Composite hydrogels with temperature sensitive heterogeneities: influence of gel matrix on the volume phase transition of embedded poly-(N-isopropylacrylamide) microgels

The thermo-responsive behaviour of poly-(N-isopropylacrylamide) (PNiPAM) microgels embedded in covalently cross-linked non-temperature-sensitive polyacrylamide (PAam) hydrogel matrixes with different compositions was investigated by using small angle neutron scattering (SANS). The composition of the composite hydrogel was varied by (a) increasing the cross-linker and acrylamide concentration leading to strong hydrogel matrixes and (b) by increasing the microgel concentration to obtain composite gels with an internal structure. Additionally we synthesized composite hydrogels by using γ-irradiation as initiation for the polymerisation. This leads to the formation of chemical bonds between the PNiPAM microgels and the surrounding polyacrylamide matrix. Thus it is possible to synthesize hydrogels without an additional cross-linker, as well as pure particle networks. Some samples were prepared at two different temperatures, below and above the volume phase transition temperature of PNiPAM, resulting in highly swollen or totally collapsed microgels during the incorporation step. The volume phase transition of microgels is not influenced by a hydrogel matrix with high acrylamide concentration independent of the preparation temperature. However, an increased cross-linker concentration leads to a corset like constraint on microgel swelling. Microgels, which are embedded in the collapsed state (at 50 °C), are not able to swell upon cooling, whereas microgels embedded in the swollen state can collapse upon heating. For samples with an increased microgel concentration, the close microgel packing was disturbed by the formation of the polyacrylamide matrix. The hydrogel matrix squeezes the microgels together and leads to partial aggregation. The experiments demonstrate how composite hydrogels with stimuli-sensitive heterogeneities can be prepared such that the full responsiveness of the embedded microgels is retained while the macroscopic dimensions of the gel are not affected by the volume phase transition of the microgels.     

Chemical composition and antimicrobial activity of Satureja kitaibelii essential oil against pathogenic microbial strains

Plant species Satureja kitaibelii Wierzb. ex Heuff. is used as a spice and as a natural preservative for food and herbal tea, owing to its characteristic scent and flavor as well as high antimicrobial activity. In the present study, the antimicrobial activity of isolated essential oil of S. kitaibelii was tested against a panel of 30 pathogenic microorganisms (foodborne microbes, selected multiresistant bacterial isolates from the patient wounds and dermatophyte isolates). Limonene (15.54%), p-cymene (9.99%), and borneol (8.91%) appeared as the main components in 44 identified compounds representing 98.44% of the oil. Essential oil of S. kitaibelii showed significant activity against a wide spectrum of foodborne microbes (MIC=0.18-25.5 microg mL(-1)) and multiresistant bacterial isolates (MIC=6.25-50.0 microg mL(-1)), as well as against dermatophyte strains (MIC=12.5-50.0 microg mL(-1)). These results demonstrate that S. kitaibelii essential oil could be used as a natural potential antimicrobial agent against pathogenic strains in the treatment of foodborne disease, wound and skin infections.     

Crystallographic report: 1‐[4‐(2‐Thienyl)phenyl]germatrane

In the title compound, germanium is penta‐coordinated and adopts a trigonal bipyramidal geometry. The (2‐thienyl)phenyl group and the nitrogen atom each occupy an apical position with a transannular N→Ge bond distances of 2.247(4) and 2.219(4) Å for the two independent molecules. Copyright © 2005 John Wiley & Sons, Ltd.     

Marginal permutation invariant covariance matrices with applications to linear models

The goal of the present paper is to perform a comprehensive study of the covariance structures in balanced linear models containing random factors which are invariant with respect to marginal permutations of the random factors. We shall focus on model formulation and interpretation rather than the estimation of parameters. It is proven that permutation invariance implies a specific structure for the covariance matrices. Useful results are obtained for the spectra of permutation invariant covariance matrices. In particular, the reparameterization of random effects, i.e., imposing certain constraints, will be considered. There are many possibilities to choose reparameterization constraints in a linear model, however not every reparameterization keeps permutation invariance. The question is if there are natural restrictions on the random effects in a given model, i.e., such reparameterizations which are defined by the covariance structure of the corresponding factor. Examining relationships between the reparameterization conditions applied to the random factors of the models and the spectrum of the corresponding covariance matrices when permutation invariance is assumed, restrictions on the spectrum of the covariance matrix are obtained which lead to “sum-to-zero” reparameterization of the corresponding factor.     

Solitary Wave Transformation Due to a Change in Polarity

Solitary wave transformation in a zone with sign-variable coefficient for the quadratic nonlinear term is studied for the variable-coefficient Korteweg–de Vries equation. Such a change of sign implies a change in polarity for the solitary wave solutions of this equation. This situation can be realized for internal waves in a stratified ocean, when the pycnocline lies halfway between the seabed and the sea surface. The width of the transition zone of the variable nonlinear coefficient is allowed to vary over a wide range. In the case of a short transition zone it is shown using asymptotic theory that there is no solitary wave generation after passage through the turning point, where the coefficient of the quadratic nonlinear term goes to zero. In the case of a very wide transition zone it is shown that one or more solitary waves of the opposite polarity are generated after passage through the turning point. Here, asymptotic methods are effective only for the first (adiabatic) stage when the solitary wave is approaching the turning point. The results from the asymptotic theories are confirmed by direct numerical simulation. The hypothesis that the pedestal behind the solitary wave approaching the turning point has a significant role on the generation of the terminal solitary wave after the transition zone is examined. It is shown that the pedestal is not the sole contributor to the amplitude of the terminal solitary wave. A negative disturbance at the turning point due to the transformation in the zone of the variable nonlinear coefficient contributes as much to the process of the generation of the terminal solitary waves.     

