Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part II: Influences of extrusion rate on morphological changes of a PLA/PVA blend through a capillary die

The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min^?1 to 2 g min^?1 with an increment of 0.5 g min^?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.     

Melt spun matrix fibers of toughened polypropylene copolymers modified by high energy electrons

Binary blends of polypropylene (PP) and ethylene‐octene copolymer (EOC) are prepared by continuous electron‐induced reactive processing at various mass ratios of the blend components and various doses without adding of any grafting agents. The influence of mass ratio and dose is investigated in order to get the optimum processing behavior of toughened PP as well as optimum properties of resulting fibers. It is found that toughened PP with a PP/EOC blend ratio of 97.5–2.5  mass % can be used advantageously as a matrix component for the process of online spinning of glass fiber/toughened PP hybrid yarns. Such hybrid yarns belong to one of the most advanced production methods for the manufacturing of fiber reinforced thermoplastic composites with an increased mechanical performance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44011.     

4‐Biphenylalanine‐ and 3‐Phenyltyrosine‐Derived Hydroxamic Acids as Inhibitors of the JumonjiC‐Domain‐Containing Histone Demethylase KDM4A

Overexpression of the histone lysine demethylase KDM4A, which regulates H3K9 and H3K36 methylation states, has been related to the pathology of several human cancers. We found that a previously reported hydroxamate‐based histone deacetylase (HDAC) inhibitor (SW55) was also able to weakly inhibit this demethylase with an IC₅₀ value of 25.4 μm . Herein we report the synthesis and biochemical evaluations, with two orthogonal in vitro assays, of a series of derivatives of this lead structure. With extensive chemical modifications on the lead structure, also by exploiting the versatility of the radical arylation with aryldiazonium salts, we were able to increase the potency of the derivatives against KDM4A to the low‐micromolar range and, more importantly, to obtain demethylase selectivity with respect to HDACs. Cell‐permeable derivatives clearly showed a demethylase‐inhibition‐dependent antiproliferative effect against HL‐60 human promyelocytic leukemia cells.     

Filler Wetting in Miscible ESBR/SSBR Blends and Its Effect on Mechanical Properties

The selective wetting behavior of silica in emulsion styrene butadiene rubber (ESBR)/solution styrene butadiene rubber (SSBR) blends is characterized by the wetting concept, which is further developed for filled blends based on miscible rubbers. It is found that not only the chemical rubber–filler affinity but also the topology of the filler surface significantly influences the selective filler wetting in rubber blends. The nanopore structure of the silica surface has been recognized as the main reason for the difference in the wetting behavior of the branched ESBR molecules and linear SSBR molecules. However, the effect of nanopore structure becomes more significant in the presence of silane. It is discussed that the adsorption of silane on silica surface constricts the nanopore to some extent that hinders effectively the space filling of the nanopores by the branched ESBR molecules but not by the linear SSBR molecules. As a result, in silanized ESBR/SSBR blends the dominant wetting of silica surface by the tightly bonded layer of SSBR molecules causes a low‐energy dissipation in the rubber–filler interphase. That imparts the low rolling resistance to the blends similar to that of a silica‐filled SSBR compound, while the ESBR‐rich matrix warrants the good tensile behavior, i.e., good abrasion and wear resistance of the blends.

     

Carbon nanotubes‐filled thermoplastic polyurethane–urea and carboxylated acrylonitrile butadiene rubber blend nanocomposites

This article reports the preparation and characterization of multiwalled carbon nanotubes (MWCNTs)‐filled thermoplastic polyurethane–urea (TPUU) and carboxylated acrylonitrile butadiene rubber (XNBR) blend nanocomposites. The dispersion of the MWCNTs was carried out using a laboratory two roll mill. Three different loadings, that is, 1, 3, and 5 wt % of the MWCNTs were used. The electron microscopy image analysis proves that the MWCNTs are evenly dispersed along the shear flow direction. Through incorporation of the nanotubes in the blend, the tensile modulus was increased from 9.90 ± 0.5 to 45.30 ± 0.3 MPa, and the tensile strength at break was increased from 25.4 ± 2.5 to 33.0 ± 1.5 MPa. The wide angle X‐ray scattering result showed that the TPUU:XNBR blends were arranged in layered structures. These structures are formed through chemical reactions of ? NH group from urethane and urea with the carboxylic group on XNBR. Furthermore, even at a very low loading, the high degree of nanotubes dispersion results in a significant increase in the electrical percolation threshold. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40341.     

