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.     

Vegetable fillers for electric stimuli responsive elastomers

Dielectric elastomer actuators (DEAs) have been studied widely in recent years for artificial muscle applications, but their implementation into production is limited due to high operating voltages required. The actuation behavior of dielectric elastomer under an applied electric field is predicted by Maxwell's pressure and thickness strain equations. According to these equations, the best electromechanical response is achieved when the relative permittivity is high and elastic modulus is low. The potential source for additives increasing the relative permittivity of rubbers can be vegetable powders that have much higher dielectric constant than common elastomers. In the present research, the dielectric and actuation properties of polyacrylate rubber (ACM) were studied after the addition of different vegetable‐based fillers such as potato starch, corn starch, garlic, and paprika. The results were compared to ACM filled with barium titanate. The compounds containing vegetable fillers showed higher relative dielectric permittivity at 1 Hz frequency than the compounds containing barium titanate due to higher interfacial polarization. The actuation studies showed that lower electric fields are required to generate certain actuation forces when the starches and garlic are used in the rubber instead of barium titanate. Therefore, the vegetable‐based fillers can be used to improve actuation performance of DEAs. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45081.     

Application of β-Sitosterol + γ-Oryzanol-Structured Organogel as Migration Barrier in Filled Chocolate Products

Oil migration in filled pralines is a phenomenon that is highly correlated with the occurrence of chocolate bloom. In this study the potential to suppress or prevent oil migration by incorporation of sterol/sterolster-structured organogels was evaluated. Different quantities, 2.5 or 14% (w/w), of gel with structurant levels of either 10 or 25% (w/w) were studied in a layered model system. The gel was either a part of the nougat or of the chocolate phase, or as a separate layer. Samples were monitored regularly for a period of 24 weeks at storage temperatures of 10, 18 and 28 °C. The amount of migrated oil was determined via DSC analysis of a surface sample. The results indicate that, despite the additional oil brought into the system via the oleogel, the level of oil found in the chocolate layer is reduced through the presence of the gel. In particular, the three-layer system and gelled chocolate appear to be promising routes to either suppress oil migration or improve nutritional profiles by incorporation of liquid oils.     

Thermodynamics of copper‐manganese and copper‐iron spinel solid solutions

High‐temperature oxide melt solution calorimetry has been performed to investigate the energetics of spinel solid solutions in the Mn₃O₄‐CuMn₂O₄ and Fe₃O₄‐CuFe₂O₄ systems. The spinel solid solutions were synthesized by a ceramic route and calcined at appropriate temperatures to obtain single phase samples. The drop solution enthalpies of the solid solutions in the Mn₃O₄‐CuMn₂O₄ system are the same within experimental error as the enthalpies of drop solution of mechanical mixtures of the end‐members, indicating a zero heat of mixing, i.e., ideal mixing in terms of enthalpy. In Fe₃O₄‐CuFe₂O₄, the drop solution enthalpy of the solid solutions shows a positive deviation from those of the mechanical mixture of the end‐members, suggesting negative mixing enthalpy. The formation enthalpies of the spinel solid solutions from their constituent oxides plus oxygen and from the elements were also determined.     

Chlorinated Polycyclic Aromatic Hydrocarbons Associated with Drinking Water Disinfection: Synthesis,Formation under Aqueous Chlorination Conditions and Genotoxic Effects

Polycyclic aromatic hydrocarbons (PAHs) are among the most persistent and toxic organic micropollutants present in water and several of them are mutagenic and carcinogenic. Although it has been shown that chlorinated derivatives of PAHs (Cl-PAHs) may be formed during the water chlorination procedure, little is known about their potential genotoxic and carcinogenic effects. The objectives of the present work were to prepare and characterize the major chlorinated derivatives of benzo[a]pyrene (BaP) and fluoranthene (Fluo), to develop an analytical methodology for their quantification in water samples and to analyse their potential genotoxicity. Chlorinated standards were prepared by a newly developed two phase method (water/n-hexane) using sodium hypochlorite. 6-Chloro-benzo[a]pyrene was selectively obtained from BaP, while 1,3-dichloro-fluoranthene and 3-chloro-fluoranthene were obtained from Fluo. All products were isolated and characterized by nuclear magnetic resonance and mass spectrometry. The formation of BaP- and Fluo-chlorinated derivatives under aqueous chlorination conditions was observed using a SPE-HPLC-FLD methodology. In addition, the cytotoxic and genotoxic activities of the three chlorinated derivatives were analyzed in comparison to their parent compounds, in a human-derived hepatoma cell line using the neutral red uptake and comet assays, respectively. The results showed that, at the equimolar doses of 100 and 125 μM, 6-Cl-BaP was able to induce a significantly higher level of DNA damage than BaP, suggesting a more potent genotoxic effect. In contrast, neither Fluo nor its chlorinated derivatives were genotoxic in the same cell line. The identification of new and possibly hazardous water chlorination by-product from PAHs emphasizes the need to minimize total organic carbon content of raw water and the implementation of safer water disinfection methods.     

