Large compound vesicles from amphiphilic block copolymer/rigid-rod conjugated polymer complexes

Morphology evolution in complexes of amphiphilic block copolymers poly(styrene)-b-poly(acrylic acid) (PS-b-PAA) and poly(styrene)-b-poly(ethylene oxide) (PS-b-PEO) in the presence of polyaniline (PANI) in aqueous solution is reported. Transmission electron microscopy, atomic force microscopy, and dynamic light scattering techniques were used to study the morphologies at various PANI contents [aniline]/[acrylic acid] ([ANI]/[AA]) ranging from 0.1 to 0.7. The interpolyelectrolyte complex formed between PAA and PANI plays a key role in the morphology transformation. Spherical micelles formed from pure block copolymers were transformed into large compound vesicles upon increasing PANI concentration due to internal block copolymer segregation. In addition to varying PANI content, the kinetic pathway of nanoparticle formation was controlled through different water addition methods and was critical in the formation of multigeometry nanoparticles.

Graphene/tri-block copolymer composites prepared via RAFT polymerizations for dual controlled drug delivery via pH stimulation and biodegradation

A novel tri-block copolymer poly(oxopentanoate ethyl methacrylate)-block-poly(pyridyl disulfide ethyl acrylate)-block-poly(ethylene glycol acrylate) [poly(OEMA-b-PDEA-b-PEGA)], retaining active keto groups and pyridyl disulfide (PDS) side functionalities, was synthesized as a drug delivery vehicle using reversible addition-fragmentation chain transfer (RAFT) polymerization method. One mimic drug pyridine-2-thione (PT) was introduced into the monomer, PDEA for copolymerization. The other mimic drug O-benzylhydroxylamine (BHA) was conjugated with tri-block copolymer via efficient oxime coupling chemistry, followed by the attachment onto graphene via π-π stacking interaction to obtain a graphene/tri-block copolymer composite. 1H NMR, UV-vis absorption spectroscopy, fluorescence spectroscopy, gel permeation chromatography (GPC), atomic force microscope (AFM) and transmission electron microscope (TEM) were used to verify the successful step-wise preparation of the tri-block copolymer and drug loaded composite. In vitro release behaviors of BHA and PT from graphene/tri-block copolymer composite via dual drug release mechanisms were investigated. BHA can be released under acid environment, while PT will be released in the presence of reducing agents, such as dithiothreitol (DTT) or glutathione (GSH). It can be envisioned that this novel composite could be exploited as a novel intracellular drug delivery system via dual release mechanisms.

Morphology and mechanical properties of nanostructured thermoset/block copolymer blends with carbon nanoparticles

Here we report the effect of multi-walled carbon nanotubes (MWCNTs) and thermally reduced graphene (TRG) on the miscibility, morphology and final properties of nanostructured epoxy resin with an amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer. The addition of nanoparticles did not have any influence on the miscibility of PEO-PPO-PEO copolymer in the resin. However, MWCNTs and TRG reduced the degree of crystallinity of the PEO-rich microphases in the blends above 10 wt.% of copolymer while they did not change the phase morphology at the nanoscale, where PPO spherical domains of 20-30 nm were found in all the samples studied. A synergic effect between the self-assembled nanostructure and the nanoparticles on the toughness of the cured resin was observed. In addition, the nanoparticles minimized the negative effect of the copolymer on the elastic modulus and glass transition temperature in the resin.

Nano-capsules of amphiphilic poly (ethylene glycol)-block-poly (bisphenol A carbonate) copolymers via thermodynamic entrapment

The synthesis of amphiphilic poly(ethylene glycol)-block-poly(bisphenol A carbonate) (PEG-b-PC) block copolymer is presented here using a simple bio-chemistry coupling reaction between poly(bisphenol A carbonate) (PC) with a monomethylether poly(ethylene glycol) (mPEG-OH) block, mediated by dicyclohexylcarbodiimide/4-dimethylaminopyridine. This method inherently allows great flexibility in the choice of starting materials as well as easy product purification only requiring phase separation and water washing. Collective data from Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR) and modulated dynamic scanning calorimetry (MDSC) confirmed the successful attachment of the poly(ethylene glycol) (mPEG-OH) and poly(bisphenol A carbonate) (PC) blocks. The preparation of nano-capsules was carried out by sudden addition of water to PEG-b-PC copolymers dispersed in THF, resulting in the controlled precipitation (i.e. thermodynamic entrapment) of the copolymer. Nano-capsules as small as 85 nm ± 30 nm were produced using this simple and fast methodology. We also demonstrate that encapsulating a water-insoluble bisphenol A diglycidyl ether (DGEBA) epoxy resin is possible highlighting the potential use of these capsules as a chemical delivery system.

