Synthesis and Properties of Carbazole Main Chain Copolymers with Oxadiazole Pendant toward Bipolar Polymer Host: Tuning the HOMO/LUMO Level and Triplet Energy

Three new carbazole copolymers, poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-3,6-diyl)s (P1), poly(9-(2,5-diarene-[1,3,4]oxadiazole)-2, 7-carbazole-alt-9-(2-ethylhexyl)-3, 6-carbazole-diyl)s (P2), and poly(9-(2,5-diarene-[1,3,4]oxadiazole)-carbazole-alt-9-(2-ethylhexyl)-carbazole-2,7-diyl)s (P3), were synthesized by the Suzuki coupling reaction

Biodegradable Interpolyelectrolyte Complexes Based on Methoxy Poly(ethylene glycol)-b-poly(alpha,L-glutamic acid) and Chitosan

We synthesized methoxy poly(ethylene glycol)-b-poly(alpha,L-glutamic acid) (mPEGGA) diblock copolymer by ring-opening polymerization of N-carboxy anhydride of gamma-benzyl-L-glutamate (NCA) using amino-terminated methoxy polyethylene glycol (mPEG) as macroinitiator. Polyelectrolyte complexation between mPEGGA as neutral-block-polyanion and chitosan (CS) as polycation has been scrutinized in aqueous solution as well as in the solid state.

Thermoplastic Elastomers Based on Compatibilized Poly(butylene terephthalate) Blends: Effect of Functional Groups and Dynamic Curing

Two sets of graft copolymers were prepared by grafting glycidyl methacrylate (GMA) or ally] (3-isocyanate-4-tolyl) carbamate (TAI) onto ethylene/propylene/diene terpolymer (EPDM) in an internal mixer. These graft copolymers were used as the compatibilizer to prepare the thermoplastic elastomers (TPEs) containing 50 wt%, of poly(butylene terephthalate), PBT, 30 wt% of compatibilizer, and 20 wt% of nitrile-butadiene rubber, NBR. The indirect, two-step mixer process was chosen for dynamic curing.

Spontaneous volume transition of polyampholyte nanocomposite hydrogels based on pure electrostatic interaction

A circular system is employed in this paper to investigate the swelling behaviors of polyampholyte hydrogels; this circular system can effectively eliminate the disturbance of various factors and keep the surrounding environment constant. It is found that there exists a spontaneous volume transition to the collapsed state of polyampholyte hydrogels, which is attributed to the overshooting effect, and the transition can occur repeatedly under certain conditions. C-13 NMR is employed to investigate the swelling behavior of polyampholyte hydrogels.

Lattice Boltzmann study of hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

By incorporating self-consistent field theory with lattice Boltzmann method, a model for polymer melts is proposed. Compared with models based on Ginzburg-Landau free energy, our model does not employ phenomenological free energies to describe systems and can consider the chain topological details of polymers. We use this model to study the effects of hydrodynamic interactions on the dynamics of microphase separation for block copolymers. In the early stage of phase separation, an exponential growth predicted by Cahn-Hilliard treatment is found. Simulation results also show that the effect of hydrodynamic interactions can be neglected in the early stage.

Band Gap Tunable, Donor-Acceptor-Donor Charge-Transfer Heteroquinoid-Based Chromophores: Near Infrared Photoluminescence and Electroluminescence

A series of D-pi-A-pi-D type of near-infrared (NIR) fluorescent compounds based on benzobis(thia diazole) and its selenium analogues were synthesized and fully characterized by H-1 and C-13 NMR, high-resolution mass spectrometry, and elemental analysis. The absorption fluorescence, and electrochemical properties were also studied. Photoluminescence of these chromophores ranges from 900 to 1600 nm and their band gaps are between 1.19 and 0.56 eV.

