Geopolymer assembly by emulsion templating: Emulsion stability and hardening mechanisms

This work investigates emulsion templating to synthesize hexadecane oil/geopolymer composites. In a system with hexadecane as the internal (dispersed) phase and an alkali activated continuous phase without added surfactant, adding aluminosilicate clay particles does not increase resistance against creaming or coalescence, while adding a surfactant (L35 or CTAB) stabilizes the solid-liquid interface. Infrared studies and rheological studies of the associated geopolymerization determined that the presence of the organic phase or surfactant has no significant effect on the geopolymerization kinetics, as determined by the change in time of the Si-O-T IR stretching frequency and the rheological moduli involved during the process. The stabilization of the organic template is reminiscent of Pickering emulsion even though we employ a much greater amount of inorganic material for geopolymer formation. Although the addition of surfactant has a significant effect on the behavior of the paste, the percolation of the network remains unmodified, highlighting the fact that the phenomenon is not dependent on viscosity. Finally, rheological measurements were used to obtain the mass fractal dimension of the as-made gel network, which is able to differentiate the interfacial effect between surfactant molecules with a slightly denser interphase when a cationic surfactant is used.     

Synthesis and characterization of the polyols by air oxidation of soybean oil and its effect on the morphology and dynamic mechanical properties of poly(vinyl chloride) blends

The use of natural additives, with low toxicity and good compatibility, for PVC is becoming increasingly attractive. In this study, soybean oil additives were prepared by air oxidation reactions and blending with PVC. The oxidation reaction produced a significant increase in the number of hydroxyl groups in soybean oil; however, this kind of reaction results in the formation of a heterogeneous structure due to free radical reactions in the medium. The oxidized soybean oil improved the compatibility with PVC due to an increase in the number of polar groups, such as hydroxyls, and thus a reduction in the amount of atactic polymer was observed. Furthermore, an increase in the molecular weight of the oxidized oil, as well as large amounts of polar groups contributes to reducing the migration of oil in the PVC. Regarding the crystallinity of PVC, the use of pure and oxidized soybean oil causes small changes in the crystalline phase of the polymer. Oxidized soybean oil has great potential for usage as a secondary plasticizer for PVC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42102.     

Behavior of Paramagnetic Iron during the Thermal Transformations of Kaolinite

Kaolinites with various degrees of structural order and iron content were heated and subsequently analyzed via electron paramagnetic resonance. Iron was present in two different states in the heated materials, either as dilute structural Fe³⁺ ions or in concentrated Fe³⁺ phases. During metakaolinization, the environment of dilute Fe³⁺ ions changed, following modifications of the Al³⁺ coordination, and the Fe³⁺ concentration increased. With the breakdown of metakaolinite, the diffusion of Fe³⁺ ions induced their exsolution in superparamagnetic iron-rich domains (Fe³⁺ clusters in γ-Al₂O₃ and/or Fe³⁺ oxide nanophases), which produced a decrease in the dilute Fe³⁺ concentration. The subsequent breakdown of γ-Al₂O₃ and the formation of mullite made the dilute Fe³⁺ concentration increase again, because of the incorporation of Fe³⁺ ions in the mullite structure.     

Recycling zinc oxide varistor blocks for electro‐active silicone composites

The recycling process toward the elimination of varistor wastes into new electro‐active silicon composites has been investigated. We studied the dependence of the E‐J characteristics on the aggregate content in the polymer matrix. Formulations with 40 vol.% metal oxide varistor aggregates in the 100‐200 μm range exhibit reliable nonlinear behavior with a switching voltage of 280±30 V/mm. The breakdown voltage of the composite decreases as both filler's diameter and filler's volume fraction increases in the 550‐220 V/mm and 440‐280 V/mm range, respectively. This paves the way for the valorization of varistors based zinc oxide (ZnO) ceramics.     

