Free-Radical Solution Copolymerization of the Ionic Liquid Monomer 1-Vinyl-3-Ethylimidazolium Bromide with Acrylonitrile

Ionic liquid monomer 1-vinyl-3-ethylimidazolium bromide (ViEtIM(+)Br(-)) was first used to copolymerize with acrylonitrile (AN) successfully under various conditions. This was achieved with azobisisobutyronitrile as the initiator and dimethyl sulfoxide as the solvent. The kinetics of this copolymerization were studied. The values of the monomer apparent reactivity ratios were calculated by the Kelen-Tudos method. The apparent reactivity ratios of ViEtIM(+)Br(-) (r(ViEtIM+Br-)) and AN (r(AN)) were similar at polymerization conversions of less than 10%, (r(AN) = 0.954, r(ViEtIM+Br-) = 0.976). The copolymers were obtained with high molecular weights and high hydrophilicides. The copolymers were characterized by H-1-NMR, differential scanning calorimetry, and thermogravimetric analysis. These copolymers may be potentially useful in the preparation of precursor fibers and carbon fibers.

A Novel Strategy to Branched Polyacrylonitrile Via One-Pot RAFT Copolymerization of Acrylonitrile and an Asymmetrical Divinyl Monomer

Branched polyacrylonitriles were prepared via the one-pot radical copolymerization of acrylonitirle and an asymmetric divinyl monomer (allyl methacrylate) that possesses both a higher reactive methacrylate and a lower reactive allyl. RAFT technique was used to keep a low-propagation chain concentration via a fast reversible chain transfer euilibration and thus the cross-linking was prevented until a high level of monomer conversions. This novel strategy was demonstrated to engenerate a branched architecture with abundant pendant functional vinyl and nitrile groups, and controlled molecular weight as a behavior of controlled/living radical polymerization characteristics. The effect of the various experimental parameters, including temperature, brancher to monomer molar ratio, and chain transfer agent to initiator molar ratio, on the control Of moleculer dimension (molecular weight and polydispersity indices) and the degree of branching were investigated in detail. Moreover, H-1 NMR and gel permeation chromatography confirm the branched architecture of the resultant polymer. The intrinsic viscosity of the copolymer is also lower than the linear counterpart.

Facile synthesis of platinum nanoelectrocatalyst with urchinlike morphology

A very simple and effective wet chemical route to direct synthesis of well-dispersed Pt nanoparticles with urchinlike morphology is proposed, which was carried out by simply mixing H2PtCl6 aqueous solution and poly(vinyl pyrrolidone) with the initial molar ratios of 1:3.5 kept constant at 30 degrees C for 3 days in the presence of formic acid. As-prepared urchinlike Pt nanostructures showed excellent electrocatalytic activity toward the reduction of dioxygen and oxidation of methanol and could be used as a promising nanoelectrocatalyst.

Poly(ethylene glycol-co-propylene glycol) as a Macromolecular Plasticizing Agent for Polylactide: Thermomechanical Properties and Aging

Finding a Suitable plasticizer for polylactide (PLA) is necessary to overcome its brittleness and enlarge its range of applications. In this study, commercial PLA was melt-blended with a new plasticizer, an ethylene glycol/propylene glycol random copolymer [poly(ethylene glycol-co-propylene glycol) (PEPG)] with a typical number-average molecular weight of 1.2 kDa and an ethylene glycol content of 78.7 mol %. The thermal properties, crystallization behavior, and mechanical properties of the quenched blends and the properties of the blends after storage for 2 months under the ambient conditions were investigated in detail. The advantage of using PEPG is that it does not crystallize at room temperature and has good compatibility with PLA. The quenched PLA/PEPG blends were homogeneous and amorphous systems. With an increase in the PEPG content (5-20%), the glass-transition temperature, tensile strength, and modulus of the blends decreased, whereas the elongation at break and crystallizability increased dramatically. The cold crystallization of PLA resulted in phase separation of the PLA/PEPG blends by annealing of the blends at the crystallization temperature.

Crystallization Behavior and Mechanical Properties of Crosslinked Plasticized Poly(L-lactic acid)

Enhancing the stability of plasticized poly(L-lactic acid) (PLLA) with poly (ethylene glycol) (PEG) is necessary for its practical application. In this study, plasticized PLLA (PLLA/PEG 80/20 wt/wt) was crosslinked under I-ray (Co-60) in the presence of triallyl isocyanurate (TALC) as crosslinking agent. FTIR analysis revealed that PLLA, PEG, and TALC formed a cocrosslinking structure. Crystallization behavior and mechanical properties of the crosslinked plasticized PLLA were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM), and tensile tests. Experimental results indicated that the crystallization behaviors of both PEG and PLLA in the blends were restrained after irradiation. The melting peak of PEG in the crystallized samples disappeared at a low irradiation doses about 10 kGy. Although PLLA still owned the behavior of crystallize, its cold crystallization temperature and glass transition temperature shifted to higher temperature. Mechanical properties of the plasticized PLLA were strengthened through crosslinking. Both yield strength and elastic modulus of the samples increased after crosslinking.

