A Structure-Properties Relationship Study of Self-Healing Materials Based on Styrene and Furfuryl Methacrylate Cross-Linked via Diels–Alder Chemistry

A series of copolymers of styrene and furfuryl methacrylate characterized by various molecular structures (linear and star, block and random) is synthesized via atom transfer radical polymerization, and cross-linked with a bismaleimide by means of thermally reversible Diels–Alder (DA) reaction, to obtain self-healing materials. The prepared materials are studied in terms of gelation, swelling, thermal, and dynamic-mechanical analysis, with the aim of correlating relevant properties to their chemical structure. It is found that the furan/styrene ratio, as well as the molecular architecture, have a major influence on the properties. It is also found that the reversibility of the DA reaction is not complete in the solid state for materials with high cross-linking density. This study provides some important tools for the design of materials characterized by thermally reversible behavior, which find usually application as self-healing thermosets, coatings, or adhesives.     

[2.2]Paracyclophane-Based TCN-201 Analogs as GluN2A-Selective NMDA Receptor Antagonists

Recent studies have shown the involvement of GluN2A subunit-containing NMDA receptors in various neurological and pathological disorders. In the X-ray crystal structure, TCN-201 ( 1 ) and analogous pyrazine derivatives 2 and 3 adopt a U-shape (hairpin) conformation within the binding site formed by the ligand binding domains of the GluN1 and GluN2A subunits. In order to mimic the resulting π/π-interactions of two aromatic rings in the binding site, a [2.2]paracyclophane system was designed to lock these aromatic rings in a parallel orientation. Acylation of [2.2]paracyclophane ( 5 ) with oxalyl chloride and chloroacetyl chloride and subsequent transformations led to the oxalamide 7 , triazole 10 and benzamides 12 . The GluN2A inhibitory activities of the paracyclophane derivatives were tested with two-electrode voltage clamp electrophysiology using Xenopus laevis oocytes expressing selectively functional NMDA receptors with GluN2A subunit. The o-iodobenzamide 12 b with the highest similarity to TCN-201 showed the highest GuN2A inhibitory activity of this series of compounds. At a concentration of 10 μM, 12 b reached 36 % of the inhibitory activity of TCN-201 ( 1 ). This result indicates that the [2.2]paracyclophane system is well accepted by the TCN-201 binding site.     

Electrical and mechanical characterization by instrumented indentation technique of La0.85Sr0.15Ga0.8Mg0.2O3−δ electrolyte for SOFCs

La_0.85Sr_0.15Ga_0.8Mg_0.2O_3?δ pellets obtained by the polymeric organic complex solution method, isostatic pressing and sintering at 1350 °C have been electrical and mechanically studied. Electrical measurements evidenced reasonable ionic conductivities (0.01 S cm^?1 at 800 °C), which were comparable to those reported for the La_1?xSr_xGa_1?yMg_yO_3?δ prepared by other synthesis methods. On the other hand, the mechanical properties (elastic modulus, E and hardness, H) have been determined at micro/nanometric scale using the instrumented indentation technique. While E did not vary significantly with the increasing indentation depth (h), H values strongly decreased with the indentation depth up to 500 nm. For h > 500 nm, both mechanical properties remained almost constant, thus obtaining E = 271 ± 6 GPa and H = 13.2 ± 0.4 GPa. Finally, the residual imprints and fracture mechanisms have been observed by atomic force microscopy (AFM).     

Fabrication of Reduced Fat Products by Controlled Heteroaggregation of Oppositely Charged Lipid Droplets

Abstract: This study describes how the rheological properties of colloidal dispersions formed by heteroaggregation of oppositely charged protein‐coated lipid droplets depend on total particle concentration. Mixed‐particle emulsions were formed by mixing single‐particle emulsions containing either β‐lactoglobulin‐coated lipid droplets (ζ≈?42 mV, d₄₃≈ 0.35 μm) or lactoferrin (LF)‐coated lipid droplets (ζ≈+26 mV, d₄₃≈ 0.32 μm). A series of single‐particle and mixed‐particle emulsions with different total fat contents (5% to 40%) were prepared, and their mean particle size, apparent viscosity, and shear modulus were measured. Mixed‐particle emulsions (40% LF: 60%β‐Lg) containing relatively high fat contents (>10%) had high viscosities and paste‐like properties. These rheological characteristics were attributed to extensive particle aggregation and network formation due to electrostatic attraction between oppositely charged droplets. The viscosities of mixed‐particle emulsions were much higher than those of single‐particle emulsions with equivalent fat contents. Measurements of the color coordinates (L*, a*, b*) of mixed‐particle emulsions with low fat contents showed that they had similar appearances as single‐particle emulsions with high fat contents. This study has important implications for the creation of reduced fat foods with similar sensory qualities as higher fat foods. Practical Application: This study describes how novel food materials can be created by mixing together negatively charged and positively charged lipid droplets. These mixed emulsions may be suitable for the creation of reduced fat products, since they have high viscosities and paste‐like properties at relatively low fat contents.     