Study of morphology and phase diagram of the H-shaped (AC)B(CA) ternary block copolymers using self-consistent field theory

By using a combinatorial screening method based on the self-consistent field theory (SCFT) for polymer systems, the micro-phase morphologies of the H-shaped (AC)B(CA) ternary block copolymer system are studied in three-dimensional (3D) space. By systematically varying the volume fractions of the components A, B, and C, six triangle phase diagrams of this H-shaped (AC)B(CA) ternary block copolymer system with equal interaction energies among the three components are constructed from the weaker segregation regime to the strong segregation regime, In this study, thirteen 3D micro-phase morphologies for this H-shaped ternary block copolymer system are identified to be stable and seven 3D microphase morphologies are found to be metastable.

Defect evolution and hydrodynamic effects in lamellar ordering process of two-dimensional quenched block copolymers

The effects of hydrodynamic interactions on the lamellar ordering process for two-dimensional quenched block copolymers in the presence of extended defects and the topological defect evolutions in lamellar ordering process are numerically investigated by means of a model based on lattice Boltzmann method and self-consistent field theory. By observing the evolution of the average size of domains, it is found that the domain growth is faster with stronger hydrodynamic effects. The morphological patterns formed also appear different. To study the defect evolution, a defect density is defined and is used to explore the defect evolutions in lamellar ordering process. Our simulation results show that the hydrodynamics effects can reduce the density of defects. With our model, the relations between the Flory-Huggins interaction parameter chi, the length of the polymer chains N, and the defect evolutions are studied.

STUDY OF COARSENING OF MICRODOMAINS IN BLOCK COPOLYMERS BY LATTICE BOLTZMANN METHODS

In order to understand the coarsening of microdomains in symmetric diblock copolymers at the late stage, a model for block copolymers is proposed. By incorporating the self consistent field theory with the free energy approach Lattice Boltzmann model, hydrodynamic interactions can be considered. Compared with models based on Ginzburg-Landau free energy, this model does not employ phenomenological free energies to describe systems. The model is verified by comparing the simulation results obtained using this method with those of a dynamical version of the self consistent mean field theory. After that,the growth exponents of the characteristic domain size for symmetric block copolymers at late stage are studied. It is found that the viscosity of the system affects the growth exponents greatly, although the growth exponents are all less than 1/3 Furthermore, the relations between the growth exponent, the interaction parameter and the chain length are studied.

Red-Emitting Polyfluorenes Grafted with Quinoline-Based Iridium Complex: "Simple Polymeric Chain, Unexpected High Efficiency"

A series of red-light emitting electrophosphorescent polyfluorenes (PFs) with varying content of a quinoline-based iridium complex, (PPQ)(2)Ir(acac) (bis(2,4-diphenylquinolyl-N,C-2') iridium(acetylacetonate)), in the side chain are synthesized by Suzuki polycondensation. Because of the efficient Forster energy transfer from the PF main chain to (PPQ)(2)Ir(acac) and direct charge trapping on the complex, the electroluminescent emission from PF is nearly completely quenched, even though the amount of iridium complex I incorporated into the polymers is as low as 1 mol %. Based on a single-layer device configuration, a luminous efficiency of up to 5.0 cd A(-1) with a luminance of 2000 cd m(-2) and Commission Internationale de L'Eclairage coordinates of (0.63, 0.35) (x, y) is realized, which is far superior to that of previously reported red-light emitting PFs containing benzothiazole- and isoquinoline-based iridium complexes.

Blends based on sulfonated poly[bis(benzimidazobenzisoquinolinones)] and poly(vinylidene fluoride) for polymer electrolyte membrane fuel cell

A new blend system consisting of an amorphous sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBI) and the semi-crystalline poly(vinylidene fluoride) (PVDF) was prepared for proton exchange membranes. The miscibility behavior of a series of blends of SPBIBI with PVDF at various weight ratios was studied by WXRD, DSC and FTIR. The properties of the blend membranes were investigated, and it was found that the introduction of PVDF in the SPBIBI matrix altered the morphological structure of the blend membranes, which led to the formation of improved connectivity channels. For instance, the conductivity of the blend membrane containing 10 wt% PVDF displayed the highest proton conductivity (i.e., 0.086 S cm(-1)) at room temperature, a value almost twofold that of the pristine SPBIBI membranes (i.e., 0.054S cm(-1)) under identical conditions.