Study on the Single Crystals of Poly(3-octylthiophene) Induced by Solvent-Vapor Annealing

Needle-like single crystals of poly(3-octylthiophene) (P3OT) have been prepared by tetrahydrofuran-vapor annealing. The morphology and structure of the crystals were characterized with optical microscopy, scanning electron microscopy, atomic force microscopy, transmission electron microscopy, and wide-angle X-ray diffraction. It is observed that the P3OT molecules are packed with the backbones parallel to the length axis of the crystal and the alkyl side chains perpendicular to the substrate. The field effect transistor based on the P3OT single crystal exhibited a charge carrier mobility of 1.54 x 10(-4) cm(2)/(Vs) and on/off current ratio of 37, and the molecular orientation of the crystal is ascribed to account for the device performance. The time-dependent morphological evolution demonstrated that the crystals underwent Ostwald ripening when annealed.

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.

Preparation, Surface Properties and Biological Activity of the Composite of Poly (lactide-co-glycolide) and Bioglass Nanoparticles Surface Grafted with Poly(L-lactide)

SiO2-CaO-P2O5 gel bioglass (BG) nanoparticles with the diameter of 40 nm were synthesized by sol-gel approach. The surface of BG nanoparticles was grafted through the ring-open polymerization of the L-lactide to yield poly (L-lactide) (PLLA) grafted gel particle (PLLA-g-BG). The PLLA-g-BG was further blended with poly(lactide-co-glycolide) (PLGA) to prepare the nanocomposites of PLLA-g-BG/PLGA with the various blend ratios of two phases. PLLA-g-BG accounted 10%, 20% and 40% in the composite, respectively. TGA, ESEM and EDX were used to analyze the graft ratio of PLLA-g-BG, the dispersion of nano-particles and the surface elements of the composites respectively. The rabbit osteoblasts were seeded and cultured on the thin films of composites in vitro. The cell adhesion, spreading and growth of osteoblasts were analyzed with FITC staining, NIH Image J software and MTT assay. The change of cell cycle was monitored by flow cytometry (FCM). The results demonstrated that the Surface modification of BG with PLLA could significantly improve the dispersing of the particles in the matrix of PLGA. The nanocomposite with 20% PLLA-g-BG exhibited superior surface properties, including roughness and plenty of silicon, calcium and phosper, to enhance the adhesion, spreading and proliferation of osteoblasts.

NOVEL COMPOSITES OF POLY(L-LACTIDE) AND SURFACE MODIFIED BIOACTIVE SiO2-CaO-P2O5 GEL NANOPARTICLES: MECHANICAL AND BIOLOGICAL PROPERTIES

Bioactive SiO2-CaO-P2O5 gel (BAG) nanoparticles with 40 nm in diameter were synthesized by the sol-gel route and further modified via the ring-opening polymerization of lactide on the surface of particles. Surface modified BAG (mBAG) was introduced in poly(L-lactide) (PLLA) matrix as bioactive filler. The dispersibility of mBAG in PLLA matrix was much higher than that of rough BAG particles. Tensile strength of the mBAG/PLLA composite could be increased to 61.2 MPa at 2 wt% filler content from 53.4 MPa for pure PLLA. The variation of moduli of the BAG/PLLA and mBAG/PLLA composites always showed an enhancement tendency with the increasing content of filler loading. The SEM photographs of the fracture surfaces showed that mBAG could be homogeneously dispersed in the PLLA matrix, and the corrugated deformation could absorb the rupture energy effectively during the breaking of materials. In vitro bioactivity tests showed that both BAG and mBAG particles could endow the composites with ability of the calcium sediment in SBF, but the surface modification of BAG particles could weaken this capability to some extent. Biocompatibility tests showed that both BAG and mBAG particles could facilitate the attachment and proliferation of the marrow cells on the surface of the composite.

Electrospinning of multicomponent ultrathin fibrous nonwovens for semi-occlusive wound dressings

This work describes the design and assembly of multifunctional and cost-efficient composite fiber nonwovens as semi-occlusive wound dressings using a simple electrospinning process to incorporate a variety Of functional components into an Ultrathin fiber. These components include non-hydrophilic poly(L-lactide) (PLLA) as fibrous backbone, hydrophilic poly(vinyl pyrrolidone)iodine (PVP-I), TiO2 nanoparticles, zinc chloride as antimicrobial, odor-controlling, and antiphlogistic agents, respectively. The process of synthesis starts with a multicomponent solution Of PLLA, PVP, TiO2 nanoparticles plus zinc chloride, in which TiO2 nanoparticles are synthesized by in situ hydrolysis of TiO2 precursors in a PVP Solution for the sake of obtaining the particle-uniformly dispersive solution. Subsequent electrospinning generates the corresponding composite fibers. A further iodine vapor treatment to the composite fibers combines iodine with PVP to produce the PVP-I complexes. Experiments indicate that the assembled composite fibers (300-400 nm) possess the ointment-releasing characteristic and the phase-separate, core-sheath structures in which PVP-I residing in fiber Surface layer becomes the sheath, and PLLA distributing inside the fiber acts as the core.

