Functional amphiphilic block copolyethers as carriers of caffeic acid phenethyl ester

Amphiphilic diblock copolymers consisting of hydrophilic polyglycidol (PG) and hydrophobic poly(allylglycidyl ether) (PAGE) were prepared by sequential anionic ring‐opening polymerization of allylglycidyl ether and ethoxyethyl glycidyl ether followed by removal of the protective ethoxyethyl groups. The polymerization was initiated by partially deprotonated dodecanol and performed in solvent‐free conditions. The copolymers were composed of a hydrophobic dodecyl residue attached to a block of PAGE with a fixed degree of polymerization (dp = 44) and differing in length of the PG block (dp = 16 and 66, corresponding to PG contents of 25 and 60 mol%, respectively). The two copolymers were spontaneously soluble in water. Above a certain critical concentration, they formed well‐defined self‐assembled nanoparticles. Their characterization parameters were determined by static and dynamic light scattering. The aggregates of the more hydrophobic copolymer, C₁₂‐PAGE‐PG25, were characterized by considerably larger dimensions and molar mass, reaching 78.6 nm and 253.0 × 10⁶ g mol^?1, respectively, than those of the more hydrophilic copolymer, C₁₂‐PAGE‐PG60. The hydrophobic moieties were proved to create a favorable environment for solubilization of caffeic acid phenethyl ester (CAPE) (the main active ingredient of propolis with cytotoxic and antioxidant activities), whereas the numerous hydroxyl groups from the PG moieties brought additional benefits related to the biocompatibility of the copolymers. Preliminary experiments with L929 fibroblast cells showed that the aggregates displayed no signs of toxicity in the applied in vitro test system, suggesting their appropriateness as a drug delivery platform. The CAPE‐loaded aggregates, however, showed dose‐dependent cytotoxic effects, indicating that CAPE retained its cytotoxic activity. © 2019 Society of Chemical Industry     

Polyaniline prepared in ethylene glycol or glycerol

Oxidations of aniline or aniline hydrochloride have been carried out in ethylene glycol or glycerol and in their mixtures with water. Ammonium peroxydisulfate was used as oxidant. The oxidation of aniline is exothermic and changes in temperature were monitored to follow its progress. The effect of the solvents on the course of oxidation, morphology, and properties of final products has been studied by scanning electron microscopy, FTIR spectroscopy, and conductivity measurements. It is proposed that the reduction of dielectric constant of the reaction medium results in the reduced dissociation of ionic species that take a part in oxidative polymerization. Consequently, the addition of an organic solvent has a similar effect as a decrease in the acidity of the reaction mixture. Conductivity and morphology depend on the mole ratio of oxidant and monomer, and the type and volume fractions of organic solvents, viz. ethylene glycol and glycerol, which were used in reactions.     

Frost resistance of clay roofing tiles: Case study

In order to give required protection of the buildings, clay roofing tiles should be resistant to freezing conditions. In the present study, clay roofing tiles were fired at different temperatures. Afterwards, direct and indirect test methods were used to evaluate their frost resistance. The direct method in standard EN 539-2 was applied, ASTM C 1167-03 was used for indirect methods, and Maage factor was calculated from Hg-porosimetry curve. It was confirmed that the temperature of firing is the main influential parameter as it affects the porosity of a ceramic body. The comparison between indirect and direct methods of prediction and test of frost resistance has also shown good correlation.     

Chemical oxidative polymerization of ethacridine

Novel electroactive paramagnetic ethacridine oligomers were synthesized by the oxidation of ethacridine lactate with ammonium peroxydisulfate in acidic aqueous solution. The oxidative coupling of ethacridine was proved by gel permeation chromatography and MALDI-TOF mass spectrometry demonstrating the presence of oligomeric chains. Theoretical study of the mechanism of oxidation of ethacridine has been based on the semi-empirical quantum chemical computations of heat of formation and ionization energy of ethacridine, protonated ethacridine, generated reactive species and reaction intermediates, taking into account influence of pH and solvation effects. It was revealed that the prevalent ethacridine dimers are N_(C6)C5 coupled. The influence of oxidant to monomer mole ratio on the molecular structure and the morphology of ethacridine oligomers has been studied by elemental analysis, FTIR, Raman, EPR and UV-Visible spectroscopies, MALDI-TOF mass spectrometry and scanning electron microscopy. Besides unoxidized monomeric units as prevalent, oligoethacridines contain the iminoquinonoid and newly formed fused phenazine units. The electroactivity of ethacridine oligomers was investigated by cyclic voltammetry.     

