Evolution of the electrical resistivity at rest and during oscillatory shearing of co-continuous morphology (PP/PMMA)/MWCNT systems

In this work, a modified parallel-disks configuration on a strain-controlled ARES rheometer (TA Instrument) was used to study the evolution of the electrical resistivity at rest and during oscillatory shearing of a co-continuous immiscible polymer blend morphology based on polypropylene and /polymethyl(methacrylate) (PP/PMMA) in which various amounts (0–3 wt%) of multiwall carbon nanotubes (MWCNT) were added. The co-continuity of both PP and PMMA phases allowed the buildup of a conductive network due to the preferential localization of the conductive MWCNT at the interface between PP and PMMA. Under a stepwise increase of the oscillatory strain amplitude below a critical value (γ_c = 6.3%), a significant decrease in the electrical resistivity was observed for MWCNT concentrations above the percolation threshold (0.3 wt%) due to the conductive paths induced by both thermal (Brownian) motion and oscillatory shearing. However, for deformation amplitudes higher than γ_c, the resistivity increased due to the destruction of the MWCNT paths induced by the large deformation imposed on the PP/PMMA interface. These observations were also confirmed by the evolution of the storage modulus (G′) which remained constant for γ_c < 6.3% (linear viscoelastic regime), while the values decreased above γ_c due to the destruction of the system's morphology.     

Synthesis of amphiphilic (meth)acrylates with oligo(ethylene glycol) and (or) oligo(propylene glycol) blocks by the esterification of (meth)acrylic acid

Thermoresponsive PEG-based (PEG stands polyethylene glycol) polymers are unique for use in medicine because of their low toxicity, good biocompatibility and biodegradability, but usually more hydrophobic and more toxic comonomers are used to adjust lower critical solution temperature (LCST). A convenient way to overcome this problem and to finely tune LCST is to use alkoxy oligo(ethylene glycol)- or alkoxy oligo(propylene glycol) (meth)acrylates as starting comonomers. Here we report on the conditions for the simple and affordable synthesis of methoxy oligo(propylene glycol) (meth)acrylate- and methoxy oligo(propylene glycol)-block-oligo(ethylene glycol) (meth)acrylate-based macromonomers with high yields (80%–98.7%) by the acid-catalyzed esterification of (meth)acrylic acid with alkoxy oligo(alkylene glycols) containing oligo(ethylene glycol) (OEG) and/or oligo(propylene glycol) (OPG) blocks. p-Toluene sulphonic acid (pTSA), alkyl(C₁₂–C₁₄)benzene sulfonic acid (ABSA) and H₂SO₄ were used as catalysts. It has been shown that pTSA and ABSA are practically the same in catalytic activity and are superior to sulfuric acid. The reaction orders with respect to catalyst was found to be close to 1 in all cases. It has been shown that the reaction is actually insensitive to the lengths of OEG and OPG blocks, as well as to the structure of the terminal alkyl group, while the esterification of acrylic acid (AA) proceeds much faster compared to methacrylic acid (MAA) one under the same conditions. The influence of temperature on the equilibrium conversions of alcohols was determined, which were found to be 89%–93% for the esterification of AA and 61%–86% for MAA in the temperature range of 60–120°C. A further increase in conversion was achieved by introducing an azeotropic agent (toluene), its optimal concentration was found to be 10%–15%.     

Synergistic toughening and electrical functionalization of an epoxy using MWCNTs and silane- /plasma-activated basalt fibers

This work studied the effects of adding short basalt fibers (BFs) and multi-walled carbon nanotubes (MWCNTs), both separately and in combination, on the mechanical properties, fracture toughness, and electrical conductivity of an epoxy polymer. The surfaces of the short BFs were either treated using a silane coupling agent or further functionalized by atmospheric plasma to enhance the adhesion between the BFs and the epoxy. The results of a single fiber fragmentation test demonstrated a significantly improved BF/epoxy adhesion upon applying the plasma treatment to the BFs. This resulted in better mechanical properties and fracture toughness of the composites containing the plasma-activated BFs. The improved BF/epoxy adhesion also affected the hybrid toughening performance of the BFs and MWCNTs. In particular, synergistic toughening effects were observed when the plasma-activated BFs/MWCNTs hybrid modifiers were used, while only additive toughening effects occurred for the silane-sized BFs/MWCNTs hybrid modifiers. This work demonstrated a potential to develop strong, tough, and electrically conductive epoxy composites by adding hybrid BF/MWCNT modifiers.     

