Mechanism of ?-caprolactone polymerization and ?-caprolactone/trimethylene carbonate copolymerization carried out with Zr(Acac)4

The paper presents the mechanism of the polymerization of ?-caprolactone with the use of Zr(Acac)₄. At the first stage of the initiation of the polymerization, a reaction consisting of proton transfer from caprolactone to acetylacetonate ligand and then ligand exchange reaction with release of free acetylacetone (HAcac) occur. Complex 1, arisen as a product of this reaction, is the actual initiator of the observed polymerization. During the conducted polymerization the molar mass increase is directly proportional to monomer conversion degree. On the basis of observed phenomenon, the polymerization of cyclic trimethylene carbonate (TMC) applying ?-caprolactone as a co-initiator is possible. Complex 1 arose in the initial phase of this reaction as well, being an equally efficient initiator for TMC polymerization. Using Zr(Acac)₄ as an initiator for an ?-caprolactone/TMC copolymerization resulted in obtaining a series of copolymers with varied, predicted composition and high molar mass values.     

Optimum deposition conditions of ultrasmooth silver nanolayers

Reduction of surface plasmon-polariton losses due to their scattering on metal surface roughness still remains a challenge in the fabrication of plasmonic devices for nanooptics. To achieve smooth silver films, we study the dependence of surface roughness on the evaporation temperature in a physical vapor deposition process. At the deposition temperature range 90 to 500 K, the mismatch of thermal expansion coefficients of Ag, Ge wetting layer, and sapphire substrate does not deteriorate the metal surface. To avoid ice crystal formation on substrates, the working temperature of the whole physical vapor deposition process should exceed that of the sublimation at the evaporation pressure range. At optimum room temperature, the root-mean-square (RMS) surface roughness was successfully reduced to 0.2 nm for a 10-nm Ag layer on sapphire substrate with a 1-nm germanium wetting interlayer. Silver layers of 10- and 30-nm thickness were examined using an atomic force microscope (AFM), X-ray reflectometry (XRR), and two-dimensional X-ray diffraction (XRD2).

PACS

63.22.Np Layered systems; 68. Surfaces and interfaces; thin films and nanosystems (structure and nonelectronic properties); 81.07.-b Nanoscale materials and structures: fabrication and characterization     

Insulin-Like Growth Factor-2 Is Induced Following 5-Aminolevulinic Acid-Mediated Photodynamic Therapy in SW620 Human Colon Cancer Cell Line

The IGF system is a family of polypeptide growth factors, which plays a significant role in the development and growth of many cells. Dysregulation of insulin-like growth factors and their pathway components has been connected with essential tumor properties, such as tumor cell proliferation, antiapoptotic properties, invasive behavior and chemotherapy resistance. However, the effects of photodynamic therapy (PDT), one of the cancer treatment methods for the regulation of the IGF signaling pathway, are still unclear. The aim of this study was to investigate the expression of IGF-2 after 5-aminolevulinic acid (5-ALA)-mediated-PDT in SW620 human colorectal cancer cells with evaluation of cell proliferation and apoptosis and to determine the effects of PDT on the IGF-2 receptor (IGF-2R), IGF-2 binding protein-1 (IGF-2BP-1) and the proapoptotic protein, BAX. Cells were treated with 5-aminolevulinic acid and its methyl ester. Changes of the expression and concentration of IGF-2 before and after treatment were assayed by immunocytochemistry, Western blot and ELISA. We found that IGF-2 was significantly overexpressed in the SW620 cell line, while its receptor and binding protein-1 were not significantly changed. Within this study, we would like to suggest that IGF-2 contributes to the effects of PDT and that its expression will influence post-PDT efficacy.     

Interleukins 6 and 15 Levels Are Higher in Subcutaneous Adipose Tissue,but Obesity Is Associated with Their Increased Content in Visceral Fat Depots

Excess adiposity is associated with chronic inflammation, which takes part in the development of obesity-related complications. The aim of this study was to establish whether subcutaneous (SAT) or visceral (VAT) adipose tissue plays a major role in synthesis of pro-inflammatory cytokines. Concentrations of interleukins (IL): 1β, 6, 8 and 15 were measured at the protein level by an ELISA-based method and on the mRNA level by real-time PCR in VAT and SAT samples obtained from 49 obese (BMI > 40 kg/m²) and 16 normal-weight (BMI 20–24.9 kg/m²) controls. IL-6 and IL-15 protein concentrations were higher in SAT than in VAT for both obese (p = 0.003 and p < 0.0001, respectively) and control individuals (p = 0.004 and p = 0.001, respectively), while for IL-1β this was observed only in obese subjects (p = 0.047). What characterized obese individuals was the higher expression of IL-6 and IL-15 at the protein level in VAT compared to normal-weight controls (p = 0.047 and p = 0.016, respectively). Additionally, obese individuals with metabolic syndrome had higher IL-1β levels in VAT than did obese individuals without this syndrome (p = 0.003). In conclusion, concentrations of some pro-inflammatory cytokines were higher in SAT than in VAT, but it was the increased pro-inflammatory activity of VAT that was associated with obesity and metabolic syndrome.     

