Acetylation of cellulose in LiCl-<Emphasis Type="Italic">N,N</Emphasis>-dimethylacetamide: first report on the correlation between the reaction efficiency and the aggregation number of dissolved cellulose

The acylation of three cellulose samples by acetic anhydride, Ac₂O, in the solvent system LiCl/N,N-dimethylacetamide, DMAc (4 h, 110 °C), has been revisited in order to investigate the dependence of the reaction efficiency on the structural characteristics of cellulose, and its aggregation in solution. The cellulose samples employed included microcrystalline, MCC; mercerized cotton linters, M-cotton, and mercerized sisal, M-sisal. The reaction efficiency expresses the relationship between the degree of substitution, DS, of the ester obtained, and the molar ratio Ac₂O/AGU (anhydroglucose unit of the biopolymer); 100% efficiency means obtaining DS = 3 at Ac₂O/AGU = 3. For all celluloses, the dependence of DS on Ac₂O/AGU is described by an exponential decay equation: DS = DS_o − Ae^{−[(Ac2O/AGU)/B]}; (A) and (B) are regression coefficients, and DS_o is the calculated maximum degree of substitution, achieved under the conditions of each experiment. Values of (B) are clearly dependent on the cellulose employed: B_(M-cotton) > B_(M-sisal) > B_(MCC); they correlate qualitatively with the degree of polymerization of cellulose, and linearly with the aggregation number, N_agg, of the dissolved biopolymer, as calculated from static light scattering measurements: (B) = 1.709 + 0.034 N_agg. To our knowledge, this is the first report on the latter correlation; it shows the importance of the physical state of dissolved cellulose, and serves to explain, in part, the need to use distinct reaction conditions for MCC and fibrous celluloses, in particular Ac₂O/AGU, time, temperature.     

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.     

Determination of trace cationic impurities in butylmethylimidazolium-based ionic liquids: from transient to comprehensive single-capillary counterflow isotachophoresis-zone electrophoresis

Determination of impurities in ionic liquids (ILs) remains a difficult task. In this work, the hyphenation of isotachophoretic (ITP) preconcentration to zone electrophoresis (ZE) has been explored for the trace analysis of the cationic impurities Na(+), Li(+), and methylimidazolium (MI(+)) in butylmethylimidazolium (BMI(+))-based ILs. Simultaneous detection of UV-transparent and UV-absorbing impurities was ensured by a BGE composed of creatinine-acetate buffer. To induce ITP, three different strategies were evaluated: (i) Sample self-stacking ensured by the addition of ammonium acetate (NH(4)Ac) to 25-50-fold diluted IL solution (transient ITP). (ii) Complete ITP-ZE separation performed in a single capillary: ITP was realized in discontinuous electrolytes comprising an 80 mM NH(4)Ac, 40 mM acetic acid, 30 mM alpha-CD, pH 5.05, leading electrolyte (LE) and a 10 mM creatinine, 10 mM acetic acid, pH 4.9, terminating electrolyte (TE). To create the ZE stage, the ITP stack of analytes was moved back toward the capillary inlet by pressure and simultaneously the capillary was filled with the BGE. This protocol made it possible to accommodate a 2.5-times diluted IL sample. (iii) Complete counterflow ITP-ZE with continuous electrokinetic sample supply: the ITP stage was performed in a capillary filled with a 150 mM NH(4)Ac, 75 mM acetic acid, 30 mM alpha-CD, pH 5.0 LE, with 40-times diluted IL at the capillary inlet. BMI(+) from IL acts as the terminating ion. The LODs reached in this latter case were at the 10 and 1 ppb levels for MI(+) and Li(+) in diluted IL matrix, respectively.     

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.     

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     

Crystal structure and luminescence properties of the barium europium tetragermanate Ba2Eu2Ge4O13

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