Ascorbic Acid-Assisted Eco-friendly Synthesis of NiCo<Subscript>2</Subscript>O<Subscript>4</Subscript> Nanoparticles as an Anode Material for High-Performance Lithium-Ion Batteries

We have synthesized NiCo₂O₄ nanoparticles (NCO NPs) using an ascorbic acid-assisted co-precipitation method for the first time. When NCO NPs are used as an anode material for lithium-ion batteries, the cell exhibits superior lithium storage properties, such as high capacity (700 mA h g^?1 after 300 cycles at 200 mA g^?1), excellent rate capabilities (applied current density range 100–1200 mA g^?1), and impressive cycling stability (at 1200 mA g^?1 up to 650 cycles). The enhanced electrochemical properties of NCO NPs are due to the nanometer dimensions which not only offers a smooth charge-transport pathway and short diffusion paths of the lithium ions but also adequate spaces for volume expansion during Li storage. Hence, this eco-friendly synthesis approach will provide a new strategy for the synthesis of various nanostructured metal oxide compounds, for energy conversion and storage systems applications.     

Improved evidence for the existence of an intermediate phase during hydration of tricalcium silicate

Tricalcium silicate (Ca₃SiO₅) with a very small particle size of approximately 50 nm has been prepared and hydrated for a very short time (5 min) by two different modes in a paste experiment, using a water/solid-ratio of 1.20, and by hydration as a suspension employing a water/solid-ratio of 4000. A phase containing uncondensed silicate monomers close to hydrogen atoms (either hydroxyl groups or water molecules) was formed in both experiments. This phase is distinct from anhydrous tricalcium silicate and from the calcium-silicate-hydrate (C-S-H) phase, commonly identified as the hydration product of tricalcium silicate. In the paste experiment, approximately 79% of silicon atoms were present in the hydrated phase containing silicate monomers as determined from ²⁹Si{¹H} CP/MAS NMR. This result is used to show that the hydrated silicate monomers are part of a separate phase and that they cannot be attributed to a hydroxylated surface of tricalcium silicate after contact with water. The phase containing hydrated silicate monomers is metastable with respect to the C-S-H phase since it transforms into the latter in a half saturated calcium hydroxide solution. These data is used to emphasize that the hydration of tricalcium silicate proceeds in two consecutive steps. In the first reaction, an intermediate phase containing hydrated silicate monomers is formed which is subsequently transformed into C-S-H as the final hydration product in the second step. The introduction of an intermediate phase in calculations of the early hydration of tricalcium silicate can explain the presence of the induction period. It is shown that heterogeneous nucleation on appropriate crystal surfaces is able to reduce the length of the induction period and thus to accelerate the reaction of tricalcium silicate with water.     

Influence of various process conditions on surface finishes induced by the direct metal deposition laser technique on a Ti–6Al–4V alloy

The direct metal deposition (DMD) with laser is a free-form metal deposition process for manufacturing dense pieces, which allows generating a prototype or small series of near net-shape structures. One of the most critical issues is that produced pieces have a deleterious surface finish which systematically requires post machining steps. This problem has never been fully addressed before.The present work describes investigations on the DMD process, using an Yb-YAG disk laser, and a widely used titanium alloy (Ti–6Al–4V) to understand the influence of the main process parameters on the surface finish quality. The focus of our work was: (1) to understand the physical mechanisms responsible for deleterious surface finishes, (2) to propose different experimental solutions for improving surface finish.In order to understand the physical mechanisms responsible for deleterious surface finishes, we have carried out: (1) a precise characterization of the laser beam and the powder stream; (2) a large number of multi-layered walls using different process parameters (P(W), V(m/min), D_m (g/min), Gaussian or uniform beam distribution); (3) a real time fast camera analysis of melt pool dynamics and melt-pool – powder stream coupling; (4) a characterization of wall morphologies versus process parameters using 2D and 3D profilometry.The results confirm that surface degradation depends on two distinct aspects: the sticking of non-melted or partially melted particles on the free surfaces, and the formation of menisci with more or less pronounced curvature radii. Among other aspects, a reduction of layer thickness and an increase of melt-pool volumes to favor re-melting processes are shown to have a beneficial effect on roughness parameters. Last, a simple analytical model was proposed to correlate melt-pool geometries to resulting surface finishes.     

Cigarette Smoke Condensate Exposure Induces Receptor for Advanced Glycation End-Products (RAGE)-Dependent Sterile Inflammation in Amniotic Epithelial Cells

Maternal smoking is a risk factor of preterm prelabor rupture of the fetal membranes (pPROM), which is responsible for 30% of preterm births worldwide. Cigarettes induce oxidative stress and inflammation, mechanisms both implicated in fetal membranes (FM) weakening. We hypothesized that the receptor for advanced glycation end-products (RAGE) and its ligands can result in cigarette-dependent inflammation. FM explants and amniotic epithelial cells (AECs) were treated with cigarette smoke condensate (CSC), combined or not with RAGE antagonist peptide (RAP), an inhibitor of RAGE. Cell suffering was evaluated by measuring lactate dehydrogenase (LDH) medium-release. Extracellular HMGB1 (a RAGE ligand) release by amnion and choriodecidua explants were checked by western blot. NF-κB pathway induction was determined by a luciferase gene reporter assay, and inflammation was evaluated by cytokine RT-qPCR and protein quantification. Gelatinase activity was assessed using a specific assay. CSC induced cell suffering and HMGB1 secretion only in the amnion, which is directly associated with a RAGE-dependent response. CSC also affected AECs by inducing inflammation (cytokine release and NFκB activation) and gelatinase activity through RAGE engagement, which was linked to an increase in extracellular matrix degradation. This RAGE dependent CSC-induced inflammation associated with an increase of gelatinase activity could explain a pathological FM weakening directly linked to pPROM.     