Homogeneous cooling of hard ellipsoids

We study the homogeneous cooling of hard, smooth ellipsoids in three dimensions using event driven numerical simulation. The elongation of the particle has a strong effect on the cooling behavior. Weakly elongated ellipsoids display two distinct cooling regimes. For small times, the translational and rotational energy decay at a different rates. Once their ratio reaches a time-independent value (different from equipartition), the overall temperature of the system decays like t ^?2, as predicted by Haff??s law. For more elongated ellipsoids the translational and rotational temperatures rapidly reach a constant ratio near unity. The cooling behavior in the homogeneous state can be predicted from Haff??s law and the equilibrium collision rate.     

Nanoemulsion-based delivery systems for poorly water-soluble bioactive compounds: Influence of formulation parameters on Polymethoxyflavone crystallization

Polymethoxyflavones (PMFs) extracted from citrus peel exhibit potent anti-cancer activity, but are highly hydrophobic molecules with poor solubility in both water and oil at ambient and body temperature, which limits their bioavailability. The possibility of encapsulating PMFs within nanoemulsion-based delivery systems to facilitate their application in nutraceutical and pharmaceutical products was investigated. The influence of oil type (corn oil, MCT, orange oil), emulsifier type (β-lactoglobulin, lyso-lecithin, Tween, and DTAB), and neutral cosolvents (glycerol and ethanol) on the formation and stability of PMF-loaded nanoemulsions was examined. Nanoemulsions (r < 100 nm) could be formed using high pressure homogenization for all emulsifier types, except DTAB. Lipid droplet charge could be altered from highly cationic (DTAB), to near neutral (Tween), to highly anionic (β-lactoglobulin, lyso-lecithin) by varying emulsifier type. PMF crystals formed in all nanoemulsions after preparation, which had a tendency to sediment during storage. The size, morphology, and aggregation of PMF crystals depended on preparation method, emulsifier type, oil type, and cosolvent addition. These results have important implications for the development of delivery systems for bioactive components that have poor oil and water solubility at application temperatures.     

Core–shell polypyrrole nanoparticles obtained by atmospheric pressure plasma polymerization

Polypyrrole hollow nanoparticles were prepared by atmospheric pressure plasma polymerization. The structure of the nanoparticles was studied using Fourier transform infrared and X‐ray photoelectron spectroscopies, thermogravimetric analysis, scanning and transmission electron microscopies and atomic force microscopy. In contrast to low‐pressure plasma polymerization of pyrrole, which can produce films and solid nanoparticles, we obtained two types of hollow nanoparticles: a fraction with single spherical core and another with a core composed of small bubbles. Thermal characterization allowed us to determine that the nanoparticles are composed of highly crosslinked polymer. A mechanism that explains the formation of both types of hollow nanoparticles as well as solid nanoparticles is proposed. Chemical characterization shows that, in addition to the expected chemical structures due to pyrrole polymerization, the high energy of the plasma at atmospheric pressure produces intense dehydrogenation and oxidation processes. The fluorescence spectrum of the nanoparticles, however, shows a peak at 482 nm indicating that some degree of π‐conjugation is present in the material. © 2014 Society of Chemical Industry     

Systematic skin segmentation: merging spatial and non-spatial data

Skin detection is used in applications ranging from face detection, tracking of body parts, hand gesture analysis, to retrieval and blocking objectionable content. We present a systematic approach for robust skin segmentation using graph cuts. The skin segmentation process starts by exploiting the local skin information of detected faces. The detected faces are used as foreground seeds for calculating the foreground weights of the graph. If local skin information is not available, we opt for the universal seed. To increase the robustness, the decision tree based classifier is used to augment the universal seed weights when no local information is available in the image. With this setup, we achieve robust skin segmentation, outperforming off-line trained classifiers. The setup also provides a generic skin detection system, using positive training data only. With face detection, we take advantage of the contextual information present in the scene. With the weight augmentation, we provide a setup for merging spatial and non-spatial data. Experiments on two datasets with annotated pixel-level ground truth show that the systematic skin segmentation approach outperforms other approaches and provides robust skin detection.