Effect of short glass fiber on structure and viscoelastic behavior of olefinic polymers synthesized with metallocene catalyst

Several composites were prepared on the basis of an ethylene homopolymer and different copolymers of ethylene and 1‐hexene, synthesized with a metallocene catalyst, as matrices and a content of a 5 wt % of short glass fiber. The effect of the fiber incorporation on the structure and mechanical and viscoelastic behaviors was analyzed for the different samples. The glass fibers induced a slightly higher crystallinity, and the crystallite morphology significantly changed (long spacings and crystal orientation). The incorporation of fibers did not reinforce the different matrices under study at this low content; consequently, the mechanical parameters, such as Young's modulus, yielding stress, and microhardness, were lower in the composites as compared with those values found in the neat polyolefins. The location and apparent activation energies of distinct relaxation processes are also discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1244–1255, 2003     

Kinetics of the thermal decomposition of bis(trifluoromethyl) peroxydicarbonate,CF3OC(O)OOC(O)OCF3

Thermal decomposition of bis(trifluoromethyl) peroxydicarbonate has been studied. The mechanism of decomposition is a simple bond fission, homogeneous first‐order process when the reaction is carried out in the presence of inert gases such as N₂ or CO. An activation energy of 28.5 kcal mol^?1 was determined for the temperature range of 50–90°C. Decomposition is accelerated by nitric oxide because of a chemical attack on the peroxide forming substances different from those formed with N₂ or CO. An interpretation on the influence of the substituents in different peroxides on the O? O bond is given. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 15–19, 2003     

Photochemistry of perfluoroacyl halides in the presence of O2 and CO

Photolyses of CF₃C(O)X and C₂F₅C(O)X (X=Cl, F) at 254 nm in the presence of O₂ yield the perfluorinated radicals C₂F₅O (C₂) and CF₃O (C₁), respectively. The C₂ radicals decompose to give CF₃ radicals:

C₂F₅O→CF₃+CF₂O

which, in turn, react with O₂ leading to the formation of C₁ radicals. When in addition to O₂, CO is present, the C₁ radicals react with it leading to its catalytic oxidation to CO₂. The trioxide CF₃OC(O)O₃C(O)OCF₃ was observed following the photolysis of all four halides in the presence of O₂ and CO.

The other radical partners coming from the initial step in the photolysis (XC(O)) as well as the products of their reaction with O₂ (XC(O)O_y, y=1, 2) do not react with CO but when X=F they lead to the formation of a new stable peroxy molecule with the formula CF₃OC(O)O₂C(O)F. Some of the properties of this new molecule, its stability and its IR features are presented in this work.     

Synthesis and kinetic evaluation of 4-deoxy-4-phosphonomethyl-d-erythronate, the first hydrolytically stable and potent competitive inhibitor of ribose-5-phosphate isomerase

4-deoxy-4-Phosphonomethyl-d-erythronate, an isosteric and hydrolytically stable analogue of the known ribose-5-phosphate isomerase inhibitor 4-deoxy-4-phospho-d-erythronate, was obtained by a 14-step synthesis from d-arabinose through an highly improved synthesis of the precursor 5-deoxy-5-phosphonomethyl-d-arabinose. The title compound appears as the first stable and potent competitive inhibitor of the enzyme catalyzed isomerization of ribose-5-phosphate to d-ribulose-5-phosphate (K_i=74 μM, K_m/K_i=100), exhibiting only a 3-fold weaker inhibitory activity than its phosphate analogue.     

Conformational study of N-substituted 8-azabicyclo[3.2.1]octan-3-ones

N-Substituted 8-azabicyclo[3.2.1]octan-3-ones have been studied by ¹H and ¹³C NMR spectroscopy. In CDCl₃ solutions, these ketones display the same preferred conformation. The pyrrolidine and piperidone rings adopt a flattened N-8 envelope and distorted chair conformation, puckered at N-8 and flattened at C-3, respectively, with the N-substituent in axial position with respect to the piperidone ring.     