Novel proton exchange membranes based on water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)]

Novel water resistant sulfonated poly[bis(benzimidazobenzisoquinolinones)] (SPBIBIs) were synthesized from 6,6'-disulfonic-4,4'-binaphthy]-1,1',8,8'-tetracarboxylic dianhydride (SBTDA) and various aromatic ether tetraamines. The resulting polymers with IEC in the range of 2.17-2.87 mequiv g(-1) have a combination of desired properties such as high solubility in common organic solvents, film-forming ability, and excellent thermal and mechanical properties. Flexible and tough membranes, obtained by casting from m-cresol solution, had tensile strength, elongation at break, and tensile modulus values in the range of 87.6-98.4 MPa, 35.8-52.8%, and 0.94-1.07 GPa. SPBIBI membranes with a high degree of sulfonation displayed high proton conductivity and a good resistance to water swelling as well. SPBIBI-b with IEC of 2.80 mequiv g(-1) displayed the conductivity of 1.74 x 10(-1) S cm(-1) at 100 degrees C, which was comparable to that of Nafion (R) 117 (1.78 x 10(-1) S cm(-1), at 100 degrees C).

Core Crosslinking of Biodegradable Block Copolymer Micelles Based on Poly(ester carbonate)

A biodegradable amphiphilic block copolymer, PEG-b-P(LA-co-MAC), was used to prepare spherical micelles consisting of a hydrophobic P(LA-co-MAC) core and a hydrophilic PEG shell. To improve their stability, the micelles were crosslinked by radical polymerization of the double bonds in the hydrophobic blocks. The crosslinked micelles had similar sizes and a narrow size distribution compared to their uncrosslinked precursor. The improved stability of the crosslinked micelles was confirmed by measurements of the CMC and a thermodynamic investigation. These micelles can internalize into Hela cells in vitro as demonstrated by inverted fluorescence microscopy and CLSM. These stabilized nanoscale micelles have potential use in biomedical applications such as drug delivery and disease diagnosis.

Hemoglobin conjugated micelles based on triblock biodegradable polymers as artificial oxygen carriers

An artificial oxygen carrier is constructed by conjugating hemoglobin molecules to biodegradable micelles. Firstly a series of triblock copolymers (PEG-PMPC-PLA) in which the middle block contains pendant propargyl groups were synthesized and characterized. After the amphiphilic copolymer was self-assembled into core-shell micelles in aqueous solution, azidized hemoglobin molecules protected by carbon monoxide (CO) were conjugated to the micelles via click reaction between the propargyl and azido groups. The conjugation causes an increase of the micelle's mean diameter. Maximum conjugation ratio is 250 wt% in the hemoglobin-conjugated micelles (HCMs). Oxygen-binding ability of the HCMs was demonstrated by converting the CO-binding state of the HCMs into O-2-binding state.

Oxygen Carrier Based on Hemoglobin/Poly(L-lysine)-block-poly(L-phenylalanine) Vesicles

An oxygen carrier was prepared by encapsulating carbonylated hemoglobin (CO-Hb) molecules into polypeptide vesicles made from poly(L-lysine)-block-poly(L-phenylalanine) (PLL-b-PPA) diblock copolymers in aqueous medium at pH 5.8. The encapsulation was confirmed by confocal laser scanning microscopy (CLSM). The morphology and size of the Vesicles were studied by field-emission scanning electron microscopy (ESEM). They had a spherical shape with it mean diameter of about 4 to 5 mu m. The encapsulation efficiency of hemoglobin was 40 wt %, and the hemoglobin content in the vesicles was 32 wt %. The CO-Hb encapsulated in the PLL-b-PPA vesicles was more stable than free CO-Hb under ambient conditions, In the presence of a O-2 atmosphere, the CO-Hb in the vesicle could be converted into oxygen-binding hemoglobin (O-2-Hb) under irradiation of visible light for 2 h. Therefore, the CO-Hb/PLL-b-PPA vesicles are expected to be used its red blood cell substitutes.