A model for swelling changes in a covalently crosslinked gel caused by unfolding of folded domains

A model describing swelling changes of covalently crosslinked gels caused by unfolding of crosslinks of folded chains built-in in the gel matrix was proposed. By unfolding, a new interacting surface is exposed which may differ from the interacting sites of the gel polymer. Non-ionic as well as ionic interactions are considered. A certain force generated by the swelling pressure acts on the ends of the folded crosslinks and unfolding starts when this force exceeds a certain limiting value. The continuation or arrest of unfolding depends on whether the exposure of the new interacting surface decreases or increases this force. The unfolding process is considered to be irreversible but possible reversibility can be considered. This model relates to biohybrid gels in which the folded domain of the crosslink is composed of elements of the muscle protein titin. The model is based on the statistical-mechanical theory of swelling of crosslinked polymers. A change in external variables such as temperature or degree of ionization can cause an abrupt change in volume of the swollen gel (transition) within a certain range of parameters characterizing the gel and polymer-solvent interactions. Received: 23 January 2001/Accepted: 12 May 2001     

Rheology and porosity control of poly(2-hydroxyethyl methacrylate) hydrogels

Swelling and dynamic mechanical behavior in a broad frequency range of homogeneous and porous poly(2-hydroxyethyl methacrylate) gels were studied in relation to their matrix structure, gel morphology and nature of the swelling medium. Very lightly cross-linked gels showed up relatively large mechanical losses caused by slow relaxation of hydrophobic physical associates still proceeding at frequency 10^?3 Hz. The macroporous gels of fused-spheres type morphology contained many dangling aggregates not bearing the stress which caused concentration of the stresses in the load bearing paths through the matrix. This is the reason for the sudden drop of storage modulus. In the α-relaxation region, the loss factors for homogeneous and porous gels merged into a single master curve. Reswelling of gels in a poor solvent caused a decrease of the swelling degree and shifted their α-relaxation to lower frequencies; reswelling in good solvent shifted the maximum of α-relaxation to higher frequencies.     

The digital agenda of virtual currencies: Can BitCoin become a global currency?

This paper identifies and analyzes BitCoin features which may facilitate BitCoin to become a global currency, as well as characteristics which may impede the use of BitCoin as a medium of exchange, a unit of account and a store of value, and compares BitCoin with standard currencies with respect to the main functions of money. Among all analyzed BitCoin features, the extreme price volatility stands out most clearly compared to standard currencies. In order to understand the reasons for such extreme price volatility, we attempt to identify drivers of BitCoin price formation and estimate their importance econometrically. We apply time-series analytical mechanisms to daily data for the 2009–2014 period. Our estimation results suggest that BitCoin attractiveness indicators are the strongest drivers of BitCoin price followed by market forces. In contrast, macro-financial developments do not determine BitCoin price in the long-run. Our findings suggest that as long as BitCoin price will be mainly driven by speculative investments, BitCoin will not be able to compete with standard currencies.     

The potential of Festuca rubra and Calamagrostis epigejos for the revegetation of fly ash deposits

Two grass species, Festuca rubra (sown) and Calamagrostis epigejos (naturally recolonised), were studied at two fly ash deposit lagoons, weathered 5 (L1) and 13 years (L2). Both species were assessed in terms of their invasive ability, photosynthetic efficiency, trace elements accumulation, and damage symptoms, while the characteristics of the habitat were assessed in terms of trace element content, and the pH and EC of the ash. In the ash weathered for 5 and 13 years, B and Mn concentrations fell within the normal range for soils, while there was an As, Mo and Cu excess, and Se and Zn deficit. There was no difference in the photosynthetic efficiency (ns) of the C. epigejos populations at the different-aged ash lagoons, but differences were found between the populations of F. rubra (P < 0.001). F. rubra displayed damage symptoms, in the form of leaf tip chlorosis and necrosis, and wilting seedlings — a result of B accumulation in toxic concentrations and a Cu and Mn deficit. After 13 years the sown F. rubra remained over 9.5% of the ash lagoon's area (L2), while over the same period the naturally recolonised C. epigejos had overgrown 87.5% of the area. The greater colonisation and survival potential of C. epigejos is a result of multiple tolerance to the conditions at ash deposits and of the competitive ability of this species to dominate the colonised habitat. Therefore, characteristics of naturally colonised species can be used for modelling future actions of biological restoration of fly ash deposits aimed at binding the ash with minimal investment (the short-term aim), and for providing conditions for revegetation, and shortening the successive phases in the revegetation of ash deposits after the closure of thermal plants (the long-term aim).