He-N2 radiofrequency discharge: Influence of N2 on discharge and afterglow

A diagnostic study q (energy transfer processes in a He-N₂ flowing discharge and afterglow has been performed in a radiofrequency-produced plasma cooled in a liquid nitrogen hath. Optical emission spectroscopy in the visible and infrared spectral range as well as Langrnuir probe diagnostics were used. The vibrational kinetics of CO injected in such an afterglow has been examined. It shows a slow cooling of the electrons in the afterglow regime. The electron kinetics responsible joy CO vibrahonal excitation is turned off when N₂ is added to the He discharge, while that for vibrationally excited N₂ molecules is turned on. The results are discussed on the basis of previous theorerical calculations and experiments on the He-N₂ system.     

Energy transfer between the flavin chromophores of electron-transferring flavoprotein fromMegasphaera elsdenii as inferred from time-resolved red-edge and blue-edge fluorescence spectroscopy

Both a mode-locked argon-ion laser and synchrotron radiation were used as excitation sources to obtain time-resolved polarized fluorescence of the two FAD cofactors in electron transferring flavoprotein fromMegasphaera elsdenii. Red-edge excited and blue-edge detected fluorescence anisotropy decay curves did not contain a fast relaxation process which was observed upon mainband excitation and detection. This relaxation was assigned to homo-energy transfer between the two FAD cofactors. Failure of energy transfer as observed with edge spectroscopy on this protein excludes restricted reorientational motion of the flavins as a possible mechanism of depolarization. From the global analysis of the fluorescence anisotropy decay surface obtained at multiple excitation and detection wavelengths, the distance between and the relative orientation of the flavins could be estimated. The methodology described has general applicability in other multichromophoric biopolymers and has the potential to acquire accurate geometrical parameters in these systems.     

N2（A）及N（2D）对IF（X）的传能研究

在微波放电系统中,对NH_3-F-F_2-CF_3I体系进行研究,结果表明,向IF(X)传能的诸多媒介中,N_2(A)及N(~2D)起着主要作用,并且这一结论在经微波激发后的N_2与CF_3I的直接反应中得到了进一步证实。     

Kinetic features of ethylene polymerization over supported catalysts [2,6‐bis(imino)pyridyl iron dichloride/magnesium dichloride] with AlR3 as an activator

The effects of polymerization temperature, polymerization time, ethylene and hydrogen concentration, and effect of comonomers (hexene‐1, propylene) on the activity of supported catalyst of composition LFeCl₂/MgCl₂‐Al(i‐Bu)₃ (L = 2,6‐bis[1‐(2,6‐dimethylphenylimino)ethyl] pyridyl) and polymer characteristics (molecular weight (MW), molecular‐weight distribution (MWD), molecular structure) have been studied. Effective activation energy of ethylene polymerization over LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a value typical of supported Ziegler–Natta catalysts (11.9 kcal/mol). The polymerization reaction is of the first order with respect to monomer at the ethylene concentration >0.2 mol/L. Addition of small amounts of hydrogen (9–17%) significantly increases the activity; however, further increase in hydrogen concentration decreases the activity. The IRS and DSC analysis of PE indicates that catalyst LFeCl₂/MgCl₂‐Al(i‐Bu)₃ has a very low copolymerizing ability toward propylene and hexene‐1. MW and MWD of PE produced over these catalysts depend on the polymerization time, ethylene and hexene‐1 concentration. The activation effect of hydrogen and other kinetic features of ethylene polymerization over supported catalysts based on the Fe (II) complexes are discussed. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5057–5066, 2007     

Synthesis,characterization, and micellization of an epoxy‐based amphiphilic diblock copolymer of ϵ‐caprolactone and glycidyl methacrylate by enzymatic ring‐opening polymerization and atom transfer radical polymerization

Amphiphilic diblock copolymer polycaprolactone‐block‐poly(glycidyl methacrylate) (PCL‐b‐PGMA) was synthesized via enzymatic ring‐opening polymerization (eROP) and atom transfer radical polymerization (ATRP). Methanol first initiated eROP of ?‐caprolactone (?‐CL) in the presence of biocatalyst Novozyme‐435 under anhydrous conditions. The resulting monohydroxyl‐terminated polycaprolactone (PCL–OH) was subsequently converted to a bromine‐ended macroinitiator (PCL–Br) for ATRP by esterification with α‐bromopropionyl bromide. PCL‐b‐PGMA diblock copolymers were synthesized in a subsequent ATRP of glycidyl methacrylate (GMA). A kinetic analysis of ATRP indicated a living/controlled radical process. The macromolecular structures were characterized for PCL–OH, PCL–Br, and the block copolymers by means of nuclear magnetic resonance, gel permeation chromatography, and infrared spectroscopy. Differential scanning calorimetry and wide‐angle X‐ray diffraction analyses indicated that the copolymer composition (?‐CL/GMA) had a great influence on the thermal properties. The well‐defined, amphiphilic diblock copolymer PCL‐b‐PGMA self‐assembled into nanoscale micelles in aqueous solutions, as investigated by dynamic light scattering and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5037–5049, 2007     

2‐Cyanoprop‐2‐yl dithiobenzoate mediated reversible addition–fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition–fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2‐cyanoprop‐2‐yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANs were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. ¹H NMR analysis confirmed the high chain‐end functionality of the resultant polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1272–1281, 2007     

Studies on O-,N-Acylation of 3-Hydroxyisoxazole and Their Regioselective Synthesis(Ⅰ)——O-,N-acylation of 5-Methyl-3-hydroxyisoxazole with 2,2-Dimethyl 3-Substituted Cyclopropanecarboxylic Chlorides

The reactions of 5-methyl-3-hydroxyisoxazole with 2, 2-dimethyl, 3-substituted cyclopropanecarboxylic chlorides give O-acyl-5-methyl-3-hydroxyisoxazole and N-acyl-5-methylisoxazolin-3-one derivatives. The ratio of O-acyl to N-acyl product depends upon the acylation reagents. O-acyl derivatives can be converted to the N-acyl compounds by isomerization under acidic conditions or heating.