Rod–coil block copolymers: An iterative synthetic approach via living free-radical procedures

A modular approach has been developed for the synthesis of rod–coil block copolymers involving the initial preparation of a macroinitiator based on the rod block followed by the growth of the coil segment with living free-radical procedures. The key feature of this strategy is the utilization of an alkoxyamine group from the beginning of the synthesis, which serves as a solubilizing group and ensures that each rod block contains a single initiating fragment. Using this approach permits block copolymers based on insoluble biphenyl ester oligomers to be conveniently prepared with coil segments that range from styrenes to acrylates to 1,3-dienes. The tendency of the rod segments to crystallize is strongly dependent on the weight fraction of the rod segment and the chemical nature of the coil segment. Rod–coil molecules containing at least 25–35 wt % polystyrene or poly(n-butyl acrylate) coil segments show a two-dimensional hexagonal arrangement of rod aggregates, as characterized by transmission electron microscopy and small-angle X-ray scattering. Polyisoprene block copolymers exhibit a lamellar microstructure with short rigid domains in which the rod units lie in an interdigitated smectic C arrangement. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3640–3656, 2003     

Polarization-Insensitive All-Optical Time-Division Demultiplexer Constructed with a Nonlinear Loop Interferometer

A polarization-insensitive 40-Gb/s time-division demultiplexer was demonstrated in a polarization-diversity loop configuration. The power penalty was measured to be 2.3 dB at a bit error rates of 10-9 for 10 Gb/s output signals.     

Dynamics of energy release in a low-voltage pulsed arc in air

The influence of the discharge conditions on the dynamics of energy release is considered for pulsed arcs in air at initial pressures from 10⁵ to 8×10⁵ Pa and a low-voltage capacitor voltage of up to 400 V. A novel method for determining the resistance of the discharge channel in the final stage of a spark discharge is proposed. The method is applied to estimating the discharge channel parameters.     

Kinetics of a photoinduced NH tautomerism of free-base porphyrins in crystalline matrices at low temperatures: Computer simulations and experiment

Photoinduced NH tautomerism, along with the reaction pathways of phototautomerization in tetrabenzoporphin and porphin free bases in n-octane polycrystalline matrices at 77 K, is studied by simulation of kinetic processes and their experimental observation. The simulation of the processes is performed by the numerical solution of the system of kinetic equations describing the populations of electronic levels and transitions between them. Kinetic dependences are obtained by measuring the perturbation of stationary fluorescence of one component of the 0-0 doublet origin upon pulsed selective photoexcitation of the other component. For two tautomeric forms related by the reversibility of the photochemical reaction, under the assumption of synchronism of the NH rearrangement, (i) analytical solutions governing the reaction rate are found, (ii) a method of measuring the rate constants of the proton rearrangement is suggested and the constants themselves are estimated, and (iii) direct evidence of the participation of T ₁ levels in the photochemical reaction is obtained. With the aid of numerical simulations, the specific features of kinetic manifestation of an asynchronous mechanism of the photoinduced NH rearrangement are studied.     

Formation of metallic NbSe2 nanotubes and nanofibers

We succeed in synthesizing NbSe₂ nanotubes along with nanofibers by chemical vapor transportation. They are stable crystalline systems and can be synthesized reproducibly in a nearly equilibrium reacting process. We have investigated these nanosize structures of NbSe₂ by transmission electron microscopy and electron diffraction. Both of the structures have a similar size of 100–200 nm in diameter. While nanotubes consist of rolled-up NbSe₂ layers, nanofibers are a pile of thin flat layers. We propose a mechanism of the formation of NbSe₂ nanotubes and nanofibers on the basis of deseleniditive transition from a NbSe₃ fiber-shaped crystal. We also measured electrical resistance of the nanofibers with conductive atomic force microscopy and demonstrated that the material show metallic behavior at room temperature.     

Thickness decrease of a grafted polyelectrolyte membrane exposed to shear flow

The effect of the shear flow on the thickness change of a polyelectrolyte membrane grafted onto a glass substrate was directly investigated with a flow cell combined with a confocal laser scanning microscope. The membrane thickness decreased proportionally to an increase in the shear stress of the flow when the shear rate exceeded a critical value of 1 s^?1. The higher the ionic strength was of the fluid, the greater the thinning effect was. The correlation between the critical shear rate and the relaxation of the polymer in the gel membrane was examined. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2808–2815, 2003