Preparation of one-dimensional CoFe2O4 nanostructures and their magnetic properties

Cobalt ferrite one-dimensional nanostructures (nanoribbons and nanofibers) were prepared by electrospinning combined with sol-gel technology. The nanoribbons and nanofibers were formed through assembling magnetic nanoparticles with poly(vinyl pyrrolidone) (PVP) as the structure-directing template. Nanoribbons and nanofibers were obtained after calcining the precursor nanoribbons at different temperatures. Successive Ostwald ripening processes occur during the formation of CoFe2O4 nanoribbons and nanofibers. The sizes of nanoparticles varied with calcination temperatures, which leads to different one-dimensional structures and variable magnetic properties. These novel magnetic one-dimensional structures can potentially be used in nanoelectronic devices, magnetic sensors, and flexible magnets.

Crystalline morphology of poly(L-lactic acid) thin films

Crystalline morphologies of spin-coated poly(L-lactic acid) (PLLA) thin films under different conditions are investigated mainly with atomic force microscopy (AFM) technique. When PLLA concentration in chloroform is varied from 0.01 to 1% gradually, disordered structure, rod-shape and larger spheres aggregates are observed in thin films subsequently. Under different annealing temperature, such as at 78, 102, 122 degrees C, respectively, we can find most rod-like crystalline aggregates. Interestingly, we observed that nucleation sites locate at the edge of the holes at the original crystalline stage. Then, these holes developed to form chrysanthemum-like and rods subsequently with annealing time meanwhile the size and the shape of crystalline aggregate are changed. In addition. effect of substrate and solvent on morphology is also discussed. On the other hand, the possible mechanism of crystalline morphology evolution is proposed.

Multi-armed poly(L-glutamic acid)-graft-oligoethylenimine copolymers as efficient nonviral gene delivery vectors

Background The application of polyethylenimine (PEI) in gene delivery has been severely limited by significant cytotoxicity that results from a nondegradable methylene backbone and high cationic charge density. It is therefore necessary to develop novel biodegradable PEI derivates for low-toxic, highly efficient gene delivery.Methods A series of novel cationic copolymers with various charge density were designed and synthesized by grafting different kinds of oligoethylenimine (OEI) onto a determinate multi-armed poly(L-glutamic acid) backbone. The molecular structures of multi-armed poly(L-glutamic acid)-graft-OEI (MP-g-OEI) copolymers were characterized using nuclear magnetic resonance, viscosimetry and gel permeation chromatography. Moreover, the MP-g-OEI/DNA complexes were measured by a gel retardation assay, dynamic light scattering and atomic force microscopy to determine DNA binding ability, particle size, zeta potential, complex formation and shape, respectively. MP-g-OEI copolymers were also evaluated in Chinese hamster ovary and human embryonic kidney-293 cells for their cytotoxicity and transfection efficiency.

Effect of peroxide crosslinking on thermal and mechanical properties of poly(epsilon-caprolactone)

Poly(epsilon-caprolactone) (PCL), a saturated polyester, derived from ring-opening polymerization of epsilon-caprolactone, was chemically crosslinked with various amounts of benzoyl peroxide (BPO) by a two-step method by first evenly dispersing the BPO into the PCL matrix and then crosslinking at elevated temperature. The gel fraction increased with an increase in BPO content. The modified Charlesby-Pinner equation was used to calculate the ratio of chain scission and crosslinking. The results showed that both scission and crosslinking occurred, and that crosslinking predominated over scission. The number-average molecular weight between the crosslinks determined by the rubber elasticity theory using the hot set test showed a decrease with increasing BPO content. The melting temperature and crystallinity decreased with an increase in BPO content, and the crystallization temperature increased after crosslinking. Dynamic mechanical analysis results showed a decrease in the glass transition temperature as a result of chemical crosslinking of PCL. This was explained by the observed reduction in crystallinity and the increase in free volume due to restrictions in chain packing.

Thermal and mechanical properties of poly(epsilon-caprolactone) crosslinked with gamma radiation in the presence of triallyl isocyanurate

Poly(epsilon-caprolactone) was crosslinked by gamma radiation in the presence of triallyl isocyanurate. The influence of gamma-radiation crosslinking on the thermal and mechanical properties of poly(epsilon-caprolactone)/triallyl isocyanurate was investigated. Differential scanning calorimetry analyses showed differences between the first and second scans. Dynamic mechanical analysis showed an increase in the glass-transition temperature as a result of the radiation crosslinking of poly(epsilon-caprolactone). Thermogravimetric analysis showed that gamma-radiation crosslinking slightly improved the thermal stability of poly(epsilon-caprolactone). The 7 radiation also strongly influenced the mechanical properties. At room temperature, crosslinking by radiation did not have a significant influence on the Young's modulus and yield stress of poly(E-caprolactone). However, the tensile strength at break and the elongation at break generally decreased with an increase in the crosslinking level. When the temperature was increased above the melting point, the tensile strength at break, elongation at break, and Young's modulus of poly(epsilon-caprolactone) were also reduced with an increase in the crosslinking level. The yield stress disappeared as a result of the disappearance of the crystallites.