Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H₂O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.     

Investigation of radiation-induced surface activation effect in austenitic stainless steel under ultraviolet and γ-ray irradiations

The radiation-induced surface activation (RISA) effect will be applied to the core design in supercritical light water reactor (SCWR) in order to achieve a high performance with excellent economy and safety. The purpose of the present study is to investigate the RISA effect in the candidate fuel cladding materials in SCWR such as PNC1520. The change of weldability due to RISA effect and the related microstructure analysis were performed in oxidized PNC1520 and 304 stainless steel with various oxidization periods. The phases contained in the surface oxide layer of the present specimen were identified as Fe₂CrO₄, γ-Fe₂O₃, and Fe₂O₃. The lifetime of 13.8 days for wettability improving factor was confirmed in the ultraviolet (UV) irradiation. Meanwhile, the long life of 13.8 days and short life of 0.8 days for wettability improving factors were identified in the γ-ray irradiation. Based on the fact that the band gap energies of Fe₂CrO₄, γ-Fe₂O₃, and Fe₂O₃ were, respectively, 2.1, 2.0, and 2.2 eV, and the photo energies of UV and γ-ray irradiation were 4.48 eV and 13.3 MeV, it is therefore clarified that the hydrophilization on the oxide layer is ascribed to the RISA effect.     

Deoxidation of Ti Melt by Newly Developed Two-Step Plasma Arc Melting Process Using Hydrogen

Metallurgical and Materials Transactions B - A two-step plasma arc melting process, comprising a first step under Ar-30 pct H2 gas flow and the second step under Ar gas flow, has been...     

Short communication: estimation of plasma osmolality from plasma electrolytes, glucose, and urea in calves

Plasma osmolality estimated from plasma concentrations of Na+, Cl-, K+, glucose, and urea was compared with measured osmolality in preweaned Holstein calves. When calves (n = 5) were fed only milk replacer after fasting for 24 h, measured osmolality fluctuated almost in parallel with estimated osmolality during the 8-h period after feeding, although estimated values were about 90% of measured values. When calves (n = 5) were fed only calf starter after fasting for more than 16 h, measured osmolality did not parallel the estimated osmolality during the 8-h period after feeding. Some factors depressed measured osmolality in the first 2 h.     

Electron beam sterilization of cyclo olefin polymer leads to polymer degradation and production of alkyl radicals

We investigated the effects of electron‐beam (EB) sterilization on syringe barrels manufactured from cyclo olefin polymer (COP). The chemical structure of the polymer was determined by interpreting the ¹³C NMR and DEPT‐135 spectra of the COP resin. The antioxidants in the resin were identified by analyzing the liquid chromatography‐photo diode array‐mass spectrometry (LC‐PDA‐MS) data for the methanol extract of the resin and the gas chromatography‐mass spectrometry (GC‐MS) data for the supercritical methanol degradation products of the extract. NMR and LC‐PDA‐MS analyses revealed that EB sterilization produces degradation products in the COP main chain and reduces the quantity of the antioxidants in the COP resin. ESR spectra of the EB‐sterilized syringe barrels indicated the presence and location of alkyl radicals, which were generated in the COP main chain by EB sterilization. ESR analyses also indicated that the quantity of alkyl radicals decreased over time. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43498.     

Infrared study of catalytic reduction of lean NOx with alcohols over alumina-supported silver catalyst

Two intense IR absorption bands due to surface isocyanate (-NCO) species have been observed at 2262 and 2232 cm^–1 when an alumina-supported silver catalyst is exposed to a mixture of NO, O₂ and ethanol at 150°C and subsequently heated to > 300°C in vacuum. The intensity of the isocyanate band is hardly affected by the water existing in the mixture. Methanol is less reactive than ethanol for the formation of isocyanate species. The reaction mechanism of catalytic reduction of lean NOx with alcohols is discussed based on these IR spectroscopic findings.     

Formation of Sm2+ lons in Sol-Gel-Derived Glasses of the System Na2 O-Al2O3-SiO2

Samarium ions (Sm²⁺) incorporated into aluminosilicate glasses by a sol-gel process showed persistent spectral hole burning at room temperature. Gels of the system Na₂O-Al₂O₃SiO₂ synthesized by the hydrolysis of Si(OC₂H₅)₄, Al(OC₄H₉)₃, CH₃ COONa, and SmCl₃·6H₂O were heated in air at 500°C, then reacted with H₂ gas to form Sm²⁺ ions. Whereas Al³⁺ ions effectively dispersed the Sm³⁺ ions in the glass structure, Na⁺ ions were not effective. The Al₂O₃-SiO₂ glasses proved appropriate for reacting the Sm³⁺ ions with H₂ gas and exhibited the intense photoluminescence of Sm²⁺ ions. The reaction of Sm³⁺ ions with H₂ in the Al₂O₂-SiO₂ glasses was determined by first-order kinetics, and the activation energy equaled 95 kJ/mol. At 800°C, the maximum photoluminescence of the Sm²⁺ ions was achieved within 20 min.     

Porous Glass-Ceramics with a Skeleton of the Fast-Lithium-Conducting Crystal Li1+xTi2−xAlx(PO4)3

Porous glass-ceramics with a skeleton of the fast-lithium-conducting crystal Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ (where x = 0.3–0.5) were prepared by crystallization of glasses in the Li₂O─CaO─TiO₂─Al₂O₃–P₂O₅ system and subsequent acid leaching of the resulting dense glass-ceramics composed of the interlocking of Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ and β-Ca₃(PO₄)₂ phases. The median pore diameter and surface area of the resulting porous Li_{1+ x} Ti_{2− x} Al _x (PO₄)₃ glass-ceramics were approximately 0.2 μm and 50 m²/g, respectively. The electrical conductivity of the porous glass-ceramics after heating in LiNO₃ aqueous solution was 8 × 10⁻⁵ S/cm at 300 K or 2 × 10⁻² S/cm at 600 K.     

Synthesis of stable and soluble one-handed helical poly(substituted acetylene)s without chiral pendant groups via polymer reaction in membrane state

A soluble and stable one-handed helical conjugated polymer without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer having two hydroxyl groups followed by desubstitution of the chiral groups in a solid membrane state. The reason for the success was the polymer reaction was carried out in the membrane state. This is an alternative method to obtain such a unique chiral polymer which was obtained only by the helix-sense-selective polymerization (HSSP) we reported before. In addition the efficiency of the chiral induction was higher than that of the HSSP. It is interesting that the “Membrane state” acted like as if a protecting group.     

Experimental investigation of melt pool behaviour during selective laser melting by high speed imaging

Melt pool behaviour and the characteristics of the surrounding metal powder during selective laser melting (SLM) are captured using high-speed imaging, and the influence of the substrate temperature and the line building sequence on the formation of the built structure and the generation of spatter particles is experimentally investigated. The results indicate that the substrate temperature has a measurable effect on the formation of droplets and the generation of spatter particles, while the volume specific energy density of the process was the principal factor affecting the built structure.