Novel A-Ring Chalcone Derivatives of Oleanolic and Ursolic Amides with Anti-Proliferative Effect Mediated through ROS-Triggered Apoptosis

A series of A-ring modified oleanolic and ursolic acid derivatives including C28 amides (3-oxo-C2-nicotinoylidene/furfurylidene, 3β-hydroxy-C2-nicotinoylidene, 3β-nicotinoyloxy-, 2-cyano-3,4-seco-4(23)-ene, indolo-, lactame and azepane) were synthesized and screened for their cytotoxic activity against the NCI-60 cancer cell line panel. The results of the first assay of thirty-two tested compounds showed that eleven derivatives exhibited cytotoxicity against cancer cells, and six of them were selected for complete dose–response studies. A systematic study of local SARs has been carried out by comparative analysis of potency distributions and similarity relationships among the synthesized compounds using network-like similarity graphs. Among the oleanane type triterpenoids, C2-[4-pyridinylidene]-oleanonic C28-morpholinyl amide exhibited sub-micromolar potencies against 15 different tumor cell lines and revealed particular selectivity for non-small cell lung cancer (HOP-92) with a GI₅₀ value of 0.0347 μM. On the other hand, superior results were observed for C2-[3-pyridinylidene]-ursonic N-methyl-piperazinyl amide 29, which exhibited a broad-spectrum inhibition activity with GI₅₀ < 1 μM against 33 tumor cell lines and <2 μM against all 60 cell lines. This compound has been further evaluated for cell cycle analysis to decipher the mechanism of action. The data indicate that compound 29 could exhibit both cytostatic and cytotoxic activity, depending on the cell line evaluated. The cytostatic activity appears to be determined by induction of the cell cycle arrest at the S (MCF-7, SH-SY5Y cells) or G₀/G₁ phases (A549 cells), whereas cytotoxicity of the compound against normal cells is nonspecific and arises from apoptosis without significant alterations in cell cycle distribution (HEK293 cells). Our results suggest that the antiproliferative effect of compound 29 is mediated through ROS-triggered apoptosis that involves mitochondrial membrane potential depolarization and caspase activation.     

Acyltransferase activities in the yolk sac membrane of the chick embryo

The activities of some enzymes of glycerolipid synthesis and fatty acid oxidation were measured in subcellular fractions of the yolk sac membrane (YSM), an extra-embryonic tissue that mediates the transfer of lipid from the yolk to the circulation of the chick embryo. The activities of monoacylglycerol acyltransferase and carnitine palmitoyl transferase-1 in the YSM (respectively, 284.8±13.2 nmol/min/mg microsomal protein and 145.6±9.1 nmol/min/mg mitochondrial protein; mean ±SE; n=4) at day 12 of development appear to be the highest yet reported for any animal tissue. Also, the carnitine palmitoyl transferase-1 of the YSM was very insensitive to inhibition by malonyl CoA. The maximal activities of glycerol-3-phosphate acyltransferase and diacylglycerol acyltransferase in the YSM (respectively, 26.7±2.2 and 36.1±2.1 nmol/min/mg microsomal protein) were also high compared with the reported values for various animal tissues. The very high enzymic capacity for glycerolipid synthesis supports the hypothesis that the yolk-derived lipids are subjected to hydrolysis followed by reesterification during transit across the YSM. The monoacylglycerol pathway appears to be the main route for glycerolipid resynthesis in the YSM. The results also suggest that the YSM has the capacity to perform simultaneously β-oxidation at a high rate in order to provide energy for the lipid transfer process.     

Community energy planning in Canada: The role of renewable energy

An emerging trend in Canada is the creation of community energy plans, where decisions that used to be left to regional level energy agencies or private individuals are now being considered at the community level. A desire to reduce greenhouse gas emissions and to become more energy self-sufficient is driving this change. Theoretically, local level management is desirable because it achieves these goals through improvements in the three areas of energy efficiency, energy conservation and switching to renewable energy sources. The analysis of 10 of the first community energy plans in Canadian communities, ranging in population size from 500 to one million, finds that communities are choosing policies and programs centred on increasing energy efficiency and conservation while renewable energy receives much less attention. Municipal operations were called upon to set higher targets than the general community. Communities that recognized the substantial potential of renewable energy often focused on technologies that the municipal sector could implement, such as bio-fuels for their transportation fleet. Wind, passive solar design, solar photovoltaics and solar thermal options were only recommended in a few cases. Overall, only one of the five larger communities (Calgary) recommended implementing multiple renewable energy technologies while three of the five smaller communities proposed multiple renewable energy sources. The implication is that smaller and more remote communities may be the most willing to lead in the planned introduction of renewable energy systems.