Heat Induced Structure Modifications in Polymer‐Layered Silicate Nanocomposites

Summary: The success of the use of layered silicates in polymer nanocomposites, to improve physical and chemical properties is strictly related to a deeper knowledge of the mechanistic aspects on which the final features are grounded. This work shows the temperature induced structural rearrangements of nanocomposites based on poly[ethylene‐co‐(vinyl acetate)] (EVA) intercalated‐organomodified clay (at 3–30 wt.‐% silicate addition) which occur in the range between 75 and 350 °C. In situ high temperature X‐ray diffraction (HT‐XRD) studies have been performed under both nitrogen and air to monitor the modifications of the nanocomposite structure at increasing temperatures under inert/oxidative atmosphere. Heating between 75 and 225 °C, under nitrogen or air, causes the layered silicate to migrate towards the nanocomposite surface and to increase its interlayer distance. The degradation of both the clay organomodifier and the VA units of the EVA polymer seems to play a key role in driving the evolution of the silicate phase in the low temperature range. The structural modifications of the nanocomposites in the high temperature range (250–350 °C), depended on the atmosphere, either inert or oxidizing, in which the samples were heated. Heating under nitrogen led to deintercalation and thus a decrease of the silicate interlayer space, whereas exfoliation was the main process under air leading to an increase of the silicate interlayer space.

Heat induced structural modification of EVA‐clay nanocomposite under nitrogen and air.     

Synthesis, biological activity, and ADME properties of novel S-DABOs/N-DABOs as HIV reverse transcriptase inhibitors

Previous studies aimed at exploring the SAR of C2-functionalized S-DABOs demonstrated that the substituent at this position plays a key role in the inhibition of both wild-type RT and drug-resistant enzymes, particularly the K103N mutant form. The introduction of a cyclopropyl group led us to the discovery of a potent inhibitor with picomolar activity against wild-type RT and nanomolar activity against many key mutant forms such as K103N. Despite its excellent antiviral profile, this compound suffers from a suboptimal ADME profile typical of many S-DABO analogues, but it could, however, represent a promising candidate as an anti-HIV microbicide. In the present work, a new series of S-DABO/N-DABO derivatives were synthesized to obtain additional SAR information on the C2-position and in particular to improve ADME properties while maintaining a good activity profile against HIV-1 RT. In vitro ADME properties (PAMPA permeation, water solubility, and metabolic stability) were also experimentally evaluated for the most interesting compounds to obtain a reliable indication of their plasma levels after oral administration.     

Molecular Targets of TRAIL-Sensitizing Agents in Colorectal Cancer

Tumor necrosis factor (TNF)-related apoptosis inducing ligand (TRAIL), a member of the TNF superfamily, interacts with its functional death receptors (DRs) and induces apoptosis in a wide range of cancer cell types. Therefore, TRAIL has been considered as an attractive agent for cancer therapy. However, many cancers are resistant to TRAIL-based therapies mainly due to the reduced expression of DRs and/or up-regulation of TRAIL pathway-related anti-apoptotic proteins. Compounds that revert such defects restore the sensitivity of cancer cells to TRAIL, suggesting that combined therapies could help manage neoplastic patients. In this article, we will focus on the TRAIL-sensitizing effects of natural products and synthetic compounds in colorectal cancer (CRC) cells and discuss the molecular mechanisms by which such agents enhance the response of CRC cells to TRAIL.     

Effects of high glucose on vascular endothelial growth factor synthesis and secretion in aortic vascular smooth muscle cells from obese and lean zucker rats

Type 1 diabetes is characterized by insulin deficiency, type 2 by both insulin deficiency and insulin resistance: in both conditions, hyperglycaemia is accompanied by an increased cardiovascular risk, due to increased atherosclerotic plaque formation/instabilization and impaired collateral vessel formation. An important factor in these phenomena is the Vascular Endothelial Growth Factor (VEGF), a molecule produced also by Vascular Smooth Muscle Cells (VSMC). We aimed at evaluating the role of high glucose on VEGF-A(164) synthesis and secretion in VSMC from lean insulin-sensitive and obese insulin-resistant Zucker rats (LZR and OZR). In cultured aortic VSMC from LZR and OZR incubated for 24 h with d-glucose (5.5, 15 and 25 mM) or with the osmotic controls l-glucose and mannitol, we measured VEGF-A(164) synthesis (western, blotting) and secretion (western blotting and ELISA). We observed that: (i) d-glucose dose-dependently increases VEGF-A(164) synthesis and secretion in VSMC from LZR and OZR (n = 6, ANOVA p = 0.002-0.0001); (ii) all the effects of 15 and 25 mM d-glucose are attenuated in VSMC from OZR vs. LZR (p = 0.0001); (iii) l-glucose and mannitol reproduce the VEGF-A(164) modulation induced by d-glucose in VSMC from both LZR and OZR. Thus, glucose increases via an osmotic mechanism VEGF synthesis and secretion in VSMC, an effect attenuated in the presence of insulin resistance.     

Activated carbon and metal organic framework as adsorbent for low-pressure methane storage applications: an overview

The aim of this comprehensive review on materials for methane storage application is to understand which are the best conditions and the best materials for their use for the implementation of storage tank. The research was focused on two different families of samples that up to now appear like the most promising. In particular, Activated carbon and metal organic framework were analyzed and an overall picture was extrapolated. Analysis of the structural parameters and adsorption capacities were evaluated and relation between them were obtained. A comparison of values available in literature was done and, when possible, laboratory tests were performed. The presented results allow to identify potential materials with high specific storage capacity and to verify their performances in optimized conditions. This work represents the starting point for a real and efficient method to the methane storage as a starting point for the development of Adsorbed Natural Gas technology for static and/or automotive applications.     

