Intramolecular motion and isotope effects in muonium‐substituted chloroalkyl radicals

Muon irradiation of pure liquid 3‐chloropropene, CH₂=CH-CH₂Cl, yields a primary radical, \dot\mboxCH₂-CHMu-CH₂Cl, and a secondary radical, MuCH₂-\rm\dot\mboxCH-CH₂Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH₂-\rm\dot\mboxC(CH₃)-CH₂Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH₃,-CH₂Cl and -CH₂Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H. This revised version was published online in August 2006 with corrections to the Cover Date.     

The layered compound poly[μ2‐4,4′‐bipyridyl‐di‐μ2‐chlorido‐mercury(II)]

The title compound, [HgCl₂(C₁₀H₈N₂)]_n, features two‐dimensional [HgCl₂(4,4′‐bipy)]_n neutral networks (4,4′‐bipy is 4,4′‐bipyridine), based on an octahedral Hg atom coordinated by four μ₂‐Cl atoms and two μ₂‐4,4′‐bipy ligands in trans positions, yielding a HgCl₄N₂ octahedron. The structure has mmm symmetry about the Hg atoms, with most of the atoms on at least one mirror plane, but the unsubstituted C atoms of the 4,4′‐bipy rings are disordered across a mirror plane. Photoluminescent investigations reveal that the title compound displays a strong emission in the green region, which probably originates from a ligand‐to‐ligand charge‐transfer transition.     

Measurement of small-signal and large-signal responses of packaged laser modules at high temperature

In this paper, the pulsed injection method is extended to measure the chip temperature of various packaged laser modules, such as the DFB laser modules, the FP laser modules, and the EML laser modules. An optimal injection condition is obtained by investigating the dependence of the lasing wavelength on the width and period of the injection pulse in a relatively wide temperature range. The small-signal frequency responses and large-signal performances of packaged laser modules at different chip temperature are measured. The adiabatic small-signal modulation characteristics of packaged LD are first extracted. In the large-signal measurement, the effects of chip temperature, bias current and driving signal on the performances of the laser modules are discussed. It has been found that the large-signal performances of the EML modules depend on the different red-shift speeds of the DFB and EAM sections as chip temperature varying, and the optimal characteristics may be achieved at higher temperature.     

Strict Stability of Impulsive Differential Equations

In this paper, we will extend the strict stability to impulsive differential equations. By using Lyapunov functions, we will get some criteria for the strict stability of impulsive differential equations, and we can see that impulses do contribute to the system＇s strict stability behavior. An example is also given in this paper to illustrate the efficiency of the obtained results.     

A copper‐based reverse atom‐transfer radical polymerization process for the living radical polymerization of polyacrylonitrile

The reverse atom‐transfer radical polymerization (RATRP) technique using CuCl₂/2,2′‐bipyridine (bipy) complex as a catalyst was applied to the living radical polymerization of acrylonitrile (AN). A hexasubstituted ethane thermal iniferter, diethyl 2,3‐dicyano‐2,3‐diphenylsuccinate (DCDPS), was firstly used as the initiator in this copper‐based RATRP initiation system. A CuCl₂ to bipy ratio of 0.5 not only gives the best control of molecular weight and its distribution, but also provides rather rapid reaction rate. The rate of polymerization increases with increasing the polymerization temperature, and the apparent activation energy was calculated to be 57.4 kJ mol^?1. Because the polymers obtained were end‐functionalized by chlorine atoms, they were used as macroinitiators to proceed the chain extension polymerization in the presence of CuCl/bipy catalyst system via a conventional ATRP process. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 226–231, 2006     

Synthesis of polyacrylonitrile via reverse atom transfer radical polymerization catalyzed by FeCl3/isophthalic acid

FeCl₃ coordinated by isophthalic acid was first used as a catalyst in the azobisisobutyronitrile‐initiated reverse atom transfer radical polymerization of acrylonitrile. N,N‐Dimethylformamide was used as a solvent to improve the solubility of the ligand. An FeCl₃‐to‐isophthalic acid ratio of 0.5 not only gave the best control of the molecular weight and its distribution but also provided rather a rapid reaction rate. The effects of different solvents on the polymerization of acrylonitrile were also investigated. The rate of the polymerization in N,N‐dimethylformamide was faster than that in propylene carbonate and toluene. The molecular weight of polyacrylonitrile agreed reasonably well with the theoretical molecular weight in N,N‐dimethylformamide. The rate of polymerization increased with increasing polymerization temperature, and the apparent activation energy was calculated to be 59.9 kJ mol^?1. Reverse atom transfer radical polymerization was first used to successfully synthesize acrylonitrile polymers with a molecular weight higher than 80,000 and a narrow polydispersity as low as 1.22. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 219–225, 2006