Impact of oxygen transport properties on the kinetic modeling of polypropylene thermal oxidation. II. Effect of oxygen diffusivity

The kinetic model, established in a previous article (François‐Heude et al., J. Appl. Polym. Sci., in press) to predict the homogeneous oxidation in iPP films typically thinner than 100 µm, is now extended to simulate the oxidation profiles in thicker plates by coupling the oxygen diffusion and its consumption by the chemical reactions. In this perspective, oxygen transport properties (namely oxygen solubility, diffusivity, and permeability) are measured by permeametry on a reference iPP. These values are compared with an exhaustive compilation of literature data to evaluate their variability among the whole iPP family, which one has been reasonably ascribed to initial differences in polymer morphology, but also to evaluate their consistency, especially their temperature dependence between 20 and 140°C. Failing to simulate oxidation profiles, the kinetic model is then used as an inverse resolution method for estimating more satisfactory values of oxygen transport properties. It is thus evidenced that the crystallinity changes induced by thermal oxidation largely explains the dramatic decrease in oxygen penetration toward the sample core just after the induction period. A strategy aimed for introducing the relationship between the polymer crystalline morphology and oxygen transport properties into the kinetic model is given in the graphical abstract, although the effect of polymer polarity remains to be established prior to this implementation. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41562.     

Field-scale analysis of water and nutrient use efficiency for vegetable production in a West African urban agricultural system

Urban agriculture increasingly supplies food and non-food services to the rapidly growing West African cities. However, with its typically heavy use of fertilizers and uncontrolled use of water, it bears severe risks of soil and groundwater pollution. This study was carried out in Bobo Dioulasso (Burkina Faso, West Africa) at two commercial gardening sites. It aimed at performing a detailed characterization of farmer’s water and nutrient management strategies. Four vegetable crops were monitored (tomato, cabbage, carrot and lettuce). Water inputs (rainfall and irrigation), nutrient inputs (organic and mineral fertilizers and nutrients in irrigation water) and crop uptake were monitored over a 1–2-year period. In addition, pan lysimeters allowed monitoring drainage. Depending on the site, 3–8% of the input water was lost by drainage, i.e., as much as 293 mm/year at one of the sites. During the dry season, when the farmer has full control over the water supply, water application exceeded plant requirements by as much as 40%, which reveals inefficient water use. Up to 800 kg N ha⁻¹, 140 kg P ha⁻¹ and 500 kg K ha⁻¹ were applied for a single crop cycle. With few exceptions, crops tended to be strongly over-fertilized, except for K at one of the two sites. Nutrient supply exceeded crop requirements by 109 to 2,012 kg N, 66 to 450 kg P and 0 to 393 kg K per year. These results, in combination with the large observed rates of drainage, are indicative of a high risk of nutrient leaching and groundwater contamination. The partial factor productivity of nutrients tended to be low. These results therefore suggested that there is scope to substantially reduce nutrient application rates in these systems without adverse effects on yields, which would be beneficial for groundwater resources and improve the economic returns.     

Involvement of GPx-3 in the Reciprocal Control of Redox Metabolism in the Leukemic Niche

The bone marrow (BM) microenvironment plays a crucial role in the development and progression of leukemia (AML). Intracellular reactive oxygen species (ROS) are involved in the regulation of the biology of leukemia-initiating cells, where the antioxidant enzyme GPx-3 could be involved as a determinant of cellular self-renewal. Little is known however about the role of the microenvironment in the control of the oxidative metabolism of AML cells. In the present study, a coculture model of BM mesenchymal stromal cells (MSCs) and AML cells (KG1a cell-line and primary BM blasts) was used to explore this metabolic pathway. MSC-contact, rather than culture with MSC-conditioned medium, decreases ROS levels and inhibits the Nrf-2 pathway through overexpression of GPx3 in AML cells. The decrease of ROS levels also inactivates p38MAPK and reduces the proliferation of AML cells. Conversely, contact with AML cells modifies MSCs in that they display an increased oxidative stress and Nrf-2 activation, together with a concomitant lowered expression of GPx-3. Altogether, these experiments suggest that a reciprocal control of oxidative metabolism is initiated by direct cell–cell contact between MSCs and AML cells. GPx-3 expression appears to play a crucial role in this cross-talk and could be involved in the regulation of leukemogenesis.     

Targeting Casein Kinase 1 (CK1) in Hematological Cancers

The casein kinase 1 enzymes (CK1) form a family of serine/threonine kinases with seven CK1 isoforms identified in humans. The most important substrates of CK1 kinases are proteins that act in the regulatory nodes essential for tumorigenesis of hematological malignancies. Among those, the most important are the functions of CK1s in the regulation of Wnt pathways, cell proliferation, apoptosis and autophagy. In this review we summarize the recent developments in the understanding of biology and therapeutic potential of the inhibition of CK1 isoforms in the pathogenesis of chronic lymphocytic leukemia (CLL), other non-Hodgkin lymphomas (NHL), myelodysplastic syndrome (MDS), acute myeloid leukemia (AML) and multiple myeloma (MM). CK1δ/ε inhibitors block CLL development in preclinical models via inhibition of WNT-5A/ROR1-driven non-canonical Wnt pathway. While no selective CK1 inhibitors have reached clinical stage to date, one dual PI3Kδ and CK1ε inhibitor, umbralisib, is currently in clinical trials for CLL and NHL patients. In MDS, AML and MM, inhibition of CK1α, acting via activation of p53 pathway, showed promising preclinical activities and the first CK1α inhibitor has now entered the clinical trials.     