NMR and structural investigations of a nonplanar iron corrolate: modified patterns of spin delocalization and coupling in a slightly saddled chloroiron(III) corrolate radical

An undecasubstituted chloroiron corrolate, octamethyltriphenylcorrolatoiron chloride, (OMTPCorr)FeCl, has been synthesized and studied by X-ray crystallography and (1)H and (13)C NMR spectroscopy. It is found that, although the structure is slightly saddled, the average methyl out-of-plane distance is only 0.63 Angstroms, while it is much greater for the dodecasubstituted porphyrinate analogue (OMTPP)FeCl (1.19 Angstroms) (Cheng, R.-J.; Chen, P.-Y.; Gau, P.-R.; Chen, C.-C.; Peng, S.-M. J. Am. Chem. Soc. 1997, 119, 2563-2569). In addition, the distance of iron from the mean plane of the four macrocycle nitrogens is also smaller for (OMTPCorr)FeCl (0.387 Angstroms) than for (OMTPP)FeCl (0.46 Angstroms). The (1)H and (13)C NMR spectra of (OMTPCorr)FeCl, as well as the chloroiron complexes of triphenylcorrolate, (TPCorr)FeCl; 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FeCl; 7,8,12,13-tetramethyl-2,3,17,18-tetraethylcorrolate, (TMTECorr)FeCl; and the phenyliron complex of 7,13-dimethyl-2,3,8,12,17,18-hexaethylcorrolate, (DMHECorr)FePh, have been assigned, and the spin densities at the carbons that are part of the aromatic ring of the corrole macrocycle have been divided into the part due to spin delocalization by corrole --> Fe pi donation and the part due to the unpaired electron present on the corrole ring. It is found that although the spin density at the beta-pyrrole positions is fairly similar to that of (TPCorr)FeCl, the meso-phenyl-carbon shift differences delta(m) - delta(p) are opposite in sign of those of (TPCorr)FeCl. This finding suggests that the radical electron is ferromagnetically coupled to the unpaired electrons on iron, rather than antiferromagnetically coupled, as in all of the other chloroiron corrolates. The solution magnetic moment was measured for (OMTPCorr)FeCl and found to be mu(eff) = 4.7 +/- 0.5 micro(B), consistent with S = 2 and ferromagnetic coupling. From this study, two conclusions may be reached about iron corrolates: (1) the spin states of chloroiron corrolates are extremely sensitive to the out-of-plane distance of iron, and (2) pyrrole-H or -C shifts are not useful in delineating the spin state and electron configuration of (anion)iron corrolates.     

Balance of hydrophobic and electrostatic forces in the pH response of weak polyelectrolyte capsules

A detailed study of the role of solution pH and ionic strength on the swelling behavior of capsules composed of the weak polyelectrolytes poly(4-vinylpyridine) (P4VP) and poly(methacrylic acid) (PMA) with different numbers of layers was carried out. The polyelectrolyte layers were assembled onto silicon oxide particles and multilayer formation was followed by zeta-potential measurements. Hollow capsules were investigated by scanning electron microscopy and atomic force microscopy. The pH-dependent behavior of P4VP/PMA capsules was probed in aqueous media using confocal laser scanning microscopy. All systems exhibited a pronounced swelling at the edges of stability, at pHs of 2 and 8.1. The swelling degree increased when more polymer material was adsorbed. The swollen state can be attributed to uncompensated positive and negative charges within the multilayers, and it is stabilized by counteracting hydrophobic interactions. The swelling was related to the electrostatic interactions by infrared spectroscopy and zeta-potential measurements. The stability of the capsules as well as the swelling degree at a given pH could be tuned, when the ionic strength of the medium was altered.     

Anti-Leishmania and cytotoxic activities of perillaldehyde epoxide synthetic positional isomers

Leishmaniasis belongs to a complex of zoonotic disease caused by protozoa of the genus Leishmania and is considered a major public health problem. Several essential oil chemical components have inhibitory effect against protozoa, including Leishmania donovani. Thus, the aim of this study was to evaluate for the first time the anti-Leishmania activity of two p-menthane monoterpene isomers (EPER-1: perillaldehyde 1,2-epoxide and EPER-2: perillaldehyde 8,9-epoxide) against L. donovani promastigotes as well as evaluating cytotoxic effect on mononuclear peripheral blood cells. Results of anti-Leishmania assay revealed that EPER-2 (IC₅₀ = 3.8 μg.mL^?1) was 16-fold more potent than its isomer EPER-1 (IC₅₀ = 64.6 μg.mL^?1). In contrast to PBMC cells, EPER-2 was not cytotoxic (IC₅₀ > 400 μg.mL^?1) when compared to positive control. These data suggest that the disposition of epoxide group into the p-menthane skeleton affects the anti-Leishmania activity, being that the presence of the exocyclic epoxide group considerably increased potency. Thus, it was possible to observe that the location of the epoxide group into the p-menthane skeleton resulted in different potencies.