Polymerization of N-(2,3,4,5,6-pentafluorophenyl)-maleimide

A novel fluorine-containing polymer, poly[N-(2,3,4,5,6-pentafluorophenyl)maleimide], was prepared by the anionic polymerization of N-(2,3,4,5,6-pentafluorophenyl)maleimide (PFPMI). Anionic polymerization with alkali metal tert-butoxides gave poly(PFPMI) in 14–32% yield. Phenyllithium and sec-butyllithium also afforded poly(PFPMI). No polymer was obtained with a radical initiator such as 2,2′-azoisobutyronitrile. The polymerization took place only via the vinylene group of PFPMI and no appreciable side-reaction occurred. The obtained poly(PFPMI) shows unimodal molecular weight distribution and begins to decompose at 325°C.     

Imposex in Sea Snails,Caused by Organotin (Tributyltin and Triphenyltin) Pollution in Japan: a Survey

A country-wide survey and laboratory experiments on imposex (a superimposition of male sex organs on female sea snails) in Japanese sea snails were carried out: 38 species were observed to be affected by imposex. For the rock shell, Thais clavigera , the percentage occurrence of imposex was 100% at almost all sites surveyed. The degree of imposex seemed to be positively correlated with the concentrations of tributyltin (TBT) and triphenyltin (TPT) in the species. The results of laboratory experiments showed that imposex in T. clavigera was initiated and promoted by both TBT and TPT. Many oviduct-blocked individuals, which were thought to be sterile, were observed in T. clavigera at sites near marinas and harbours. The effects of organotin pollution on the population of T. clavigera were observed at the sites near marinas. From the results of the additional country-wide survey on imposex in T. clavigera during 1993–1995, serious organotin pollution and imposex symptoms in the species are still continuing in Japan. © 1997 by John Wiley & Sons, Ltd.     

Stability of the linear chain structure for ~(12)C in covariant density functional theory on a 3D lattice

The stability of the linear chain structure of three α clusters for ~(12)C against the bending and fission is investigated in the cranking covariant density functional theory, in which the equation of motion is solved on a 3D lattice with the inverse Hamiltonian and the Fourier spectral methods. Starting from a twisted three α initial configuration, it is found that the linear chain structure is stable when the rotational frequency is within the range of ～2.0-～2.5 MeV. Beyond this range, the final states are not stable against fission. By examining the density distributions and the occupation of single-particle levels, however, these fissions are found to arise from the occupation of unphysical continuum with large angular momenta. To properly remove these unphysical continuum, a damping function for the cranking term is introduced. Eventually, the stable linear chain structure could survive up to the rotational frequency ～3.5 MeV, but the fission still occurs when the rotational frequency approaches ～4.0 MeV.     

Ab initio GB study of chemical intermediates in solution; Ethylenesulfonium ion in hydrolysis of 2-chloroethyl methyl sulfide

Ab initio MO theory including solvent effects has been applied to the structure and reactivity of methyl ethylenesulfonium ion, 1 , in aqueous solution as a model of the three-membered cyclic sulfonium intermediate expected in the toxic action of sulfur mustard. The 6-31 + G* geometry optimization of the cyclic sulfonium ion 1 suggested that the ring size of 1 is expanded slightly by solvation. The contour lines map of the interaction energy between 1 and Cl⁻ has a very shallow and wide well at 5–6 Å distance from 1 . This is the solvent-separated ion pair, and the contact ion pair was not found between 1 and Cl⁻. The calculated energy diagrams for the S_N2-type reactions of 1 with Cl⁻, H₂O, and OH⁻ that give ring-opened compounds indicated the following: (1) The energy of the 1 + Cl⁻ system is similar to that of chloroethyl methyl sulfide (CEMS, 2 ), and the interconversion between 1 + Cl⁻ and 2 occurs easily in aqueous solution. The 3-21 + G(*) and 6-31 + G* activation energies for the 2 → 1 + Cl⁻ reaction, 20–22 kcal/mol, agree well with the experimental enthalpy of activation for the hydrolysis of 2 . (2) The reaction of 1 with OH⁻ gives a very stable hydroxyl compound, 4 , and no transition state was found. (3) The reaction of 1 with H₂O gives an unstable addition product that is expected to be converted to 4 with the assistance of another H₂O molecule. This mechanism is consistent with that proposed by Bartlett and Swain in their pioneering work on the hydrolysis of sulfur mustard. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:503–510, 1998     

Effect of the substituents on radical copolymerization of dialkyl fumarates with some vinyl monomers

Radical copolymerization of dialkyl fumarates (DRF) with various vinyl monomers was carried out in benzene at 60°C. The monomer reactivity ratios, r₁ and r₂, were determined from the comonomer-copolymer composition curves. The relative reactivity of DRFs with various ester substituents toward a polystyryl radical was revealed to depend on both steric and polar effects of the ester groups. It has also been clarified that α-substituents of the polymer radical have a significant role in addition of DRF, from the comparison of the monomer reactivity ratios determined in copolymerizations with monosubstituted and 1,1-disubstituted ethylenes. The absolute cross-propagation rate constants were also evaluated and discussed. © 1992 John Wiley & Sons, Inc.     

Design and experimental verification of multiple delay feedback control for time-delay nonlinear oscillators

This study aims to show that a multiple delay feedback control method can stabilize unstable fixed points of time-delay nonlinear oscillators. The boundary curves of stability in a control parameter space are derived using linear stability analysis. A simple procedure for designing a feedback gain is provided. The main advantage of this procedure is that the designed controller can stabilize a system even if the controller delay times are long. These analytical results are experimentally verified using electronic circuits.