Toxicity increases in ice containing monochlorophenols upon photolysis: environmental consequences

The toxic effects of photoproducts formed upon the photolysis of 2- and 4-chlorophenol (CP) frozen solutions in polycrystalline ice phase were determined with a bacterial luminescence test (Vibrio fisheri), and in vitro biomarker assay for dioxin-like effects (inductions of AhR-dependent luciferase in H4IIE-luc cells) and compared to the toxic effects of products of the same photoreaction in aquatic phase. Coupling photoproducts formed in ice samples (3'-chlorobiphenyl-2,4'-diol and 3-chlorobiphenyl-2,2'-diol from 2-CP photolysis and 5-chlorobiphenyl-2,4'-diol from 4-CP photolysis) were found to be more toxic to V. fisheri than parent CPs and elicited significant inductions of dioxin-like effects (the effective concentrations EC50 approximately 3 x 10(-5) mol L(-1) corresponded to known weaker ligands of AhR, such as nonplanar polychlorinated biphenyls or polycyclic aromatic hydrocarbons). To complete the picture, a photoproduct formed from 4-CP (5-chlorobiphenyl-2,4'-diol) was synthesized, and a detailed toxicity assessment with purified compound confirmed the results obtained with irradiated samples. Our findings support a recently proposed model according to which solar radiation can trigger the formation of new types of organic pollutants in polar ice or tropospheric ice cloud particles, presenting possibly greater risk to the environment than the parent compounds.     

Variation in fatty acid composition of ewes' colostrum and mature milk fat

Temporal content variations of approximately 70 C4–C24 fatty acids (FA) in colostrum and milk of ewes consuming winter diet were determined by gas chromatography. The content of monounsaturated, polyunsaturated and straight-chain saturated FA 14:0–16:0 in colostrum was higher whereas the content of 4:0–12:0, 18:0 and branched-chain saturated FA 15:0–17:0 was lower than that in mature milk. The effect of ewe breed on the FA profiles was not significant. The composition of FA changed most significantly 1–2 days after lambing in agreement with the time schedule of colostrum formation. Nevertheless, the content of FA further successively changed up to approximately the 6th day of lactation, whereas further changes up to the 60th day of lactation were smaller. This is consistent with the recommendation that ewes' milk is suitable for human consumption after six-to-eight days of lactation. The higher contents of palmitic and myristic acids in colostrum compared with mature milk suggest that FA composition in colostrum matches the changing needs of the growing lambs.     

Determination of micromechanical properties of a hen’s eggshell by means of nanoindentation

The work describes the suitability and applicability of the nanoindentation method for the determination of the micromechanical properties of a hen’s eggshell. The values of elastic modulus E were monitored in five different locations along the eggshell’s meridian line. Detailed maps of elastic moduli at particular eggshell cross-sections revealed high variations in local values of E-moduli at individual points, but not significant differences of their means at distant parts of the eggshell. Mean values of E-modulus in different meridian positions did not vary significantly and ranged from 47.4 to 53 GPa. Experimental histograms were created of all elastic moduli showing the frequency of their occurrence and these revealed a rather high variation in E-moduli throughout the cross-section. The probability density function can be characterised by a symmetrical shape and the distribution of E-moduli can be approximated with the Gauss distribution. The nanoindentation technique proved to be a suitable, easy-to-use, and powerful tool for assessing local variations of the mechanical properties of hen’s eggshells.     

Phase transition in swollen gels

Summary The photoelastic behaviour of two networks — polyacrylamide (PAAm) and of a network prepared by the copolymerization of acrylamide with 5 mol.% sodium methacrylate — was investigated in water-acetone mixtures. For the PAAm network the dependence of all photoelastic characteristics on the composition of the mixture is continuous. At 54 vol.% acetone in the mixture, the ionized network undergoes a transition which gives rise to jumpwise changes in the shear modulus, deformational-optical coefficient, C, and in the refractive index of the gel, n_g. While in the collapsed state the optical anisotropy of the statistical segment is negative, –3×10^–24 cm³ (indicating an interaction between the side chains), in the expanded state it is positive, 0.5 × 10^–24 cm³. The dependence of all optical characteristics on the composition of the mixtures suggests that: (a) in both networks we have a transition between two conformational states of the chain; while for the ionized network the transition is a discrete one, for the nonionized network it takes place in the range between 30 and 45 vol.% acetone in the mixture; (b) in both networks the gels are optically homogeneous throughout the whole range of compositions of the mixtures (and thus also in the close vicinity of the collapse of the ionized network).     

The participation of crown ethers in the initiation of group-transfer polymerisation

Summary The use of crown ethers in conjunction with alkali metal salts, as catalysts in group-transfer polymerization, is discussed.     

