Formation of polyketone particle structure by hexafluoroisopropanol solvent evaporation and effects of plasticizer addition

Few solvents are capable of dissolving polyketones (PKs). 1,1,1,3,3,3‐Hexafluoro‐2‐propanol (hexafluoroisopropanol, HFIP) is a better solvent than trifluoroethanol and m‐cresol. When HFIP was evaporated from a PK/HFIP solution, a porous cast‐film with a microparticle structure was formed because the isotactic PKs adopted a helical conformation, and convection during evaporation of the high polarity and low‐boiling‐point HFIP caused aggregation and rolling of the polymer molecules. The addition of plasticizer suppressed particle formation, improving the surface structure and mechanical properties of the film. In particular, the dielectric properties of the film improved significantly. This will enable PKs, which are rigid insulating materials, to be used as dielectric materials, broadening their range of applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 887–892     

Syntheses of Key Monomers for Advanced Polymer Materials Using Cyclodextrin as Catalyst

Terephthalic acid was synthesized by the carboxylation of benzoic acid with carbon tetrachloride in aqueous sodium hydroxide solution in the presence of cyclodextrin (CyD) and copper powder as catalyst. By the use of β-CyD at the initial molar ratio to benzoic acid of 0.5, the carboxylation at 60 °C for 7 hours produced terephthalic acid in 75 mol% yield with 87% selectivity. The selective synthesis of 4,4'-biphenyldicarboxylic acid in 70 mol% yield was achieved by the carboxylation of 4-biphenylcarboxylic acid with carbon tetrachloride in the presence of β-Cyd under similar conditions. The carboxylation of 2-naphthalene carboxylic acid with carbon tetrachloride using β-Cyd under similar conditions produced 2,6-naphthalenedicarboxylic acid in 67 mol% yield with 84% selectivity. When α-CyD and γ-CyD were used in place of β-Cyd, both the yields and the selectivities of the dicarboxylic acids were markedly small. In the absence of CyD, carboxylation did not proceed. Inclusion complex formations between β-Cyd and aromatic monocarboxylic acids were indicated by the ¹H chemical shifts of the β-Cyd. The reaction mechanism was discussed on the basis of inclusion complex formation.     

Macromolecule-Metal Complexes for Gas Separation

Macromolecule-copper(I) chloride complexes have been prepared for the separation of carbon monoxide and ethylene from gas mixtures with hydrogen, nitrogen, carbon dioxide, methane, and water. A toluene solution of a polystyrene-aluminum copper(I) chloride complex can separate carbon monoxide selectively and retains this function even on contact with gas containing water. Strong charge-transfer absorption bands have been found in the 380-500 nm region for the toluene solution of polystyrene-aluminum copper(I) chloride complex. A solution of 1, 3-diphenylpropane-aluminum copper(I) chloride complex also exhibits similar absorption bands. A continuous variation plot using the chemical shift change in ¹³C-NMR shows a 1:1 interaction between 1,3-diphenylpropane and aluminum copper(I) chloride. These results suggest a two-way interaction between the adjacent phenyl groups of polystyrene and aluminum copper(I) chloride. A resin bead of crosslinked polystyrene-aluminum copper(I) chloride complex has been prepared as a solid adsorbent. The water resistance of the solid macromolecular complex depends on the nature of the solvent used in the preparation of the solid adsorbent. Carbon disulfide is a suitable solvent. A selective adsorbent of ethylene has been prepared from a macroreticular polystyrene resin with primary and secondary amino groups and copper(I) chloride. The selectivity of ethylene against ethane and that of carbon monoxide against carbon dioxide increase with an increasing amount of supported copper(I) chloride.     

Control of the Orientation and Photoinduced Phase Transitions of Macrocyclic Azobenzene

Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer.     

Effects of post-deposition annealing on chemical composition of SiNx film in SiO2/SiNx/SiO2/Si stacked structure

To systematically evaluate the quality of SiN_x films in multi-stacked structures, we investigated the effects of post-deposition annealing (PDA) on the film properties of SiN_x within the SiO₂/SiN_x/SiO₂/Si stacked structure by performing X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), Fourier transform infrared (FT-IR) spectroscopy, and scanning transmission electron microscope–electron energy loss spectroscopy (STEM-EELS) analyses. The XPS results showed that PDA induces the oxidation of the SiN_x layer. In particular, new finding is that Si-rich SiN_x in the SiN_x layer is preferentially oxidized by PDA even in multi-stacked structure. The XRR results showed that the SiN_x layer becomes thinner, whereas the interface layer between the SiN_x layer and Si becomes thicker. It is concluded by STEM-EELS and XPS that this interface layer is SiON layer. The density of N–H and Si–H bonding within the stacked structure strongly depends on the PDA temperature. Our study helps elucidate the properties of SiN_x films in stacked structures from various perspectives.     

Hyperpolarized 13C Magnetic Resonance Imaging of Fumarate Metabolism by Parahydrogen-induced Polarization: A Proof-of-Concept in vivo Study

Hyperpolarized [1-¹³C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-¹³C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-¹³C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-¹³C]fumarate at sufficient ¹³C polarization for ex vivo detection of hyperpolarized ¹³C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo ¹³C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis.     

Bleaching effect of a 405-nm diode laser irradiation used with titanium dioxide and 3.5% hydrogen peroxide

A 405-nm diode laser has recently been developed for soft tissue problems in dentistry. A new in-office bleaching agent consisting of a titanium dioxide photocatalyst and 3.5% hydrogen peroxide has proven to react well with light irradiated at a wavelength of around 400 nm. In this study, we evaluated the bleaching efficacy of a newly developed 405-nm diode laser on bovine teeth treated with a bleaching agent composed of titanium dioxide and 3.5% hydrogen peroxide. Sixteen bovine incisors were randomly divided into two groups: Group A, irradiated by the 405-nm diode laser at 200 mW; Group B, irradiated by the 405-nm diode laser at 400 mW. The bleaching agent with titanium dioxide and 3.5% hydrogen peroxide was applied to bovine enamel and irradiated for 1 min. The specimens were then washed and dried, and the same procedure was repeated nine more times. After irradiation, we assessed the effects of bleaching on the enamel by measuring the color of the specimens with a spectrophotometer and examining the enamel surfaces with a scanning electron microscope. L* rose to a high score, reaching a significantly higher post-treatment level in comparison to pretreatment. In a comparison of the color difference (ΔE) between Group A and Group B, the specimens in Group B showed significantly higher values after 10 min of irradiation for the post-treatment. No remarkable differences in the enamel surface morphology were found between the unbleached and bleached enamel. The use of a 405-nm diode laser in combination with a bleaching agent of titanium dioxide and 3.5% hydrogen peroxide may be an effective method for bleaching teeth without the risk of tooth damage.