Polysilazane derived micro/nano Si3N4/SiC composites

The pyrolised polysilazanes poly(hydridomethyl)silazane NCP 200 and poly(urea)silazane CERASET derived Si–C–N amorphous powders were used for preparation of micro/nano Si₃N₄/SiC composites by hot pressing. Y₂O₃–Al₂O₃ and Y₂O₃–Yb₂O₃ were used, as sintering aids. The resulting ceramic composites of all compositions were dense and polycrystalline with fine microstructure of average grain size <1 μm of both Si₃N₄ and SiC phases. The fine SiC nano-inclusions were identified within the Si₃N₄ micrograins. Phase composition of both composites consist of , β modifications of Si₃N₄ and SiC. High weight loss was observed during the hot pressing cycle, 12 and 19 wt.% for NCP 200 and CERASET precursors, respectively. The fracture toughness of both nanocomposites (NCP 2000 and CERASET derived) was not different. Indentation method measured values are from 5 to 6 MPa m^1/2, with respect to the sintering additive system. Fracture toughness is slightly sensitive to the SiC content of the nanocomposite. Hardness increases with the content of SiC in the nanocomposite. The highest hardness was achieved for pyrolysed CERASET precursor with 2 wt.% Y₂O₃ and 6 wt.% Yb₂O₃, HV 23 GPa. This is a consequence of the highest SiC content as well as the chemical composition of additives.     

Sol—Gel Synthesis of Strontium-Doped Lanthanum Manganite

Strontium-doped lanthanum manganite powders were prepared using a peroxide acetate salt based solution. The stable sol was peptized by reacting ammonium hydroxide with the precursor solution. The amorphous dried gel powders exhibit a high energy level, due to their high cations coordination and small particles, to develop the perovskite phase. This crystalline phase development from powders containing monocarboxylate ligands was characterized by thermal analysis (TG, DTG, DTA), X-ray diffraction, and IR spectroscopy. The transformation from amorphous powders into a crystallized homogeneous oxycarbonate phase in a first stage corresponds to an exothermal DTA peak at 270°C. X-ray diffraction patterns and IR spectra showed similar behavior of the powders after complete organic removal, during the conversion into perovskite phase starting at approximately 630°C and achieved about 700°C and achieved about 700°C, as well as during the sintering process.     

Stress relaxation in low‐shrink‐force polyolefin films

The morphology and stress relaxation of coextruded five‐layer LLDPE (linear low‐density polyethylene)/EVA (ethylene‐vinyl‐acetate) copolymer films were studied. Increasing VA (vinyl acetate) content in EVA causes a decrease of shrink tension in the films, which can be explained by a decrease in amount of crystallinity. The relaxation time spectrum of the coextruded crosslinked LLDPE/EVA films is similar to the relaxation time spectrum of crosslinked LLDPE film at room temperature. However, at elevated temperatures, an additional peak appears on the spectrum of coextruded film. The cause of this peak is temperature‐ and stress‐induced recrystallization of EVA during the relaxation test. This recrystallization was confirmed with DSC and wide angle X‐ray analysis. Polym. Eng. Sci. 44:1716–1720, 2004. © 2004 Society of Plastics Engineers.     

From clay- to organoclay-film modified electrodes: tuning charge selectivity in ion exchange voltammetry

The surface of two natural smectite-type clay samples was chemically modified by covalent grafting of amine groups, by reaction with γ-aminopropyltriethoxysilane, which were easily protonated in HCl medium. Multisweep cyclic voltammograms of clay-film modified glassy carbon electrodes made of either the raw clays or the propylammonium-functionalized samples exposed to Ru(NH₃)₆³⁺ or Fe(CN)₆³⁻ electroactive probes were obtained. The results indicated a permselective behavior of these clay and organoclay-films based on either favorable or unfavorable electrostatic interactions. The cation-exchanging raw clay film modified electrodes exhibited accumulation properties for Ru(NH₃)₆³⁺ species while rejecting Fe(CN)₆³⁻, whereas the anion-exchanging organoclay coatings acted as a barrier against Ru(NH₃)₆³⁺ while increasing dramatically the concentration of Fe(CN)₆³⁻ species at the electrode surface. Strong binding of the probe to the organoclays resulted in a potential shift of ca. 0.1 V of the voltammetric signals characteristic of the Fe(CN)₆^3−/4− couple in the anodic direction. Their good preconcentration efficiency at low analyte concentration highlighted their interest for electroanalytical applications.     

Synthesis and biological activity of medium range molecular weight polymers containing exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid

A new monomer, exo‐3,6‐epoxy‐1,2,3,6‐tetrahydrophthalimidocaproic acid (ETCA), was prepared by reaction of maleimidocaproic acid and furan. The homopolymer of ETCA and its copolymers with acrylic acid (AA) or with vinyl acetate (VAc) were obtained by photopolymerizations using 2,2‐dimethoxy‐2‐phenylacetophenone as an initiator at 25 °C. The synthesized ETCA and its polymers were identified by FTIR, ¹H NMR and ¹³C NMR spectroscopies. The apparent average molecular weights and polydispersity indices determined by gel permeation chromatography (GPC) were as follows: M_n = 9600 g mol^?1, M_w = 9800 g mol^?1, M_w/M_n = 1.1 for poly(ETCA); M_n = 14 300 g mol^?1, M_w = 16 200 g mol^?1, M_w/M_n = 1.2 for poly(ETCA‐co‐AA); M_n = 17 900 g mol^?1, M_w = 18 300 g mol^?1, M_w/M_n = 1.1 for poly(ETCA‐co‐VAc). The in vitro cytotoxicity of the synthesized compounds against mouse mammary carcinoma and human histiocytic lymphoma cancer cell lines decreased in the following order: 5‐fluorouracil (5‐FU) ≥ ETCA > polymers. The in vivo antitumour activity of the polymers against Balb/C mice bearing sarcoma 180 tumour cells was greater than that of 5‐FU at all doses tested. © 2001 Society of Chemical Industry