Modeling of Ethylene Polymerization Kinetics over Supported Chromium Oxide Catalysts

Summary: Silica supported chromium oxide catalysts have been used for many years to manufacture polyethylene and they still account for more than 50% of world production of high‐density polyethylene. Along with its commercial success, the catalytic mechanism and polymerization kinetics of silica supported chromium oxide catalysts have been the subject of intense research. However, there is a lack of modeling effort for the quantitative prediction of polymerization rate and polymer molecular weight properties. The chromium oxide catalyzed ethylene polymerization is often characterized by the presence of an induction period followed by a steady increase in polymerization rate. The molecular weight distribution is also quite broad. In this paper, a two‐site kinetic model is developed for the modeling of ethylene polymerization over supported chromium oxide catalyst. To model the induction period, it is proposed that divalent chromium sites are deactivated by catalyst poison and the reactivation of the deactivated chromium sites is slow and rate controlling. To model the molecular weight distribution broadening, each active chromium site is assumed to have different monomer chain transfer ability. The experimental data of semibatch liquid slurry polymerization of ethylene is compared with the model simulations and a quite satisfactory agreement has been obtained for the polymerization conditions employed.

Polymerization rates at different reaction temperatures: symbols – data, lines – model simulations.     

Directing Polymorphism in the Helical Nanofilament Phase

Herein, it is reported that the polymorphism in the helical nanofilament (HNF, B₄) liquid-crystalline phase depends on the fabrication methods, that is, UV-driven formation and template-assisted self-assembly in the nanoconfined geometry. As a result, uniaxially oriented HNFs with different helical structures were obtained, in which generation of the twisted-ribbon and cylindrical-ribbon polymorphs showed that even the molecular lattice has a different orientation. The detailed structures were directly observed by SEM and grazing-incidence X-ray diffraction with synchrotron radiation. The resultant polymorphs could be used in chiro-optical applications due to the capability for fine control of the helical structures.     

Control of on-off or off-on fluorescent and optical [Cu²⁺] and [Hg²⁺] responses via formal Me/H substitution in fully characterized thienyl "scorpionate"-like BODIPY systems

One 8-phenyl and two 8-mesityl-substituted "scorpionate"-like BODIPY-type species of the formula [3,4,4-tris(5-R-(2-thienyl))-8-(2,4,6-R'-phenyl)-4-bora-3a,4a-diaza-s-indacene (R = H, R' = H, 3a; R, = H, R' = Me, 2a; R, = Me, R' = Me, 2b)] have been synthesized and fully characterized. Importantly, differences in their solution (MeCN) optical Cu(2+) and Hg(2+) probing capacity via SSS-chelation were investigated. Compounds 2a-3a were prepared from the requisite 8-substituted BODIPY complexes. They were characterized first by complete (1)H, (11)B and (13)C NMR spectroscopic assignments (CD(3)Cl or CD(3)C(O)CD(3)); the molecular structures of 2a and 3a were determined by X-ray crystallography. Compounds 2a-3a were studied by UV-vis and fluorescence spectroscopy [Φ(F) = 0.27 ± 0.013 (2a); 0.024 ± 0.0016 (2b); 0.0034 ± 0.00047 (3a)]. Importantly, low [Cu(2+)] with 3a (<3.0 × 10(-5) M) gave rise to an increase of fluorescence intensity (off-on; 6.3-fold), whereas with 2a it decreased (on-off). When [Hg(2+)] (<3.0 × 10(-5) M) was added to 2b, the λ(em,max) value increased (off-on; 3.2-fold), and for 2a, it decreased (on-off). The association constant (K(a)) for Hg(2+)·2a was determined to be 3120 ± 307 M(-1). An approximate stoichiometric 1:1 binding determined by Job plot analysis is in line with successful DFT modeling of SSS-Cu(2+) binding for this system type. (1)H NMR spectroscopy also revealed tentative sets of product complex peaks. These simple differences caused by formal ligand Me-group incorporation are the first for any related fluorophores, to the best of our knowledge.     

Rapid synthesis and consolidation of nanostructured Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>–MgSiO<Subscript>3</Subscript> composites by high frequency induction heated sintering

Rapid synthesis and sintering of nanostructured MgSiO₃–Mg₂SiO₄ composites was investigated via a high-frequency induction heating sintering process. The advantage of this process is that it enables very quick densification to near theoretical density and prohibition of grain growth in nanostructured materials. High-density nanostructured MgSiO₃–Mg₂SiO₄ composites were produced by simultaneous application of 80 MPa pressure under an induced output power of 15 kW within 2 min. The grain sizes and hardness of MgSiO₃–Mg₂SiO₄ composites were investigated.     

