Well‐Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

Low‐temperature anionic ring‐opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal‐free catalyst system, 3‐phenyl‐1‐propanol (PPA) (an initiator) and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris‐(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄) (a promoter) in order to obtain well‐defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring‐opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well‐defined linear AGE‐homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE‐homopolymer in a unimodal narrow molecular‐weight distribution. In this case, however, a side reaction (i.e., chain‐transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well‐defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post‐modification products are examined. Overall, this study demonstrates that a low‐temperature metal‐free anionic ROP using the PPA/t‐Bu‐P₄ catalyst system is suitable for the production of well‐defined linear AGE‐homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post‐modifications, nanostructures, and their applications.     

Boroxine Nanotubes: Moisture‐Sensitive Morphological Transformation and Guest Release

Boroxines, (R‐BO)₃, which can be easily synthesized via a dehydration reaction of boronic acids, R–B(OH)₂, selectively self‐assemble in toluene into nanofibers, nanorods, nanotapes, and nanotubes, depending on the aromatic substituent (R). Spectroscopic measurements show that the nanotube consists of a J‐aggregate of the boroxine. Humidification converts the morphology from the nanotube to a sheet as a result of the hydrolysis of the boroxine components and subsequent molecular‐packing rearrangement from the J‐aggregate to an H‐aggregate. Such a transformation leads to the compulsive release of guest molecules encapsulated in the hollow cylinder of the nanotube. The hydrolysis and the molecular‐packing rearrangement described above are suppressed by coordination of pyridine to the boron atom, with the resulting moiety acting as a Lewis acid of the boroxine component. The pyridine‐coordinated nanotube is transformed into a helical coil by humidification. Guest release during the nanotube‐to‐helical‐coil transformation is much slower than during the nanotube‐to‐sheet transformation, but faster than from a nanotube that did not undergo morphological transformation. The storage and release of guest molecules from the boroxine nanotubes can be precisely controlled by adjusting the moisture level and the concentration of Lewis bases, such as amines.     

Preparation and mesostructure control of highly ordered zirconia particles having crystalline walls

Mesostructured zirconia particles having monoclinic-type crystalline walls were prepared using a low-temperature crystallization technique. Crystalline zirconia particles with highly-ordered mesostructures were obtained through the sol–gel process of zirconium sulfate tetrahydrate at 333 K in the presence of molecular self-assemblies of cetyltrimethylammonium bromide (CTAB) or mixtures of CTAB and anionic molecules such as sodium dodecyl sulfate and sodium p-toluenesulfonate. Variations in the molar ratios of CTAB and the chemical species of anionic molecules led to the variations in the periods of highly-ordered zirconia having crystalline walls. Calcination of the mesostructured zirconia particles prepared using templates consisting solely of CTAB yielded crystalline mesoporous zirconia particles.     

Compression molding and melt‐spinning of the blends of poly(lactic acid) and poly(butylene succinate‐co‐adipate)

Poly(lactic acid) (PLA) is a biobased polymer made from biomass having high mechanical properties for engineering materials applications. However, PLA has certain limited properties such as its brittleness and low heat distortion temperature. Thus, the aim of this study is to improve toughness of PLA by blending with poly(butylene succinate‐co‐adipate) (PBSA), the biodegradable polymer having high toughness. Polymer blends of PLA and PBSA were prepared using a twin screw extruder. The melt rheology and the thermal property of the blends were examined. Further the blends were fabricated into compression molded parts and melt‐spun fiber and were subjected to tensile and impact tests. When the PBSA content was low, PBSA phase was finely dispersed in the PLA matrix. On the other hand, when the PBSA content was high, this minor phase dispersed as a large droplet. Mechanical properties of the compression molded parts were affected by the dispersion state of PBSA minor component in PLA matrix. Impact strength of the compression molded parts was also improved by the addition of soft PBSA. The improvement was pronounced when the PBSA phase was finely dispersed in PLA matrix. However, the mechanical property of the blend fibers was affected by the postdrawing condition as well as the PBSA content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41856.     

Homogeneous Strain Introduction Using Reciprocation Technique in High-Pressure Sliding

Metallurgical and Materials Transactions A - This study examines strain distribution occurring in the high-pressure sliding (HPS) processing for rods of pure Al and an AZ61 alloy. The strain...     

On-off switching properties of one-dimensional photonic crystals consisting of azo-functionalized polymer liquid crystals having different methylene spacers and polyvinyl alcohol

In this paper, photoresponsive behavior of multi-bilayered films having precisely controlled layer thickness prepared by stacking an azo-functionalized polymer liquid crystal, PMAzXAc, and polyvinyl alcohol alternatively, PVA, is described. The multi-bilayered films were found to reflect a light of specific wavelength depending on the layer thickness and refractive index, and showed the reversible change in the reflection intensity by irradiation with visible and UV lights. The change in the reflection intensity was brought about by change in the molecular orientation of PMAzXAc between an out-of-plane orientation and a photo-induced isotropic state, and was strongly dependent on the number of methylene spacer of PMAzXAc linking the azobenzene side group with the acrylate polymer main chain. PMAz6Ac with hexa-methylene spacer showed the largest change in the reflection intensity, while smaller change in the reflection intensity was observed for PMAzXAc having shorter or longer methylene spacer than 6. The effect of the methylene spacers on the photochemical change in the molecular orientation of azobenzene chromophores in the multi-bilayered films will be discussed.     

Accelerator-driven system for transmutation of high-level waste

The accelerator-driven transmutation system has been studied at the Japan Atomic Energy Research Institute. This system is a hydrid system which consists of a high intensity accelerator, a spallation target and a subcritical core region. In the conceptual design study, two types of system concepts, sodium cooled and lead-bismuth cooled system, are being studied. In this study, we fucus on our lead-bismuth cooled accelerator-driven transmutation system to investigate basic characteristics. The fuel compositions were optimized for efficient transmutation of minor actinide. The transmutation of long-lived fission products was also considered.     

Crystalline Sodium Selenocarboxylates – synthesis and characterization

A series of sodium selenocarboxylates 2 were isolated from the reaction of diacyl selenides with sodium ethanolate and characterized. A convenient preparation of the sodium salts 2 by the direct reaction of acyl chlorides with sodium selenide was also established. The salts are colourless to slightly pale yellow crystals and labile towards moisture. They readily react with alkyl iodides at room temperature to give the corresponding Se-alkyl esters 3 .     

Vitamin E reduces cholesterol esterification and uptake of acetylated low density lipoprotein in macrophages

The effects of vitamin E on cholesteryl ester (CE) metabolism in 1774 cells were examined. Pretreatment of 1774 cells with vitamin E at concentrations above 50 μM significantly decreased acetylated low density lipoprotein (LDL)-induced incorporation of [¹⁴C]oleate into CF in cells in a dose-dependent manner. This was partly due to vitamin E Also significantly inhibiting the uptake of [³H]CE-labeled acetylated LDL by 1774 cells. A trend existed toward suppression of acyl-CoA:cholesterol acyltransferase (ACAT) activity in the cell lysate at high vitamin E concentration, but there was no effect on hydrolysis of CE. These data indicate that vitamin E reduces the uptake of modified LDL and suppresses ACAT activity, resulting in less cholesterol esterification in macrophages; a novel mechanism underlying the antiatherogenic properties of vitamin E.