Self‐assembled structures in polystyrene‐block‐polyisoprene‐blend‐polystyrene and polystyrene‐block‐poly(methyl methacrylate)‐blend‐polystyrene or ‐blend‐poly(methyl methacrylate) in the strong segregation regime

This study deals with the investigation of microphase‐separated morphology and phase behaviour in blends of polystyrene‐block‐polyisoprene with homopolystyrene and blends of polystyrene‐block‐poly(methyl methacrylate) with homopoly(methyl methacrylate) or homopolystyrene in the strong segregation regime using small‐angle X‐ray scattering and transmission electron microscopy as a function of composition, molecular weight of homopolymers, r_M and temperature. Parameter r_M = M_H/M_C (where M_H is the molecular weight of homopolymer and M_C that of the corresponding block copolymer) was selected to encompass behaviour of the chains denoted as a ‘wet brush’ (i.e. r_M < 1). The relative domain spacing D/D_o increases in the regime 0 < r_M?1 with increasing concentration of homopolymer w_P and increasing r_M but depends on the specific implemented morphology. We tested a new approximate D/D_o versus w_P relation in the strong segregation regime using block copolymers of high molecular weights. It is shown that the parameters r_M and χ^3/2N determine the slope of the D/D_o versus w_P relation in the strong segregation regime and the new approximation generally matches the experimental data better than the approximations used so far. Copyright © 2010 Society of Chemical Industry     

Polyaniline–silver composites prepared by the oxidation of aniline with silver nitrate in solutions of sulfonic acids

Aniline was oxidized with silver nitrate in aqueous solutions of sulfonic acids: camphorsulfonic, methanesulfonic, sulfamic, or toluenesulfonic acids. Polyaniline–silver composites were produced slowly in 4 weeks in good yield, except for the reaction, which took place in sulfamic acid solution, where the yield was low. Polyaniline in the emeraldine form was identified with UV–visible, FTIR, and Raman spectra. Thermogravimetric analysis was used to determine the silver content, which was close to the theoretical prediction of 68.9 wt.%. Transmission electron microscopy demonstrated the presence of silver nanoparticles of ca 50 nm average sizes as the dominating species, and hairy polyaniline nanorods having diameter 150–250 nm accompanied them. The highest conductivity of 880 S cm⁻¹ was found with the composite prepared in methanesulfonic acid solution. Its conductivity decreased with temperature increasing in the 70–315 K range, which is typical of metals such as silver. The conductivity of composites prepared in solutions of other acids was lower and increased with increasing temperature. Such dependence is typical of semiconductors, reflecting the dominating role of polyaniline in the conductivity behaviour. It is proposed that interfaces between the polyaniline matrix and dispersed silver nanoparticles play a dominating role in macroscopic level of conductivity.     

Biodiesel from rapeseed oil,methanol and KOH. 3. Analysis of composition of actual reaction mixture

Detailed analysis is described of the samples taken after suitable reaction times from the actual reaction mixture during the production of biodiesel fuel using methanolysis of rapeseed oil catalyzed by KOH. Three methods for stoppage of reaction (neutralisation of catalyst, dilution by two suitable solvents) in the sample are used. The contents of mono‐, di‐ and triacylglycerols, methylesters of fatty acids (biodiesel) and potassium salts of fatty acids of rapeseed oil, glycerol (by HPLC method), basicity (by potentiometric titration) and water (by GC and Karl‐Fischer method) in the samples are determined. An example of these determinations is described.     

Impact of particle morphology on structure,crystallization kinetics,and properties of PCL composites with TiO<Subscript>2</Subscript>-based particles

Crystallization kinetics of polycaprolactone (PCL) filled with TiO₂-based particles (TiX) was shown to depend on the TiX particle type and concentration, which were associated with a slight polymer matrix degradation. The partially degraded, shorter, and more mobile polymer chains increased the overall crystallization rate at the initial stage of crystallization, while at the later stages, the non-nucleating TiX particles acted as a sterical hindrance, slowing down the crystallization process. The PCL/TiX composites were prepared by melt-mixing and contained 2.5 and 5 wt% of the filler. The investigated TiX particles included isometric anatase microparticles (mTiO₂) and titanate nanotubes with high-aspect ratio (TiNT). Light and electron microscopy showed very homogeneous dispersion of the mTiO₂ particles in the PCL matrix, while the TiNT formed large agglomerates. In situ polarized light microscopy displayed faster isothermal crystallization of all PCL/TiX composites, but the micrographs indicated that the TiX particles did not act as nucleation centres. Isothermal DSC experiments, evaluated in terms of Avrami theory, confirmed the PLM results and showed that the overall rate of isothermal crystallization increased in the following order: PCL <PCL/TiNT <PCL/mTiO₂. Non-isothermal DSC and rheological measurements revealed the correlation between the crystallization rate and the polymer matrix degradation—the well-dispersed mTiO₂ particles with high specific surface caused the highest PCL degradation and, consequently, the earliest start of non-isothermal crystallization as well as the fastest isothermal crystallization. Microindentation hardness measurements confirmed that the partial degradation of the polymer matrix did not have a significant impact on the mechanical performance of PCL/mTiO₂ composites.     