Influence of a cyclic butylene terephthalate oligomer on the processability and thermoelectric properties of polycarbonate/MWCNT nanocomposites

The thermoelectric properties of melt-processed nanocomposites consisting of a polycarbonate (PC) thermoplastic matrix filled with commercially available carboxyl (–COOH) functionalized multi-walled carbon nanotubes (MWCNTs) were evaluated. MWCNTs carrying carboxylic acid moieties (MWCNT-COOH) were used due the p-doping that the carboxyl groups facilitate, via electron withdrawing from the electron-rich π-conjugated system. Preliminary thermogravimetric analysis (TGA) of MWCNT-COOH revealed that the melt-mixing was limited at low temperatures due to thermal decomposition of the MWCNT functional groups. Therefore, PC was mixed with 2.5 wt% MWCNT-COOH (PC/MWCNT-COOH) at 240 °C and 270 °C. In order to reduce the polymer melt viscosity, a cyclic butylene terephthalate (CBT) oligomer was utilized as an additive, improving additionally the electrical conductivity of the nanocomposites. The melt rheological characterization of neat PC and PC/CBT blends demonstrated a significant decrease of the complex viscosity by the addition of CBT (10 wt%). Optical and transmission electron microscopy (OM, TEM) depicted an improved MWCNT dispersion in the PC/CBT polymer blend. The electrical conductivity was remarkably higher for the PC/MWCNT-COOH/CBT composites compared to the PC/MWCNT-COOH ones. Namely, the PC/MWCNT-COOH/CBT processed at 270 °C exhibited the best values with electrical conductivity; σ = 0.05 S/m, Seebeck coefficient; S = 13.55 μV/K, power factor; PF = 7.60 × 10⁻⁶μW/m K⁻², and thermoelectric figure of merit; ZT = 7.94 × 10⁻⁹. The PC/MWCNT-COOH/CBT nanocomposites could be ideal candidates for large-scale thermal energy harvesting, even though the presently obtained ZT values are still too low for commercial applications.     

Nucleation and growth behavior of β-nucleated iPP during shear induced crystallization investigated by in-situ synchrotron WAXS and SAXS

Polymer crystallization under flow was investigated because final properties of polymers strongly depend on the crystalline structure and morphology formed during processing. In-situ synchrotron WAXS and SAXS were used to investigate the structure formation and morphological developments during quiescent and shear-induced crystallization of iPP with 3 different concentrations (0.01, 0.03 and 0.1 wt%) of β-nucleating agent. Under quiescent conditions, a high β-content was obtained at all those concentrations indicating the high β-nucleating efficiency of the nucleating agent. After application of shear, the β-nucleating ability at small concentration was retained, while at larger concentrations it was strongly retarded. Furthermore, the addition of β-nucleating agent was beneficial for the molecular alignment during processing, the anisotropic particles of β-nucleating agent were much more effective to align the molecular chains in the flow direction compared to isotropic ones. A crystallization scheme for the iPP β-nucleating agent under shear was proposed.     

Diazoverbindungen. 72. (Diazoalkyl)phosphane – Synthese durch elektrophile Diazoalkansubstitution und oxidative Additionsreaktionen am Phosphor

Diazo Compounds. 72. Diazoalkylphosphanes – Synthesis by Electrophilic Diazoalkane Substitution and Oxidative Addition Reactions at Phosphorus Electrophilic diazoalkane substitution of the diazomethyl compounds 1a,b with the chloro phosphanes 2a-o in the presence of lithium diethylamide yields the diazoalkyl phosphanes 3a-z . Oxidative addition of oxygen, sulfur and selenium at phosphorus leads into the series of oxo, thioxo and selenoxo phosphanes having diazoalkyl substituents ( 4a-d, 5a-m and 7a-d ). The silyl group of 5n,o is cleaved by chromatography on aluminium oxide to yield the (diazomethyl)phosphane sulfides 6a,b .     

Impact of neurite alignment on organelle motion

Intracellular transport is pivotal for cell growth and survival. Malfunctions in this process have been associated with devastating neurodegenerative diseases, highlighting the need for a deeper understanding of the mechanisms involved. Here, we use an experimental methodology that leads neurites of differentiated PC12 cells into either one of two configurations: a one-dimensional configuration, where the neurites align along lines, or a two-dimensional configuration, where the neurites adopt a random orientation and shape on a flat substrate. We subsequently monitored the motion of functional organelles, the lysosomes, inside the neurites. Implementing a time-resolved analysis of the mean-squared displacement, we quantitatively characterized distinct motion modes of the lysosomes. Our results indicate that neurite alignment gives rise to faster diffusive and super-diffusive lysosomal motion than the situation in which the neurites are randomly oriented. After inducing lysosome swelling through an osmotic challenge by sucrose, we confirmed the predicted slowdown in diffusive mobility. Surprisingly, we found that the swelling-induced mobility change affected each of the (sub-/super-)diffusive motion modes differently and depended on the alignment configuration of the neurites. Our findings imply that intracellular transport is significantly and robustly dependent on cell morphology, which might in part be controlled by the extracellular matrix.