Novel proresolving aspirin-triggered DHA pathway

Endogenous mechanisms in the resolution of acute inflammation are of interest because excessive inflammation underlies many pathologic abnormalities. We report an aspirin-triggered DHA metabolome that biosynthesizes a potent product in inflammatory exudates and human leukocytes, namely aspirin-triggered Neuroprotectin D1/Protectin D1 [AT-(NPD1/PD1)]. The complete stereochemistry of AT-(NPD1/PD1) proved to be 10R,17R-dihydroxydocosa-4Z,7Z,11E,13E,15Z,19Z-hexaenoic acid. The chirality of hydroxyl groups and geometry of the conjugated triene system essential for bioactivity were established by matching biological materials with stereochemically pure isomers prepared by organic synthesis. AT-(NPD1/PD1) reduced neutrophil (PMN) recruitment in murine peritonitis in a dose-dependent fashion whereby neither a Δ(15)-trans-isomer nor DHA was effective. With human cells, AT-(NPD1/PD1) decreased transendothelial PMN migration as well as enhanced efferocytosis of apoptotic human PMN by macrophages. These results indicate that AT-(NPD1/PD1) is a potent anti-inflammatory proresolving molecule.     

Novel polycarbonate-based polyurethane elastomers: Composition–property relationship

Novel all-aliphatic polycarbonate-based polyurethane (PC-PU) elastomers, as well as PC-PU nanocomposites filled with organic-modified clays were synthesized, characterized and studied. It was found that they have very attractive mechanical properties (e.g., elongation at break between 600% and 800%). The prepared PC-PUs possess a distinctly segmented structure, which is the key prerequisite for their behavior as strong physical rubbery networks. All synthesized materials melt at elevated temperatures (between 110 and 200 °C) and hence can be processed like normal thermoplastics. The dispersion of the clay nanofiller was achieved by its one day swelling in the alcohol and a brief successive stirring. This procedure is very successful and leads to a partial exfoliation of the clay (documented by X-ray diffraction and TEM). The best nanocomposites with very good tensile properties, particularly with significantly increased moduli were obtained using the bentonite nanofiller. The study shows that the nanofiller interacts strongly with the hard domains and influences their melting temperature (DMTA and DSC), but it does not affect the glass transition temperature of soft domains. While Cloisite 15A was found to interact preferentially with the hard domains, the organic modified bentonite shows a strong interaction with both soft and hard segments, behaving as a blending agent. Hard domains in neat matrices, formed by hydrogen bonding of hard segments, were practically invisible by X-ray or TEM, but were successfully detected by AFM. Besides excellent mechanical properties, the prepared elastomers and their nanocomposites showed an interesting phase behavior (which was studied by combining DMTA and modulated DSC).     

Induction period in the low‐temperature thermal oxidation of saturated hydrocarbons: Example of polyethylene

Thermal oxidation of hydrocarbon substrates at low‐to‐moderate temperature, typically T ≤ 150^°C, results from a radical chain process initiated by hydroperoxide decomposition and displays an induction period. A reliable model exists to simulate oxidation kinetics, but an incertitude remains on initial steps because they are out of reach of all available analytical methods. This work is aimed to have a kinetic approach of the problem, by comparing various mechanisms, i.e., (A) bimolecular decomposition of initially present hydroperoxides; (B) combined uni‐ and bimolecular decomposition of hydroperoxides; (C) the presence of radicals at the beginning of the exposure; and (D) radicals generation at (low) constant rate from irradiation, for instance by ionizing radiation linked to natural radioactivity or from a direct oxygen–substrate reaction. Scheme A is not realistic at low initial hydroperoxide concentrations. All the other mechanisms generate similar behaviors: the induction time tends toward a constant value almost independent of the nature of initial steps, when the concentration of precursors (initially present hydroperoxides or radicals) or the rate of their initial production (from species other than hydroperoxides) tends toward zero. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 769–777, 2008     

Zur Berechnung des Dampf—Flüssigkeits-Gleichgewichtes in ternären flüssigen Systemen

A simple method for predicting ternary vapor—liquid equilibria is presented and experimentally verified. The method is based on the solution of algebraic equations derived by the integration of the differential equations characterizing the dependence of the equilibrium properties of the ternary system on the state variables with the assumption that the partial derivates enter as constants. The values of the partial derivates are approximately evaluated from the binary experimental data.     

Magnetically responsive carboxylated magnetite-polydipyrrole/polydicarbazole nanocomposites of core-shell morphology. Preparation, characterization, and use in DNA hybridization

Novel bis-heterocyclic mono- and dicarboxylated dipyrrole and dicarbazole monomers have been synthesized in a modular manner. Their oxidative polymerization around magnetite nanosized particles has been investigated and optimized toward new magnetic magnetite-polydipyrrole/polydicarbazole nanocomposites (NCs) of a core-shell morphology. These NCs were thoroughly characterized by FT-IR, TGA (Thermal Gravimetric Analysis), low- and high-resolution TEM/HR-TEM microscopies, and M?ssbauer spectroscopy along with magnetization studies. Exploiting the versatile COOH chemistry (activation by water-soluble diimides) introduced by the polymeric shell, DNA hybridization experiments have been conducted onto NC surfaces using an efficient blue-colored HRP-based enzymatic screening biological system. Highly parallel NC-supported DNA hybridization experimentations revealed that these NCs presented an interesting potential for DNA-based diagnostic applications.     

About Landau–Hopf scenario in a system of coupled self-oscillators

The conditions are discussed for which an ensemble of interacting oscillators may demonstrate the Landau–Hopf scenario of successive birth of multi-frequency quasi-periodic motions. A model is proposed that is a network of five globally coupled oscillators characterized by controlled degree of activation of individual oscillators. Illustrations are given for successive birth of tori of increasing dimension via quasi-periodic Hopf bifurcations.     

Synthesis and structure of complexes of phosphorus pentachloride with 4‐dimethylaminopyridine and n‐methylimidazole

Complexes of phosphorus pentachloride with 4‐dimethylaminopyridine and N‐methylimidazole were synthesized. The molecular structure of the phosphorus pentachloride complex with N‐methylimidazole was determined by single‐crystal X‐ray diffraction. In the cationic part of the complex, the phosphorus atom possesses four P Cl bonds within the range 2.109–2.148 Å and two cis‐P–N bonds (1.811 and 1.832 Å) with N‐methylimidazole and exhibits slightly distorted octahedral coordination with angles at phosphorus atom in the range 87.57°–91.50°. The relative stability of the cis and trans conformations of the complex was studied by DFT calculations. The chemical properties and reactivity of the compounds obtained are determined; their utility as condensing agents in the synthesis of amides from acids and amines was shown. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:171–177, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20392     

Nucleophilic catalysis of phosphorus trichloride oxygen oxidation

The effect of nucleophilic catalysis on phosphorus trichloride oxygen oxidation is discovered. A number of nucleophilic catalysts for the phosphorus trichloride oxidation are found. Triethylamine, 4‐dimethylaminopyridine (DMAP), and tetramethylurea are amongst them. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:408–411, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20439     

Causes of the double maximum conductivity of nanocomposite polymer electrolytes for lithium power sources

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