Synthesis and characterization of poly(arylene ether)s containing 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one or 6‐(4‐hydroxyphenyl)pyridazine moieties

A series of novel soluble pyridazinone‐ or pyridazine‐containing poly(arylene ether)s were prepared by a polycondensation reaction. The pyridazinone monomer, 6‐(4‐hydroxyphenyl)pyridazin‐3(2H)‐one ( 1 ), was synthesized from the corresponding acetophenone and glyoxylic acid in a simple one‐pot reaction. The pyridazinone monomer was successfully copolymerized with bisphenol A (BPA) or 1,2‐dihydro‐4‐(4‐hydroxyphenyl)phthalazin‐1(2H)‐one (DHPZ) and bis(4‐fluorophenyl)sulfone to form high‐molecular‐weight polymers. The copolymers had inherent viscosities of 0.5–0.9 dL/g. The glass‐transition temperatures (T_g's) of the copolymers synthesized with BPA increased with increasing content of the pyridazinone monomer. The T_g's of the copolymers synthesized from DHPZ with different pyridazinone contents were similar to those of the two homopolymers. The homopolymers showed T_g's from 202 to 291 °C by differential scanning calorimetry. The 5% weight loss temperatures in nitrogen measured by thermogravimetric analysis were in the range of 411–500 °C. 4‐(6‐Chloropyridazin‐3‐yl)phenol ( 2 ) was synthesized from 1 via a simple one‐pot reaction. 2 was copolymerized with 4,4′‐isopropylidenediphenol and bis(4‐fluorophenyl)sulfone to form high‐T_g polymers. The copolymers with less than 80 mol % pyridazinone or chloropyridazine monomers were soluble in chlorinated solvents such as chloroform. The copolymers with higher pyridazinone contents and homopolymers were not soluble in chlorinated solvents but were still soluble in dipolar aprotic solvents such as N‐methylpyrrolidinone. The soluble polymers could be cast into flexible films from solution. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3328–3335, 2006     

Meshless simulation of equilibrium swelling/deswelling of pH‐sensitive hydrogels

Hydrogels have been widely used in microelectromechanical systems (MEMS) and Bio‐MEMS devices. In this article, the equilibrium swelling/deswelling of the pH‐stimulus cylindrical hydrogel in the microchannel is studied and simulated by the meshless method. The multi‐field coupling model, called multi‐effect‐coupling pH‐stimulus (MECpH) model, is presented and used to describe the chemical field, electric field, and the mechanical field involved in the problem. The partial differential equations (PDEs) describing these three fields are either nonlinear or coupled together. This multi‐field coupling and high nonlinear characteristics produce difficulties for the conventional numerical methods (e.g., the finite element method or the finite difference method), so an alternative—meshless method is developed to discretize the PDEs, and the efficient iteration technique is adopted to solve the nonlinear problem. The computational results for the swelling/deswelling diameter of the hydrogel under the different pH values are firstly compared with experimental results, and they have a good agreement. The influences of other parameters on the mechanical properties of the hydrogel are also investigated in detail. It is shown that the multi‐field coupling model and the developed meshless method are efficient, stable, and accurate for simulation of the properties of the stimuli‐sensitive hydrogel. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 326–337, 2006     

Crystallization of Arthrobacter sp. strain 1C N-(1-D-carboxyethyl)-L-norvaline dehydrogenase and its complex with NAD+

The novel NAD+-linked opine dehydrogenase from a soil isolate Arthrobacter sp. strain 1C belongs to an enzyme superfamily whose members exhibit quite diverse substrate specificites. Crystals of this opine dehydrogenase, obtained in the presence or absence of co-factor and substrates, have been shown to diffract to beyond 1.8 ? resolution. X-ray precession photographs have established that the crystals belong to space group P21212, with cell parameters a = 104.9, b = 80.0, c = 45.5 ? and a single subunit in the asymmetric unit. The elucidation of the three-dimensional structure of this enzyme will provide a structural framework for this novel class of dehydrogenases to enable a comparison to be made with other enzyme families and also as the basis for mutagenesis experiments directed towards the production of natural and synthetic opine-type compounds containing two chiral centres.     

Conversion estimates for gas-solid reactions: Improved estimates for irreversible systems

Solid conversion has been of much interest to research workers and the Cumulative Gas Concentration Method (CGCM) has been developed to provide bounds for the reactant solid in irreversible systems having power-law type kinetics. This CGCM is used in conjunction with the Pseudo-Steady-State (PSS) assumption and these bounds appear to be good under certain conditions and for long times.

In this work, the PSS condition is not assumed when deriving the bounds on the cumulative gas concentration and the effect of the inclusion of the transient part is analysed. A technique, based on an iterative scheme incorporating the CGCM, is developed to provide improved estimates for the reactant solid.     

Dynamics of phase separation in mesomorphic mixtures

We describe the dynamics of phase separation and transition processes, in binary mesomorphic mixtures with the help of a system of two coupled partial derivative equations. We emphasize, both analytically and numerically, that, depending on the regions of the phase diagram, the dynamical behaviour may result either from a two step process (first the phase transition, then the phase separation) or from a process showing salient features of the Cahn-Hilliard spinodal decomposition (bicontinuous periodic networks in the transient stages). The dynamics of evolution of the domain patterns are illustrated with the help of numerical simulations in which homeotropic and planar anchorages are visualized.     

Variation of U-microdistribution in fossil Hipparion teeth as a complicating factor in dating studies

Five Upper Miocene fossil Hipparion molars were studied for U-distribution by Fission Track. U uptake has reached the whole mass of the teeth and no saturation fronts seem to occur in the interior layers. Mean U-concentration in dentine, cement and enamel was 157, 139 and 78 ppm, respectively. U_enamel/U_dentine 0.5 is considerably higher than 0.1 reported in the past for Upper-Quaternary mammoth teeth. These features are disadvantageous for ESR-dating in Hipparion enamel, although a long-lived signal (g=2.0018) is apparent. Leaching phenomena occur in the outer regions of these teeth. Inner enamel folding seems to have hindered a more uniform U-distribution in the teeth.     

THE QUANTUM EFFICIENCY FOR THE INTERPHOTOCONVERSION OF THE BLUE and PINK FORMS OF PURPLE MEMBRANE

When the cations bound to purple membrane are removed it turns blue, and when this blue membrane is irradiated its color changes to pink. Irradiation of pink membrane leads to the reformation of blue membrane. We have determined that the quantum efficiency for the formation of pink membrane from deionized blue membrane is 1.6 ± 0.6 ± 10 ⁴ at 0^oC, pH 5.0. We also found that the quantum efficiency for the back photoconversion, i.e. the formation of blue membrane from pink membrane, is 8.8 ± 1.6 ± 10^-3 at 0^oC, 55 times greater than that of the forward photoconversion reaction. The extinction coefficients of the pink membrane and blue membrane were determined to be 44 500 ± 670 cm^-1 M^-1 at 491 nm and 54 760 ± 830 cm^-1 M ^-1 at 603 nm, respectively, assuming light-adapted purple membrane is 63 000 cm^-1 M ^-1 at 568 nm. The quantum efficiency for forming pink membrane from blue membrane is much lower than that for forming the photointermediate of the blue membrane's photocycle. Their relationship is similar to that of light-adaptation and photocycle of the dark-adapted purple membrane.