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     

Synthesis and optoelectronic properties of silole‐containing polyfluorenes with binary structures

2,5‐Bis(2‐bromofluorene‐7‐yl)silole was prepared by a modified one‐pot synthesis with a reverse addition procedure, from which novel silole‐containing polyfluorenes with binary random and alternating structures (silole contents between 4.5 and 25% and high M_w up to 509 kDa were successfully synthesized. The well‐defined repeating unit of the alternating copolymer comprises a terfluorene and a silole ring. Optoelectronic properties including UV absorption, electrochemistry, photoluminescence (PL), and electroluminescence (EL) of the copolymers were examined. The different excitation energy transfers from fluorene to silole of the copolymers in solution and in the solid state were compared. The films of the copolymers showed silole‐dominant green emissions with high absolute PL quantum yields up to 83%. EL devices of the copolymers with a configuration of ITO/PEDOT/copolymer/Ba/Al displayed exclusive silole emissions peaked at around 543 nm and the highest EL efficiency was achieved with the alternating copolymer. Using the alternating copolymer and poly(9,9‐dioctylfluorene) as the blend‐type emissive layer, a maximum external quantum efficiency of 1.99% (four times to that of the neat film) was realized, which was a high efficiency so far reported for silole‐containing polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 756–767, 2007     

Superconvergence of discontinuous Galerkin finite element method for the stationary Navier‐Stokes equations

This article focuses on discontinuous Galerkin method for the two‐ or three‐dimensional stationary incompressible Navier‐Stokes equations. The velocity field is approximated by discontinuous locally solenoidal finite element, and the pressure is approximated by the standard conforming finite element. Then, superconvergence of nonconforming finite element approximations is applied by using least‐squares surface fitting for the stationary Navier‐Stokes equations. The method ameliorates the two noticeable disadvantages about the given finite element pair. Finally, the superconvergence result is provided under some regular assumptions. © 2006 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 23: 421–436, 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     

Implementation of some higher-order convection schemes on non-uniform grids

A generalized formulation is applied to implement the quadratic upstream interpolation (QUICK) scheme, the second-order upwind (SOU) scheme and the second-order hybrid scheme (SHYBRID) on non-uniform grids. The implementation method is simple. The accuracy and efficiency of these higher-order schemes on non-uniform grids are assessed. Three well-known bench mark convection-diffusion problems and a fluid flow problem are revisited using non-uniform grids. These are: (1) transport of a scalar tracer by a uniform velocity field; (2) heat transport in a recirculating flow; (3) two-dimensional non-linear Burgers equations; and (4) a two-dimensional incompressible Navier-Stokes flow which is similar to the classical lid-driven cavity flow. The known exact solutions of the last three problems make it possible to thoroughly evaluate accuracies of various uniform and non-uniform grids. Higher accuracy is obtained for fewer grid points on non-uniform grids. The order of accuracy of the examined schemes is maintained for some tested problems if the distribution of non-uniform grid points is properly chosen.     

Viscometric properties of dilute polystyrene/dioctyl phthalate solutions

We report viscometric data collected in a Couette rheometry on dilute, single‐solvent polystyrene (PS)/dioctyl phthalate (DOP) solutions over a variety of polymer molecular weights (5.5 × 10⁵ ≤ M_w ≤ 3.0 × 10⁶ Da) and system temperatures (288 K ≤ T ≤ 318 K). In view of the essential viscometric features, the current data may be classified into three categories: The first concerns all the investigated solutions at low shear rates, where the solution properties are found to agree excellently with the Zimm model predictions. The second includes all sample solutions, except for high‐molecular‐weight PS samples (M_w ≥ 2.0 × 10⁶ Da), where excellent time–temperature superposition is observed for the steady‐state polymer viscosity at constant polymer molecular weights. No similar superposition applies at a constant temperature but varied polymer molecular weights, however. The third appears to be characteristic of dilute high‐molecular‐weight polymer solutions, for which the effects of temperature on the viscosity curve are further complicated at high shear rates. The implications concerning the relative importance of hydrodynamic interactions, segmental interactions, and chain extensibility with increasing polymer molecular weight, system temperature, and shear rate are discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 787–794, 2006     

Anchoring Properties of Nematic Liquid Crystals Studied Using the Attenuated Total Reflection Method

By using the attenuated total reflection method associated with the excitation of surface plasmons, the tilt angle of the liquid crystal director and its gradient at the surface are measured in a planar nematic cell as a function of the applied voltage. The surface anchoring anisotropy δπ of the liquid crystal and the surface elastic constant k_s, are found to be δπ = 0.288 erg/cm and k_s, = 9·12 × 10^-11 erg, respectively, when the boundary condition suggested by Barbero et al is used. The theoretical and experimental values obtained with this boundary condition and that of Mada are discussed. The results show that the boundary condition proposed by Barbero et al is in better agreement with the experiment.     

Bioaccumulation and excretion of arsenic compounds by a marine unicellular alga,polyphysa peniculus

Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment.     

A note on an SOR-like method for augmented systems

Golub et al. (2001, BIT, 41, 71–85) gave a generalizedsuccessive over-relaxation method for the augmented systems.In this paper, the connection between the SOR-like method andthe preconditioned conjugate gradient (PCG) method for the augmentedsystems is investigated. It is shown that the PCG method isat least as accurate (fast) as the SOR-like method. Numericalexamples demonstrate that the PCG method is much faster thanthe SOR-like method.