Rhodium(I) complex catalyst immobilized on terpolymers of N‐vinylpyrrolidinone and 1‐vinylimidazole

The hydrosilylation of cyclohexanone and acetone with triethysilane and diphenysilane catalyzed by polymer‐supported Rh(I) complex has been investigated. Two terpolymers of styrene, divinylbenzene, and 1‐vinylimidazole (S/DVB/VI) or N‐vinylpyrrolidinone (S/DVB/NVP) were used as the catalysts supports. Physical characterization of these materials has involved the measurements of the structural parameters in the dry and swollen states by DSC, the nitrogen BET adsorption method and inverse steric exclusion chromatography ISEC. From these results it can be concluded that the original polymer structure has been changed during the complex attachment giving rise to materials of higher porosity. X‐ray photoelectron spectroscopy XPS, IR, and AAS spectroscopy were used to characterization of heterogeneous complexes before and after use. The effect of the morphology of the support on the catalytic properties of the polymer‐supported Rh(I) species was tested in the hydrosilylation of ketones and correlated with the reaction mechanism. It was demonstrated that the high selectivity of homogeneous rhodium complex toward the silyl ethers can be partially reversed to the dehydrogenative silylation products by a proper choice of polymer support with favorable microporous structure. Recycling tests demonstrated high stability of the supported catalysts during prolonged use. The constant selectivity of the supported catalysts demonstrated during recycling experiments showed that they could be useful for practical application. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Relaxation processes and intermolecular interactions in PVME hydrogels in sub-zero temperatures: Glass transition and pre-melting of ice

The phase transition observed by various methods in poly(vinyl methyl ether)/water systems at around 18 °C has been assigned by some investigators to the pre-melting of water and by others to a glass transition of the polymer. In this study, broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry were used to identify this transition in radiationally crosslinked poly(vinyl methyl ether) hydrogels, as well as to analyse sub-zero relaxation processes in such a three-phase (polymer/ice/liquid water) system. The process at 18 °C was related to the pre-melting of water induced by the segmental motions of the polymer; however, it was seen to be one transition due to the cooperative motions of both compounds. The atypical (two regimes) temperature dependence of the segmental motion process was observed and was related to confinement of the polymer chains between ice clusters below approximately ?24 °C; furthermore, the main dielectric process of hexagonal ice was identified and a Maxwell-Wagner effect was observed.     

A Stochastic Petri Net-Based Model of the Involvement of Interleukin 18 in Atherosclerosis

Interleukin 18 (IL-18) is a proinflammatory and proatherogenic cytokine with pleiotropic properties, which is involved in T and NK cell maturation and the synthesis of other inflammatory cytokines and cell adhesion molecules. It plays a significant role in orchestrating the cytokine cascade, accelerates atherosclerosis and influences plaque vulnerability. To investigate the influence of IL-18 cytokine on atherosclerosis development, a stochastic Petri net model was built and then analyzed. First, MCT-sets and t-clusters were generated, then knockout and simulation-based analysis was conducted. The application of systems approach that was used in this research enabled an in-depth analysis of the studied phenomenon. Our results gave us better insight into the studied phenomenon and allow revealing that activation of macrophages by the classical pathway and IL-18-MyD88 signaling axis is crucial for the modeled process.     

New 1,3,4-Oxadiazole Derivatives of Pyridothiazine-1,1-Dioxide with Anti-Inflammatory Activity

Numerous studies have confirmed the coexistence of oxidative stress and inflammatory processes. Long-term inflammation and oxidative stress may significantly affect the initiation of the neoplastic transformation process. Here, we describe the synthesis of a new series of Mannich base-type hybrid compounds containing an arylpiperazine residue, 1,3,4-oxadiazole ring, and pyridothiazine-1,1-dioxide core. The synthesis was carried out with the hope that the hybridization of different pharmacophoric molecules would result in a synergistic effect on their anti-inflammatory activity, especially the ability to inhibit cyclooxygenase. The obtained compounds were investigated in terms of their potencies to inhibit cyclooxygenase COX-1 and COX-2 enzymes with the use of the colorimetric inhibitor screening assay. Their antioxidant and cytotoxic effect on normal human dermal fibroblasts (NHDF) was also studied. Strong COX-2 inhibitory activity was observed after the use of TG6 and, especially, TG4. The TG11 compound, as well as reference meloxicam, turned out to be a preferential COX-2 inhibitor. TG12 was, in turn, a non-selective COX inhibitor. A molecular docking study was performed to understand the binding interaction of compounds at the active site of cyclooxygenases.