X-Ray Structure and Proton NMR Study of a Hexacoordinated Lithium Complex

The structure of the lithium complex with1,3,5-tris[oxymethylene(N,N-dicyclohexyl)carboxyamido]cyclohexanehas been determined by the X-ray method.The compound is triclinic, space group P¯1,a = 15.623(3), b = 19.279(4),c = 19.295(4)Å = 102.32(3), = 92.45(3), = 105.67(3)0, V = 5436(2)Å3, Z = 4. Itscomposition is represented by the formulaC48H82N3O6LiI 0.5H2O. The lithium cationis encapsulated in a polar pseudo-cavity of six oxygen atoms of the ligandmolecule and displays a distorted trigonal prism coordination. The conformationof the ligand in the solid state complex has been compared with the conformationof the complex in solution determined by 1H-NMR measurements.Supplementary data relevant to this publication have been deposited with the British Library, No. SUP 82224 (21 pages).     

Synthesis and characterization of trifluoromethyl fluoroformyl peroxycarbonate,CF3OC(O)OOC(O)F

The synthesis of CF(3)OC(O)OOC(O)F is accomplished by the photolysis of a mixture of (CF(3)CO)(2)O, FC(O)C(O)F, CO, and O(2) at -15 degrees C using a low-pressure mercury lamp. The new peroxide is obtained in pure form in low yield after repeated trap-to-trap condensation and is characterized by NMR, IR, Raman, and UV spectroscopy. Geometrical parameters were studied by ab initio methods [B3LYP/6-311+G(d)]. At room temperature, CF(3)OC(O)OOC(O)F is stable for many days in the liquid or gaseous state. The melting point is -87 degrees C, and the boiling point is extrapolated to 45 degrees C from the vapor pressure curve log p = 8.384 - 1715/T (p/mbar, T/K). A possible mechanism for the formation of CF(3)OC(O)OOC(O)F is discussed, and its properties are compared with those of related compounds.     

Effects of citrate on the composition and enzymic coagulation of colloidal bovine casein aggregates

Colloidal casein aggregates (CCA) prepared from soluble whole bovine caseinates in the presence of Ca²⁺ and phosphate (Pi) ions by addition of different citrate (Cit) concentrations showed different mineral and proteic composition. Citrate concentration conditions the Ca and Pi concentrations incorporated into CCA, probably due to the complexing effect of this anion on calcium. A significant change in the incorporated Ca/Pi ratio at 8 mM citrate could very likely be associated to changes in CCA net charge. The incorporation of individual caseins to the colloidal particles obtained, as well as their average size and size distribution, depended also on the Cit concentration used [Cit]_P. α_S- and β-caseins assembled in the CCA structure sharply decreased at a [Cit]_P higher than 15 mM, i.e., at a low Ca²⁺ concentration in the aggregates, showing that the presence of this cation is necessary for the incorporation of these caseins. An inverse relationship between the aggregation step rate in CCA enzymic coagulation and their average size was observed. The aggregation rate vs the average size curve obtained at [Cit]_P 8 mM clearly differed from the curves obtained at 10 and 12 mM, respectively, a fact probably related to a change in the CCA net charge. This behavior showed the effect of citrate concentration on CCA functional properties.     

High‐efficiency polymer solar cells based on phenylenevinylene copolymer with BF2‐azopyrrole complex and CN‐PC70BM with solvent additive

Power conversion efficiency (PCE) of phenylenevinylene‐based copolymer with BF₂ azopyrrole complex (PB)/modified PC₇₀BM, that is, CN‐PC₇₀BM bulk heterojunction solar cells improves from 2.16 to 4.90% using a processing additive and drying condition. The results demonstrate that a processing additive and drying condition provides an effective means to control both the surface roughness and finer interpenetrating networks to enhance the exciton dissociation into free charge carriers, charge transportation, and collection. Taking into the account of simple device fabrication process without thermal annealing, the PCE of the polymer solar cell can further improved by chloronapthalene (CN) additive under the fast drying condition. The average carrier lifetimes extracted from the impedance spectra and found to correlate with measured PCEs. At short circuit conditions and illumination, the average charge carrier lifetime was found vary from 16.8 to 32 μs with power conversion efficiencies ranging from 3.0 to 4.9%. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012