC analyses. Transmission electron microscope (TEM) micrographs of PP-g-P(PEGMA) revealed the nanometer level microphase-separation morphology between the PP segment and the P(PEGMA) segment. The obtained PP-g-P(PEGMA) showed water-absorbing property as well as thermostability.     

Flowrate effects on the lateral coalescence of two growing bubbles

The coalescence of two growing bubbles presents unique characteristics compared to static bubble coalescence. The gas injection flowrate significantly affects the different stages of bubble evolution, which is poorly understood. In this study, we investigate the flowrate effects on the lateral coalescence of two growing bubbles experimentally. The synchronous bubbling from adjacent needles is achieved using water to push air. During the bubble growth process, we find that the initial nonlinear evolution of bubble volume is because the bubble emerges as a small spherical cap with a large curvature radius and apparent contact angle. As the neck expands after bubble coalescence, the injection flowrate accelerates the neck evolution compared to the case without air injection. We find the neck expansion time decreases linearly with increasing flowrate, while the expansion speed increases with flowrate, but only in the early stage. Moreover, we propose a new theoretical expression that predicts the neck radius well at all the flowrates. At the post-coalescence oscillation stage, the average projection area of the coalesced bubble increases linearly with time, except for periodic oscillations. Besides, we find that the injected air primarily influences the coalesced bubble's height, which in turn affects the projection area.     

On-Site Fabrication of Crystalline Cerium Oxide Films and Patterns by Ink-Jet Deposition Method at Moderate Temperatures

Crystalline CeO₂ films and patterns have been successfully fabricated in a "single-step process" at moderate temperature. In this process, the combination of the ink-jet technique and depositing the precursor on a hot substrate (≤300°C) gave crystalline CeO₂ without further heat treatment. X-ray diffraction analysis revealed that the phase formed was crystallized ceria with nanosized (<10 nm) crystallites. The film thickness was several hundred nanometers and the pattern width was about 150 μm. Scanning electron microscopy analysis showed that the films and patterns were free of cracks and adhered to the substrate. This is the first report about the direct patterning of crystalline CeO₂ without postfiring or posttreatments like masking, etching, etc.     

Hydrothermal synthesis of hydroxyapatite whiskers with sharp faceted hexagonal morphology

We report an effective method for the synthesis of hydroxyapatite whiskers with sharp faceted hexagonal shape employing a low temperature (90 °C) hydrothermal route with calcium nitrate tetrahydrate, diammonium phosphate and urea as starting materials. The key parameters of the synthesis process i.e. duration, temperature cycle of the treatment and starting pH value are carefully varied and the end products are investigated using powder X-ray diffraction (XRD), Raman-scattering, infrared spectroscopy (IR), elemental analysis, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), electron diffraction (ED), and high-resolution TEM (HRTEM) in order to find the optimal reaction conditions that lead to the desired hexagonal morphology of HA whiskers. The results demonstrate that gradual and greater increase in solution pH during the hydrothermal process favors large quantity of the single-crystalline hydroxyapatite whiskers with well defined hexagonal morphology.     

Liposome‐Based in Vitro Evolution of Aminoacyl‐tRNA Synthetase for Enhanced Pyrrolysine Derivative Incorporation

Methanosarcina species pyrrolysyl‐tRNA synthetase (PylRS) attaches Pyl to its cognate amber suppressor tRNA. The introduction of two mutations (Y384F and Y306A) into PylRS was previously shown to generate a mutant, designated LysZ‐RS, that was able to attach N‐benzyloxycarbonyl‐L ‐lysine (LysZ) to its cognate tRNA. Despite the potential of LysZ derivatives, further LysZ‐RS engineering has not been performed; consequently, we aimed to generate LysZ‐RS mutants with improved LysZ incorporation activity through in vitro directed evolution. Using a liposome‐based in vitro compartmentalization (IVC) approach, we screened a randomly mutagenized gene library of LysZ‐RS and obtained a mutant that showed increased LysZ incorporation activity both in vitro and in vivo. The ease and high flexibility of liposome‐based IVC should enable the evolution of not only LysZ‐RS that can attach various LysZ derivatives but also of other enzymes involved in protein translation.     

First-Principles Study on the Grain Boundary Embrittlement of Metals by Solute Segregation: Part II. Metal (Fe,Al, Cu)-Hydrogen (H) Systems

The microscopic mechanism of grain boundary (GB) embrittlement in metals by hydrogen segregation (trapping) has been not well understood for many years. From first-principles calculations, we show here that the calculated cohesive energy of bcc Fe Σ3(111) and fcc Al(Cu) Σ5(012) symmetrical tilt GBs can be significantly reduced if many hydrogen atoms segregate at the GBs. This indicates that the reduction of the cohesive energy of the GB may cause the hydrogen-induced GB embrittlement in Fe, Al, and Cu. Considering the “mobile” effect of hydrogen during fracture, especially for the Fe system, more hydrogen atoms coming from solid solution state can segregate on the gradually formed two fracture surfaces and reduce further the cohesive energy. We suggest a new idea about the upper and lower critical stresses observed in the constant-load test of hydrogen-induced delayed fracture in high-strength steels; the upper critical stress is determined by the amount (density) of “immobile” hydrogen atoms segregated at the GB before fracture, and the lower critical stress is determined by the total amount (density) of immobile and mobile hydrogen atoms, the latter of which segregate on the two fracture surfaces during fracture.