Penetration of PBSU spherulite into P(VDC-VC) spherulite observed with microbeam- and macrobeam-SAXS/WAXS measurements

PBSU/P(VDC-VC) is a crystalline/crystalline miscible polymer blend, which has characteristics that (1) the melting temperature difference is small (ΔT=33 °C), (2) the spherulite of both components can be observed with polarized optical microscope (POM), and (3) the interpenetrated spherulite is formed under specific condition: Interpenetrated spherulite means a structure formed by the penetration of PBSU spherulite growing into P(VDC-VC) spherulite. In order to clarify the nano-structure of penetrated P(VDC-VC) spherulite and penetrating PBSU lamella, we have performed the microbeam (beam size: about 10×10 μm²) SAXS/WAXS simultaneous measurements as well as macrobeam SAXS/WAXS during formation of the interpenetrated spherulite. From our experimental results, we have concluded that P(VDC-VC) lamellae hardly stack and isolate from each other, and that PBSU penetrates into the inter-fibril region of P(VDC-VC) spherulite. Further, it is found that PBSU lamella penetrating into P(VDC-VC) spherulite excludes amorphous P(VDC-VC) from PBSU inter-lamella region.     

Influence of Fatty Acid Moieties of Sorbitan Esters on Polymorphic Occurrence of the Palm Mid‐Fraction

The influence of chain length and subcell packing of fatty‐acid moieties in sorbitan esters (SE) on the polymorphism of the palm midfraction (PMF) was examined. SE with different fatty‐acid moieties (sorbitan tripalmitate; sorbitan tristearate [STS]; and sorbitan tribehenate [STB]) were blended with PMF and PMF polymorph formation was examined using synchrotron radiation X‐ray diffraction and differential interference contrast microscopy. PMF without additives was crystallized in the β′ form under the isothermal condition at 22 °C; however, the addition of STS, which forms an α subcell structure, promoted the crystallization of PMF in the α form. In contrast, crystallization of PMF in the β′ form was accelerated by the addition of STB. These results showed that when the chain length of the fatty‐acid moiety between fat and emulsifiers was similar, the crystallization of PMF in the α form was promoted by the α subcell packing in STS crystals that were nucleated prior to PMF crystallization. In contrast, STB crystals, which have an α subcell packing, accelerated the crystallization of PMF in the β′ form because of the large difference between the chain lengths of STB and PMF. Therefore, structural similarities in both the chain length and the subcell packing are essential features that regulate the template effect, and the promotion of the crystallization of PMF in the β′ form by the addition of STB was caused by heterogeneous nucleation.     

Structure and properties of plasticized polyvinyl butyral‐silica nanocomposite films and test production of laminated glass using films

Plasticized polyvinyl butyral (PVB)‐silica nanocomposite films were formed by mixing PVB ethanol solution and silica sol, which was prepared from tetraethyl orthosilicate. The nanocomposite films were colorless and transparent even though the content of silica was 70 wt%. The glass transition temperature of PVB in the silica 2.5 wt% nanocomposites was higher by about 10°C than that of plasticized PVB. The PVB‐silica nanocomposite films were applied as an interlayer for laminated glass. The laminated glass made with the nanocomposite films containing less than 10 wt% silica showed good penetration resistance, not only at room temperature but also at 70°C. J. VINYL ADDIT. TECHNOL., 25:E59–E63, 2019. © 2018 Society of Plastics Engineers     

Differences in the Central Energy Metabolism of Cancer Cells between Conventional 2D and Novel 3D Culture Systems

The conventional two-dimensional (2D) culture is available as an in vitro experimental model. However, the culture system reportedly does not recapitulate the in vivo cancer microenvironment. We recently developed a tissueoid cell culture system using Cellbed, which resembles the loose connective tissue in living organisms. The present study performed 2D and three-dimensional (3D) culture using prostate and bladder cancer cell lines and a comprehensive metabolome analysis. Compared to 3D, the 2D culture had significantly lower levels of most metabolites. The 3D culture system did not impair mitochondrial function in the cancer cells and produce energy through the mitochondria simultaneously with aerobic glycolysis. Conversely, ATP production, biomass (nucleotides, amino acids, lipids and NADPH) synthesis and redox balance maintenance were conducted in 3D culture. In contrast, in 2D culture, biomass production was delayed due to the suppression of metabolic activity. The 3D metabolome analysis using the tissueoid cell culture system capable of in vivo cancer cell culture yielded results consistent with previously reported cancer metabolism theories. This system is expected to be an essential experimental tool in a wide range of cancer research fields, especially in preclinical stages while transitioning from in vitro to in vivo.     

Self-germination inhibitors fromColletotrichum fragariae

The conidial germination ofColletotrichum fragariae in water was dependent on population, size germination was inhibited at higher concentrations of conidia in water. The inhibition was considered to be caused by some germination-inhibiting substances exuded from conidia, since the germination did occur after washing the conidia repeatedly. The germination-inhibiting substances were searched for in the acetone extract of potato-sucrose-agar (PSA) cultures of the fungus and five active compounds were isolated. Their structures were characterized spectroscopically. HPLC analysis indicated that one of the isolated compounds among these was exuded not only from mycelia but also from the conidia in water under crowded conditions. We suggest that these compounds control the conidial germination of the fungi.     