Antagonistic effects on mechanical properties of microfibrillar composites with dual reinforcement: Explanation by FEA model of soft interface

Nanofillers (NF) in microfibrillar composites support melt‐drawing and may lead to improved performance. However, antagonistic effects have also been found. The deterioration of mechanical properties by drawing in the presence of NF, as found by other authors in analogous undrawn systems, has not yet been explained. Experiments indicating the importance of NF migration between the HDPE matrix and the PA6 fibrils in the course of drawing have led to a tentative conclusion of changed crystallinity in the interfacial area resulting in a layer with reduced modulus. This was confirmed by the finite element analysis considering the formation of a “soft” interface as a result of reduced content of HDPE spherulites at the fiber surfaces. The results show a marked impact of this phenomenon on modulus. This original concept presents a basis for explaining some antagonistic effects in multicomponent polymer systems and a tool for the more rational design of composite materials. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44712.     

Gradient Composites of Alkaline Poly(6‐hexanelactam) with Graphite: One‐Step Synthesis,Structure, and Mechanical Properties

In a one‐step synthesis of gradient composites, molten monomer of 6‐hexanelactam was mixed with graphite (5 wt.‐%) and alkaline polymerization was performed under quasi‐isothermal conditions at about 170°C. The following initiator/activator system insensitive to traces of water and other low‐molecular‐weight compounds adsorbed on filler surface was used: the sodium salt was prepared through the reaction of sodium dicaprolactamobis(2‐methoxyethoxo)aluminate with 6‐hexanelactam; N‐acyllactam was formed in situ in molten monomer by solving flexible or rigid polyurethane foam consisting of either toluene diisocyanate or diphenylmethane‐4,4′‐diisocyanate, and a poly(propylene oxide) based polyol. To obtain gradient composites with a compositional variation between plane‐parallel surfaces, the incorporated filler underwent sedimentation due to gravity during initial stages of polymerization. The graphite‐free surface is suitable for treatment with adhesives, while the graphite‐rich surface layer (containing about 11 wt.‐% of graphite) possesses improved friction characteristics. Graphite slightly (i) reduces the polymer yield and the mean spherulite diameter; (ii) increases the crystallinity due to its nucleation activity; (iii) decreases the compliance, but does not affect its time dependence given by the matrix and (iv) reduces the yield strength, tensile strength and elongation at break. The friction coefficient of the graphite‐rich surface is reduced to almost 50% of that found for the graphite‐free surface; composites with cross‐linked matrix also show better wear properties.     

Automated resolution of connector architectures using constraint solving (ARCAS method)

In current software systems, connectors play an important role by encapsulating the communication and coordination logic. Since they share common patterns (elements) depending on characteristics of the connections, the elements can be predefined and reused. A method of connector implementation based on a composition of predefined elements naturally comprises two steps: resolution of the connector architecture, and creation of the actual connector code based on the architecture. However, manual resolution of a connector architecture is very difficult due to the number of factors to be considered. Thus, the challenge is to come up with an automated method, able to address all the important factors. In this paper, we present a method for automated resolution of connector architectures based on constraint solving techniques. We exploit a propositional logic with relational calculus for defining a connector theory, a constraint specification reflecting both the predefined parts and the important resolution factors, and employ a constraint solver to find a suitable connector architecture as a model of the theory. As a proof of the concept, we show how the theory can be captured in the Alloy language and resolved via the Alloy Analyzer.     

Phase transition in swollen gels

Summary The dynamic mechanical behaviour of 4% aqueous solutions and networks of poly (N, N-diethylacrylamide) and copolymers of diethylacrylamide with sodium methacrylate (MNa) (molar ratio x_MNA=0–0.05) swollen in water was measured in the temperature range 20–80 °C. With increasing temperature, at T_c polymer chains collapse from random coil to more compact globular conformations. While in the region of coil conformations (T > T_c) the mechanical behaviour of solutions has a liquid-like character (the loss modulus G″ is higher than the storage modulus G′ for a constant frequency ω=1 Hz), in the region of globular conformations (T > T_c) a heterogeneous physical network is built in solutions, and the mechanical behaviour has a solid-like character (G′ > G″). In networks the collapse is reflected in an increase of storage modulus G′; the magnitude of this increase decreases with ionization. The dependence of the loss modulus G″ on the temperature of solutions and networks allows us to conclude that the magnitude of losses in the collapsed state is affected rather by x_MNa (the modulus G″ increases with increasing ionization) than by the heterogeneous structure of the samples.     

Polypyrrole and polyaniline prepared with cerium(IV) sulfate oxidant

The conducting polymers, polypyrrole and polyaniline, were synthesized by chemical oxidative polymerization of the corresponding monomers in 0.1 M sulfuric acid using cerium(IV) sulfate as the oxidant at mole ratios of oxidant-to-monomer ranging from 0.5 to 3. The yields of the oxidation products were determined, and the samples were characterized with respect to their elemental composition, molecular structure, and morphology. The conductivity of polypyrrole prepared in 0.1 M sulfuric acid, 10^?1 to 10⁰ S cm^?1, was higher compared with the conductivity of polyaniline prepared under the same conditions, 10^?3 to 10^?1 S cm^?1. The loss of mass after deprotonation with ammonium hydroxide is reported, and discussed in terms of the type of protonation as also reflected by FTIR spectroscopy. The conductivity of polypyrrole bases remained at relatively high level, 10^?5 to 10^?3 S cm^?1, while PANI bases became non-conducting, 10^?12 to 10^?10 S cm^?1. The polymers had a granular morphology in all cases.