Cationic polymerization of 2,4,6,8-tetramethylcyclotetrasiloxane processed by tuning the pH of the miniemulsion

The preparation of 2,4,6,8-tetramethylcyclotetrasiloxane () miniemulsions stabilized by commercial surfactants, i.e. sodium dodecylbenzenesulfonate (NaDBSA) and sodium laurate/lauric acid mixture, was studied and is first reported. Then, the pH was tuned in order to process polymerization through interfacial protonic initiation. With lauric acid, no polymerization was observed, even at high temperature or large acid contents. Such effect is ascribed to the poor dissociation and reactivity of high pKa's carboxylic acids. With NaDBSA, acidification by HCl was enough to initiate the polymerization, but the pH of the continuous phase was shown to have a strong effect on the polymerization process. Optimal conditions (at pH 5) gave chains with average number molar masses around 16,000 g mol⁻¹ and polydispersity index close to 1.6, for a total conversion in polymer of about 60% after 2 h reaction. Lower pH (4.2) quickly led to a cross-linked network whereas at higher pH (6.1), conversions were too slow (around 10% after 350 min).     

Methane calibration burner and C‐factor determination with cone calorimeter – validation of the standardized calibration protocol

The cone calorimeter is one of the major fire tests. In its reference standard ISO 5660‐1, the apparatus (and especially a characteristic of its orifice plate mass flow meter, called C‐Factor) is calibrated using a methane burner set at 5 kW. However, measurements performed in end‐use are in the range 1–10 kW. In addition, standard proposes to check linearity at 1 and 3 kW, which means in the lowest part of the range. This communication establishes the validation of the linearity on the whole range and determines the optimal condition for C‐factor determination. It justifies the technical choices of the standard. Copyright © 2014 John Wiley & Sons, Ltd.     

Discovery of Riociguat (BAY 63‐2521): A Potent,Oral Stimulator of Soluble Guanylate Cyclase for the Treatment of Pulmonary Hypertension

Direct stimulation of soluble guanylate cyclase (sGC) represents a promising therapeutic strategy for the treatment of a range of diseases, including the severely disabling pulmonary hypertension (PH). Optimization of the unfavorable DMPK profile of previous sGC stimulators provided riociguat, which is currently being investigated in phase III clinical trials for the oral treatment of PH.

     

BRAF Modulates Stretch-Induced Intercellular Gap Formation through Localized Actin Reorganization

Mechanical forces acting on cell–cell adhesion modulate the barrier function of endothelial cells. The actively remodeled actin cytoskeleton impinges on cell–cell adhesion to counteract external forces. We applied stress on endothelial monolayers by mechanical stretch to uncover the role of BRAF in the stress-induced response. Control cells responded to external forces by organizing and stabilizing actin cables in the stretched cell junctions. This was accompanied by an increase in intercellular gap formation, which was prevented in BRAF knockdown monolayers. In the absence of BRAF, there was excess stress fiber formation due to the enhanced reorganization of actin fibers. Our findings suggest that stretch-induced intercellular gap formation, leading to a decrease in barrier function of blood vessels, can be reverted by BRAF RNAi. This is important when the endothelium experiences changes in external stresses caused by high blood pressure, leading to edema, or by immune or cancer cells in inflammation or metastasis.     

Adipose-Derived Stem Cells in the Treatment of Perianal Fistulas in Crohn’s Disease: Rationale,Clinical Results and Perspectives

Between 20 to 25% of Crohn’s disease (CD) patients suffer from perianal fistulas, a marker of disease severity. Seton drainage combined with anti-TNFα can result in closure of the fistula in 70 to 75% of patients. For the remaining 25% of patients there is room for in situ injection of autologous or allogenic mesenchymal stem cells such as adipose-derived stem/stromal cells (ADSCs). ADSCs exert their effects on tissues and effector cells through paracrine phenomena, including the secretome and extracellular vesicles. They display anti-inflammatory, anti-apoptotic, pro-angiogenic, proliferative, and immunomodulatory properties, and a homing within the damaged tissue. They also have immuno-evasive properties allowing a clinical allogeneic approach. Numerous clinical trials have been conducted that demonstrate a complete cure rate of anoperineal fistulas in CD ranging from 46 to 90% of cases after in situ injection of autologous or allogenic ADSCs. A pivotal phase III-controlled trial using allogenic ADSCs (Alofisel^®) demonstrated that prolonged clinical and radiological remission can be obtained in nearly 60% of cases with a good safety profile. Future studies should be conducted for a better knowledge of the local effect of ADSCs as well as for a standardization in terms of the number of injections and associated procedures.