Polymer layered silicate nanocomposites

Polymers filled with low amounts of layered silicate dispersed at nanoscale level are most promising materials characterized by a combination of chemical, physical and mechanical properties that cannot be obtained with macro‐ or microscopic dispersions of inorganic fillers. Polymer layered silicate nanocomposites can be obtained by insertion of polymer molecules in the galleries between the layers of phyllosilicate. Here, hydrated alkaline or alkaline earth metal cations are hosted which neutralize the negative charge resulting from isomorphous substitutions of Mg or Al cations within the silicate. Insertion of polymer molecules to prepare “intercalation hybrids” can be carried out by replacing the water hydration molecules in the galleries by polymers containing polar functional groups, using the so called ion‐dipole method. A more general technique involves compatibilization of the silicate by intercalation of an organic molecule, typically an organic alkylammonium salt, that replaces the cations in the interlayer galleries to form an organically modified layered silicate (OLS). The aliphatic chain of the OLS favors the intercalation of any type of polymer. Intercalated or delaminated polymer‐silicate hybrids are obtained depending on whether the stack organization of the silicate layers is preserved or is lost, with single sheets being distributed in the polymer matrix. The methods currently used for preparing polymer layered silicate (PLS) nanocomposites are: in situ polymerization, from polymer solution, or from polymer melt. Although PLS nanocomposites have been known for a long time, it is the possibility of preparing them by melt intercalation of OLS in processing that is boosting the present interest in these materials and their properties. So far PLS nanocomposites have been characterized by X‐ray diffractometry, transmission electron microscopy, differential scanning calorimetry, and NMR. Published results on PLS nanocomposites are reviewed concerning their characterization and properties with particular reference to fire retardant behavior.     

Fluoroelastomers-dependence of relaxation phenomena on composition

The dynamic-mechanical properties of some fluoroelastomers were determined as a function of composition at low frequency (≈ 1 Hz), by means of a free oscillation torsion pendulum, between −180°C and the softening point. Vinylidenefluoride (VDF)-hexafluoropropene (HFP) copolymers of molar composition 0–39% HFP and terpolymers of VDF and HFP with up to 30mol% tetrafluoroethylene (TFE) and a constant VDF to HFP molar ratio of 3.4 were considered. Two relaxation processes typical of the amorphous phase were found. The first, located at about −87°C, is related to local motions and the transition temperature was found to be independent of composition for copolymers, while it depends on TFE molar content for terpolymers. The second is related to the glass transition and the transition temperature depends on the composition. However, for semicrystalline copolymers the double glass transition phenomenon was observed. When crystallinity goes to zero at about 20 mol% HFP, only one transition is observed. It was also found that ordered structures can take place for terpolymers when TFE molar concentration exceeds 20%. The crystal disorder transition of pure PVDF (75°C) is observed also for low HFP concentrations but the transition temperature is strongly reduced. Analogies between the VDF-HFP and E-P systems are also discussed.     

Structure-activity relationship study of 16 a-thiocamptothecins: an integrated in vitro and in silico approach

The instability of the hydroxylactone E ring represents a critical drawback of camptothecins, because the lactone ring is recognized to be essential for stabilization of topoisomerase I‐mediated DNA cleavage. In an attempt to investigate the effect of the thiopyridone pharmacophofore on the molecular and pharmacological features of the drug, we prepared a series of novel 16 a‐thiocamptothecin analogues. Due to the sulfur atom, a destabilization of the hydrogen bond between the hydroxy group in position 17 of the opened E ring and the carbonyl of the pyridone moiety is predicted, thus shifting the equilibrium toward the closed lactone form and increasing the lipophilic properties of the compounds. This feature was associated with superior antiproliferative potency, with reduced interaction with the human serum albumin and with substantial increase of the persistence of the topoisomerase I–DNA cleavable complex. These effects were prominent for thio‐SN38, the most active compound of the series. The favorable interactions at the molecular and cellular level of the reported thiocamptothecins confer promising features, and these compounds warrant preclinical development.     

Structure and thermal properties of heat treated plasma sprayed ceria–yttria co-stabilized zirconia coatings

Thick plasma sprayed thermal barrier coatings are suitable for thermal and hot corrosion protection of metal components in land-based turbine and diesel engines. In this work, ceria–yttria co-stabilized zirconia coatings were deposited by atmospheric plasma spraying in a mixture of non-transformable tetragonal t′ and cubic c zirconia phases. Free-standing coatings were isothermally annealed at 1315 °C for different times and their crystal structure was studied by XRD. No phase decomposition occurred. Columnar grains grew in the molten splats with increasing annealing time according to a preferential direction and, after 50 h of heat treatment, they were partially replaced by equiaxed grains. Both in-plane and out-of-plane thermal expansion coefficients (CTEs) were measured from coating expansion during heating. The CTE was slightly sensitive to thermal exposure in out-of-plane direction, whereas it kept almost constant in plane direction. The specific heat capacity Cp of annealed coatings, measured by differential scanning calorimetry (DSC), decreased in comparison with as-sprayed coating, due to high-temperature sintering.