Thermal and chemical recycle of waste polymers

Catalytic degradations of polyethylene into fuel oils and of polystyrene into styrene monomer have been studied using solid acids and bases as catalysts. Solid acids such as silica-aluminas and ZSM-5 zeolite were found to be effective to degrade waste polyethylene into fuel oils, and solid bases such as BaO and K₂O were concluded to be effective to convert waste polystyrene into styrene monomer. A design of recyclable polystyrene films will be briefly mentioned.     

Effect of Triacylglycerol Compositions and Physical Properties on the Granular Crystal Formation of Fat Blends

The effect of triacylglycerol (TAG) compositions and physical properties related to solid fat content (SFC) on the behavior of granular crystal formation was investigated. Four fat blends involving different 1,3-dipalmitoyl-2-oleoyl-sn-glycerol (POP) and 1-palmitoyl-2,3-dioleoyl-sn-glycerol (POO) compositions or SFC were prepared, and crystallization was investigated using polarizing microscopy, X-ray diffraction, SFC, whereas hardness was determined using a texture analyzer. Samples containing a higher saturated fatty-acid content from palm and higher SFC showed higher β-type crystals in the initial period, yielding a number of small-sized crystals, with no growth occurring afterward. Growth of the granular crystals as a function of time was observed in the samples, transforming from the β’- to β-type polymorph gradually. Large granular crystals at the initial stage were observed in the sample with a higher POO content and lowest SFC. These results suggested that POO promotes the rate of the crystals’ polymorphic transformation, resulting in the growth of granular crystals. In contrast, excess high-melting-point TAG content, such as tripalmitin and POP, retarded granular crystal growth regardless of the increased β’ to β transition rate. We concluded that the behavior of the growth of granular crystals is influenced by the combined effect of TAG composition and SFC.     

Identification of novel nonmethylene-interrupted fatty acids, 7E,13E-20∶2, 7E,13E,17Z-20∶3, 9E,15E,19Z-22∶3, and 4Z,9E,15E,19Z-22∶4, in ophiuroidea (Brittle star) lipids

Fatty acids of Ophiuroidea (brittle star) Ophiura sarsi have been investigated by gas-liquid chromatography (GLC). About 2–13% of four unidentified fatty acids were found in total fatty acids from a sample caught at a depth of 1,100 m. Structural analyses were undertaken after partial hydrogenation of their concentrates with hydrazine hydrate and subsequent isolation of the monoenoate products by argentation thin-layer chromatography. The structures of the unidentified fatty acids were determined as 7E,13E-eicosadienoic (20∶2), 7E,13E,17Z-eicosatrienoic (20∶3), 9E,15E,19Z-docosatrienoic (22∶3), and 4Z,9E,15E,19Z-docosatetraenoic (22∶4) acids by gas chromatography-mass spectrometry of dimethyl disulfide adducts and GLC of the monoenoates on a polar column. These fatty acids belong to a family of nonmethylene-interrupted (NMI) polyunsaturated fatty acids frequently observed in marine invertebrates and conifer seeds. As far as the authors know, however, these NMI fatty acid types with mixed geometry of ethylenic bonds have not been reported previously.     

Dislocation Loop Formation in Nonstoichiometric (Ba,Ca)TiO3 and BaTiO3 Ceramics

Dislocation loops observed in nonstoichiometric and stoichiometric (Ba,Ca)TiO₃, and in stoichiometric BaTiO₃ sintered in a reducing atmosphere, were characterized by conventional transmission electron microscopy (TEM) under two-beam conditions and high-resolution TEM atomic structure analysis. Dislocation loops mostly lay on {100} planes with Burgers vectors of type 〈100〉. The dynamic behavior of these dislocation loops during the electron beam irradiation (EBI), however, was classified into two different types of dislocation loops: in A-site-excess (Ba,Ca)TiO₃, contrasts of dislocation loops faded completely away; in BaTiO₃ and B-site-excess (Ba,Ca)TiO₃, fine-line contrasts remained. Dislocation loops with Burgers vectors of type 1/2〈100〉 and the resultant crystallographic shear (CS) structure with a displacement vector of type 1/2〈110〉 after EBI were proposed to interpret residual line images. Disappearance of these line images in A-site-excess (Ba,Ca)TiO₃ strongly suggests preferential Ca ion site occupancy at the CS structure.     

Miscibility of segmented polyurethane/poly(vinyl chloride) blends

Miscibilities of segmented polyurethanes (SPUs) and poly(vinyl chloride) (PVC) or functionalized poly(vinyl chloride) (FPVC) were studied with dynamic mechanical analysis, differential scanning calorimetry, and X‐ray diffraction. Mechanical properties of the blends were also studied with tensile measurements. The miscibility of the blends depended greatly on the hard‐segment content of SPU and the existence of the functional groups. The combination of SPU with a low hard‐segment content and PVC with functional groups made the blend system miscible. Moreover, controlling the blend composition of SPU/FPVC allowed us to modify the mechanical properties of SPU, where the elongation at break was multiplied without a significant change in its tensile strength. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3022–3029, 2001