Soluble polybenzimidazoles with intrinsic porosity: Synthesis,structure, properties and processability

We have explored two novel comonomers, namely, 4,16‐dicarboxyl[2.2]paracyclophane and 5,5′,6,6′‐tetraamino‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobi[indane], for the synthesis of co‐polybenzimidazoles (co‐PBIs) with intrinsic porosity. Both these monomers possess twisted structures that can lead to “awkward” macromolecular shapes that cannot pack efficiently. The consequences of introducing these two monomers on the structure and properties of PBIs are reported. The random copolymers synthesized are amorphous and possess glass transition temperatures (T_gs) greater than 400 °C. T_g decreases with increasing comonomer content indicating an increase in fractional free volume. The copolymers have low surface area. TEM and BET measurements show evidence of mesopore formation. The copolymers show significant carbon dioxide adsorption. Single chain molecular dynamics simulation of 24‐mer repeat units shows intramolecular void spaces arising as a result of distorted polymer chain with reduced conformational mobility. These studies define a new synthetic strategy for “bottoms‐up” synthesis of PBIs with intrinsic porosity. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1046–1057     

Tuning the frontier molecular orbital energy levels of n‐type conjugated copolymers by using angular‐shaped naphthalene tetracarboxylic diimides,and their use in all‐polymer solar cells with high open‐circuit voltages

An angular‐shaped naphthalene tetracarboxylic diimide (NDI) was designed and synthesized as a new building block for n‐type conjugated polymers to tune their energy levels. Three n‐type copolymers incorporating this angular‐shaped NDI as the acceptor moiety were obtained by Stille coupling reactions and had number average molecular weights of 18.7–73.0 kDa. All‐polymer bulk‐heterojunction solar cells made from blends of these polymers with poly(3‐hexylthiophene) gave a power conversion efficiency up to 0.32% and exhibited an open‐circuit voltage (V_oc) up to 0.94 V due to their relative high‐lying lowest unoccupied molecular orbital energy levels. The high V_oc of 0.94 V is higher than that of solar cells based on linear‐shaped NDI‐containing polymers (<0.6 V). The results indicate that the angular‐shaped NDI is a promising building block for constructing nonfullerene polymer acceptors for solar cells with high open‐circuit voltages. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Characteristics and structure of turbulent 3D offset jets

Three-dimensional turbulent offset jets were investigated using a particle image velocimetry technique. The measurements were performed at three different exit Reynolds numbers and for four offset heights. The results in the early region of flow development clearly show significant effects of Reynolds number and offset height on the decay of maximum mean velocity and growth of the shear layer. On the contrary, the decay and spread rates were found to be nearly independent of offset height at larger downstream distances. The decay rates of 1.18 ± 0.03 as well as the spread rates of 0.055 ± 0.001 and 0.250 ± 0.005 obtained, respectively, in the wall-normal and lateral directions fall in the range of values reported in previous studies. The locations of the maximum mean velocities increased nearly linearly with streamwise distance in the self-similar region. Analysis from two-point velocity correlations revealed substantially larger structures in the outer layer and self-similar region than in the inner layer and developing region. It was also observed that the hairpin vortices in the inner regions of the wall jets are inclined at angles of 11.2° ± 0.6°, which are in good agreement with reported values in boundary layer studies.     

Explicit characteristic‐based finite volume element method for level set equation

Accurate modeling of interfacial flows requires a realistic representation of interface topology. To reduce the computational effort from the complexity of the interface topological changes, the level set method is widely used for solving two‐phase flow problems. This paper presents an explicit characteristic‐based finite volume element method for solving the two‐dimensional level set equation. The method is applicable for the case of non‐divergence‐free velocity field. Accuracy and performance of the proposed method are evaluated via test cases with prescribed velocity fields on structured grids. By given a velocity field, the motion of interface in the normal direction and the mean curvature, examples are presented to demonstrate the performance of the proposed method for calculating interface evolutions in time. Copyright © 2010 John Wiley & Sons, Ltd.     

High‐order finite difference schemes for incompressible flows

This paper presents a new high‐order approach to the numerical solution of the incompressible Stokes and Navier–Stokes equations. The class of schemes developed is based upon a velocity–pressure–pressure gradient formulation, which allows: (i) high‐order finite difference stencils to be applied on non‐staggered grids; (ii) high‐order pressure gradient approximations to be made using standard Padé schemes, and (iii) a variety of boundary conditions to be incorporated in a natural manner. Results are presented in detail for a selection of two‐dimensional steady‐state test problems, using the fourth‐order scheme to demonstrate the accuracy and the robustness of the proposed methods. Furthermore, extensions to higher orders and time‐dependent problems are illustrated, whereas the extension to three‐dimensional problems is also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Rapid and Simple Method to Determine Tamoxifen and Its Major Metabolites in Human Liver Microsomes by High Performance Liquid Chromatography with Fluorescence Detection

Abstract

Sensitive and reproducible analyses were developed for assaying tamoxifen, desmethyltamoxifen, didesmethyltamoxifen and hydroxytamoxifen in human liver microsomes by high performance liquid chromatography (H.P.L.C.) following protein precipitation. Detection was by fluorimetry of phenanthrene derivatives formed by on-stream U.V. irradiation with a photochemical reactor enhanced detection (P.H.R.E.D.) for post-column irradiation of the H.P.L.C. stream. The method is highly sensitive (1 ng/ml). A C8,5 μm column (4.6 x 150 mm) was used, with a mobile phase of acetonitrile / 100 mM ammonium acetate (1:1) pH 5. Precipitation of the microsomal protein was carried out by adding methanol and concentrated chloric acid to the reaction mixture, and extraction efficiencies were approximately 100 % for tamoxifen and its metabolites. The assay has been optimised for the identification and quantitation of the 4-hydroxylated metabolite, as well as the two metabolites formed by N-oxidative demethylation of the side chain. The latter catalytic activity involves cytochrome P450 3A enzymes.     

Discontinuous Galerkin methods for the Navier–Stokes equations using solenoidal approximations

An interior penalty method and a compact discontinuous Galerkin method are proposed and compared for the solution of the steady incompressible Navier–Stokes equations. Both compact formulations can be easily applied using high‐order piecewise divergence‐free approximations, leading to two uncoupled problems: one associated with velocity and hybrid pressure, and the other one only concerned with the computation of pressures in the elements interior. Numerical examples compare the efficiency and the accuracy of both proposed methods. Copyright © 2009 John Wiley & Sons, Ltd.     

UV‐curable bismaleimides containing poly(dimethylsiloxane): Use as hydrophobic agent

The synthesis and characterization of poly(dimethylsiloxanes) bearing maleimides end‐groups (PDMSM) were carried out through imidization of maleic anhydride with three poly(dimethylsiloxanes) diamines of different molecular weights. Self‐photopolymerization of PDMSM was studied by Real‐Time Fourier Transform infrared spectroscopy (RT‐FTIR) and was possible even without photoinitiator (Darocur 1173). The reaction was found to proceed within seconds upon exposure to ultraviolet (UV) radiation to generate highly crosslinked polymer networks. The results indicated that these polymerizations were less sensitive to oxygen inhibition than the radical processes carried out on conventional UV‐curable acrylate resins. The thermal and mechanical properties of these resulting materials were studied starting from PDMS precursors with different molecular weights. These materials exhibit a low glass transition temperature (相似文献