Effect of plasma etching on photoluminescence of SnO(x)/Sn nanoparticles deposited on DOPC lipid membrane

The photoluminescence characteristic of the SnO(x)/Sn nanoparticles deposited on a solid supported liquid-crystalline phospholipid (1,2-dioleoyl-sn-glycero-3-phosphocholine) membrane was probed after plasma etching the nanoparticle monolayer. It was shown that the plasma etching of the nanoparticle surface greatly altered the particle morphology and enhanced the PL effect, especially when the particle size was below 10 nm in spite of strong presence of surrounding carbon. The enhancement mainly stemmed from the growth of a new PL peak due to the additional defect states produced on the nanoparticle surface by the plasma etching. It was also shown that hydrating the SnO(x)/Sn nanoparticles similarly improved the PL response of the nanoparticles as the hydration produced an additional oxygen-rich oxide layer on the particle surface.     

Adenovirus adenine nucleotide translocator-2 shRNA effectively induces apoptosis and enhances chemosensitivity by the down-regulation of ABCG2 in breast cancer stem-like cells

Cancer stem cells (CSCs) are resistant to chemo- and radio-therapy, and can survive to regenerate new tumors. This is an important reason why various anti- cancer therapies often fail to completely control tumors, although they kill and eliminate the bulk of cancer cells. In this study, we determined whether or not adenine nucleotide translocator-2 (ANT2) suppression could also be effective in inducing cell death of breast cancer stem-like cells. A sub-population (SP; CD44+/ CD24-) of breast cancer cells has been reported to have stem/progenitor cell properties. We utilized the adeno- ANT2 shRNA virus to inhibit ANT2 expression and then observed the treatment effect in a SP of breast cancer cell line. In this study, MCF7, MDA-MB-231 cells, and breast epithelial cells (MCF10A) mesenchymally-transdifferentiated through E-cadherin knockdown were used. ANT2 expression was high in both stem-like cells and non-stem-like cells of MCF7 and MDA-MB-231 cells, and was induced and up-regulated by mesenchymal transdifferentiation in MCF10A cells (MCF10A(EMT)). Knockdown of ANT2 by adeno-shRNA virus efficiently induced apoptotic cell death in the stem-like cells of MCF7 and MDA-MB-231 cells, and MCF10A(EMT). Stem-like cells of MCF7 and MDA-MB-231, and MCF10A(EMT) cells exhibited increased drug (doxorubicin) resistance, and expressed a multi-drug resistant related molecule, ABCG2, at a high level. Adeno-ANT2 shRNA virus markedly sensitized the stem-like cells of MCF7 and MDA-MB-231, and the MCF10A(EMT) cells to doxorubicin, which was accompanied by down-regulation of ABCG2. Our results suggest that ANT2 suppression by adeno-shRNA virus is an effective strategy to induce cell death and increase the chemosensitivity of stem-like cells in breast cancer.     

Carbonic Anhydrase Immobilized on Encapsulated Magnetic Nanoparticles for CO(2) Sequestration

Bovine carbonic anhydrase (BCA) was covalently immobilized onto OAPS (octa(aminophenyl)silsesquioxane)-functionalized Fe(3) O(4) /SiO(2) nanoparticles by using glutaraldehyde as a spacer. The Fe(3) O(4) nanoparticles were coated with SiO(2) , onto which was grafted OAPS, and the product was characterized using SEM, TEM, XRD, IR, X-ray photoelectron spectroscopy (XPS), and magnetometer analysis. The enzymatic activities of the free and Fe(3) O(4) /SiO(2) /OAPS-conjugated BCA (Fe?CA) were investigated by hydrolyzing p-nitrophenylacetate (p-NPA), and hydration and sequestration of CO(2) to CaCO(3) . The CO(2) conversion efficiency and reusability of the Fe?CA were studied before and after washing the recovered Fe?CA by applying a magnetic field and quantifying the unreacted Ca(2+) ions by using ion chromatography. After 30?cycles, the Fe?CA displayed strong activity, and the CO(2) capture efficiency was 26-fold higher than that of the free enzyme. Storage stability studies suggested that Fe?CA retained nearly 82?% of its activity after 30?days. Nucleation of the precipitated CaCO(3) was monitored by using polarized light microscopy, which revealed the formation of two phases, calcite and valerite, at pH?10 upon addition of serine. The magnetic nanobiocatalyst was shown to be an excellent reusable catalyst for the sequestration of CO(2.).