ENGINEERING ASPECTS OF PENICILLIN G TRANSFER AND CONVERSION TO 6-AMINOPENICILLANIC ACID IN A BIOREACTOR WITH A MOBILE BED OF IMMOBILIZED PENICILLIN AMIDASE

This article presents studies on the external and internal mass transfers of penicillin G for 6-aminopenicillanic acid enzymatic production using a bioreactor with a stirred bed of immobilized penicillin amidase. By means of the substrate mass balance for a single particle of biocatalyst and considering the kinetic model adapted for competitive and noncompetitive inhibitions, specific mathematical models were developed for describing the profiles of penicillin G concentration in the outer and inner regions of biocatalyst and for estimating its mass flows in the liquid boundary layer surrounding the particle and inside the particle. The values of the mass flows are significantly influenced by the internal diffusion velocity and rate of the enzymatic conversion of substrate. These cumulated influences led to the appearance of an enzymatic inactive region near the particle center, its magnitude varying from 0 to 9.2% of the overall volume of particles.     

Biodegradable Polycaprolactone-Titania Nanocomposites: Preparation,Characterization and Antimicrobial Properties

Nanocomposites obtained from the incorporation of synthesized TiO₂ nanoparticles (≈10 nm average primary particle size) in different amounts, ranging from 0.5 to 5 wt.%, into a biodegradable polycaprolactone matrix are achieved via a straightforward and commercial melting processing. The resulting nanocomposites have been structurally and thermally characterized by transmission electron microscopy (TEM), wide/small angle X-ray diffraction (WAXS/SAXS, respectively) and differential scanning calorimetry (DSC). TEM evaluation provides evidence of an excellent nanometric dispersion of the oxide component in the polymeric matrix, with aggregates having an average size well below 100 nm. Presence of these TiO₂ nanoparticles induces a nucleant effect during polymer crystallization. Moreover, the antimicrobial activity of nanocomposites has been tested using both UV and visible light against Gram-negative Escherichia coli bacteria and Gram-positive Staphylococcus aureus. The bactericidal behavior has been explained through the analysis of the material optical properties, with a key role played by the creation of new electronic states within the polymer-based nanocomposites.     

UV Radiation and the Skin

UV radiation (UV) is classified as a “complete carcinogen” because it is both a mutagen and a non-specific damaging agent and has properties of both a tumor initiator and a tumor promoter. In environmental abundance, UV is the most important modifiable risk factor for skin cancer and many other environmentally-influenced skin disorders. However, UV also benefits human health by mediating natural synthesis of vitamin D and endorphins in the skin, therefore UV has complex and mixed effects on human health. Nonetheless, excessive exposure to UV carries profound health risks, including atrophy, pigmentary changes, wrinkling and malignancy. UV is epidemiologically and molecularly linked to the three most common types of skin cancer, basal cell carcinoma, squamous cell carcinoma and malignant melanoma, which together affect more than a million Americans annually. Genetic factors also influence risk of UV-mediated skin disease. Polymorphisms of the melanocortin 1 receptor (MC1R) gene, in particular, correlate with fairness of skin, UV sensitivity, and enhanced cancer risk. We are interested in developing UV-protective approaches based on a detailed understanding of molecular events that occur after UV exposure, focusing particularly on epidermal melanization and the role of the MC1R in genome maintenance.     

Specific interactions in blends containing Chitosan and functionalized polymers. Molecular dynamics simulations

Chitosan (CS)/poly(vinyl alcohol) (PVA) and Chitosan/poly(2-hydroxyethyl methacrylate) (P2HEM) blends have been studied through molecular dynamic simulations. In a previous work it was found miscibility between these polymers and it was attributed to hydrogen bonding formation. However, the experimental information obtained was not enough to know which of the interacting groups of Chitosan, i.e. -CH₂OH or -NH₂, are responsible of the interaction. Therefore, we have performed molecular dynamics simulation runs of 1 ns in order to calculate radial distribution functions (RDF) for the groups tentatively involved in the interaction. The results are correlated with our previous experimental data. This way, we have obtained a more precise conclusive information about the interactions involved as function of the blends composition. For low compositions of PVA and P2HEM the interaction is predominantly with the hydroxymethyl groups of CS while as the composition of PVA and P2HEM increases, the interaction with the amine groups increases.     

Dependence of the phase separation process on the relative onset of network formation in simultaneous interpenetrating polymer networks

Morphology development during the synthesis at room temperature of an interpenetrating polyurethane/poly(methyl methacrylate) network was investigated by small-angle X-ray scattering in relation with their relative kinetics of formation, determined by Fourier transform infra red spectroscopy. When the time lag between the onset of the two reactions is short, macroscopic phase separation occurs as the polyurethane network is incompletely formed. However, when the time lag increases, the poly(methyl methacrylate) forms into a more continuous network which limits the growth of phase separation to a close environment.