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.     

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.     

IL-6 in the Ecosystem of Head and Neck Cancer: Possible Therapeutic Perspectives

Interleukin-6 (IL-6) is a highly potent cytokine involved in multiple biological processes. It was previously reported to play a distinct role in inflammation, autoimmune and psychiatric disorders, ageing and various types of cancer. Furthermore, it is understood that IL-6 and its signaling pathways are substantial players in orchestrating the cancer microenvironment. Thus, they appear to be potential targets in anti-tumor therapy. The aim of this article is to elucidate the role of IL-6 in the tumor ecosystem and to review the possible therapeutic approaches in head and neck cancer.     

A Complex Evaluation of the In-Vivo Biocompatibility and Degradation of an Extruded ZnMgSr Absorbable Alloy Implanted into Rabbit Bones for 360 Days

The increasing incidence of trauma in medicine brings with it new demands on the materials used for the surgical treatment of bone fractures. Titanium, its alloys, and steel are used worldwide in the treatment of skeletal injuries. These metallic materials, although inert, are often removed after the injured bone has healed. The second-stage procedure—the removal of the plates and screws—can overwhelm patients and overload healthcare systems. The development of suitable absorbable metallic materials would help us to overcome these issues. In this experimental study, we analyzed an extruded Zn-0.8Mg-0.2Sr (wt.%) alloy on a rabbit model. From this alloy we developed screws which were implanted into the rabbit tibia. After 120, 240, and 360 days, we tested the toxicity at the site of implantation and also within the vital organs: the liver, kidneys, and brain. The results were compared with a control group, implanted with a Ti-based screw and sacrificed after 360 days. The samples were analyzed using X-ray, micro-CT, and a scanning electron microscope. Chemical analysis revealed only small concentrations of zinc, strontium, and magnesium in the liver, kidneys, and brain. Histologically, the alloy was verified to possess very good biocompatibility after 360 days, without any signs of toxicity at the site of implantation. We did not observe raised levels of Sr, Zn, or Mg in any of the vital organs when compared with the Ti group at 360 days. The material was found to slowly degrade in vivo, forming solid corrosion products on its surface.     

Conversion kinetics of container glass batch melting

Understanding the batch-to-glass conversion process is fundamental to optimizing the performance of glass-melting furnaces and ensuring that furnace modeling can correctly predict the observed outcome when batch materials or furnace conditions change. To investigate the kinetics of silica dissolution, gas evolution, and primary foam formation and collapse, we performed X-ray diffraction, thermal gravimetry, feed expansion tests, and evolved gas analysis of batch samples heated at several constant heating rates. We found that gas evolving reactions, foaming, and silica dissolution depend on the thermal history of the batch in a similar manner: the kinetic parameters of each process were linear functions of the square root of the heating rate. This kinetic similarity reflects the stronger-than-expected interdependence of these processes. On the basis of our results, we suggest that changes in furnace operating conditions, such as firing or boosting, influence the melting rate less than what one would expect without consideration of batch conversion kinetics.     

Mesenchymal Stromal Cell Therapy in Novel Porcine Model of Diffuse Liver Damage Induced by Repeated Biliary Obstruction

In liver surgery, biliary obstruction can lead to secondary biliary cirrhosis, a life-threatening disease with liver transplantation as the only curative treatment option. Mesenchymal stromal cells (MSC) have been shown to improve liver function in both acute and chronic liver disease models. This study evaluated the effect of allogenic MSC transplantation in a large animal model of repeated biliary obstruction followed by partial hepatectomy. MSC transplantation supported the growth of regenerated liver tissue after 14 days (MSC group, n = 10: from 1087 ± 108 (0 h) to 1243 ± 92 mL (14 days); control group, n = 11: from 1080 ± 95 (0 h) to 1100 ± 105 mL (14 days), p = 0.016), with a lower volume fraction of hepatocytes in regenerated liver tissue compared to resected liver tissue (59.5 ± 10.2% vs. 70.2 ± 5.6%, p < 0.05). Volume fraction of connective tissue, blood vessels and bile vessels in regenerated liver tissue, serum levels of liver enzymes (AST, ALT, ALP and GGT) and liver metabolites (albumin, bilirubin, urea and creatinine), as well as plasma levels of IL-6, IL-8, TNF-α and TGF-β, were not affected by MSC transplantation. In our novel, large animal (pig) model of repeated biliary obstruction followed by partial hepatectomy, MSC transplantation promoted growth of liver tissue without any effect on liver function. This study underscores the importance of translating results between small and large animal models as well as the careful translation of results from animal model into human medicine.