Assembled block copolymer stabilized high internal phase emulsion hydrogels for enhancing oil safety

Accidental spills and subsequent fires during oil storage and transportation periods cause serious damage to environments. Herein, we present a novel route to enhance oil safety by transforming oils into high internal phase emulsion (HIPE) hydrogels. These HIPE hydrogels are stabilized by solvent- or pH-driven assembled block copolymer (BCP), namely poly(4-vinylpyridine)-block-poly(ethylene glycol)-block-poly(4-vinylpyridine) (4VPm-EGn-4VPm). The assembled BCP shows high efficiency to stabilize HIPE hydrogels with a low concentration of 1.0 (w/v) % relative to the continuous aqueous phase. The volume fraction of the dispersed organic phase can be as high as 89% with a variety of oils, including toluene, xylene, blended vegetable oil, canola oil, gasoline, diesel, and engine oil. These smelly and flammable liquids were formed into HIPE hydrogels and thus their safety was enhanced. As the assembly is pH sensitive, oils trapped in the HIPE hydrogels can be released by simply tuning pH values of the continuous aqueous phase. The aqueous phase containing BCP can be reused to stabilize HIPE hydrogels after naturalization. These assembled BCP stabilized HIPE hydrogels offer a novel and safe approach to preserve and transport these smelly and flammable liquid oils, avoiding environmental damage.

Enhanced homogeneity and interfacial compatibility in melt-extruded cellulose nano-fibers reinforced polyethylene via surface adsorption of poly(ethylene glycol)-block-poly(ethylene) amphiphiles

In this paper, we demonstrate that an amphiphilic block copolymer such as polyethylene glycol-b-polyethylene can be used as both dispersing and interfacial compatibilizing agent for the melt compounding of LLDPE with cellulose nano-fibers. A simple and effective spray drying methodology was first used for the first time for the preparation of a powdered cellulose nano-fibers extrusion feedstock. Surface adsorption of the amphiphilic PEG-b-PE was carried out directly in solution during this process. These various dry cellulosic feedstock were subsequently combined with LLDPE via extrusion to produce a range of nano-composites. The collective outcomes of this research are several folds. Firstly we show that presence of surface adsorbed PEG-b-PE effectively hindered the aggregation of the cellulose nano-fibers during the extrusion, affording clear homogenous materials with minimum aggregation even at the highest loading of cellulose nano-fibers (∼23 vol.%). Secondly, the tailored LLDPE/cellulose interface arising from intra- and inter-molecular hydrogen and Van der Waals bonds yielded significant levels of mechanical improvements in terms of storage and tensile modulus. We believe this study provides a simple technological template to produce high quality and performant polyolefins cellulose-based nano-composites.

Effect of synthesis parameters on the electrical conductivity of polypyrrole-coated poly(ethylene terephthalate) fabrics

The effects of pyrrole, anthraquinone-2-sulphonic acid (AQSA) and iron(III) chloride (FeCl3) concentrations, reaction time and temperature on the electrical conductivity of polypyrrole (PPy) - coated poly(ethylene terephthalate) (PET) fabrics were investigated. With an increase in both the AQSA and FeCl3 concentrations, resistivity decreased to a point beyond which higher concentrations led to increased surface resistivity. Erosion of the polymer coating, in dynamic synthesis from continual abrasion, manifested as an exponential increase in the resistance of the coated textile substrate. This was not encountered in static synthesis conditions. Temperature affected the degree of surface and bulk polymerisation. The effect of polymerisation temperature on conductivity was negligible. Conductive polymer coating on textiles through chemical polymerisation enabled a smooth coherent film to encase individual fibres, which did not affect the tactile properties of the host substrate. The optimum FeCl3/pyrrole and AQSA FeCl3/pyrrole molar ratios were found to be 2.22 and 0.40 respectively.

Miscibility, crystallization κinetics and real-time small-Angle x-ray scattering investigation of the semicrystalline morphology in thermosetting polymer blends of epoxy resin and poly(ethylene oxide)

Thermosetting polymer blends of poly(ethylene oxide) (PEO) and bisphenol-A-type epoxy resin (ER) were prepared using 4,4′-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA) as curing agent. The miscibility and crystallization behavior of MCDEA-cured ER/PEO blends were investigated by differential scanning calorimetry (DSC). The existence of a single composition-dependent glass transition temperature (Tg) indicates that PEO is completely miscible with MCDEA-cured ER in the melt and in the amorphous state over the entire composition range. Fourier-transform infrared (FTIR) investigations indicated hydrogen-bonding interaction between the hydroxyl groups of MCDEA-cured ER and the ether oxygens of PEO in the blends, which is an important driving force for the miscibility of the blends. The average strength of the hydrogen bond in the cured ER/PEO blends is higher than in the pure MCDEA-cured ER. Crystallization kinetics of PEO from the melt is strongly influenced by the blend composition and the crystallization temperature. At high conversion, the time dependence of the relative degree of crystallinity deviated from the Avrami equation. The addition of a non-crystallizable ER component into PEO causes a depression of both the overall crystallization rate and the melting temperature. The surface free energy of folding σe displays a minimum with variation of composition. The spherulitic morphology of PEO in the ER/PEO blends exhibits typical characteristics of miscible crystalline/amorphous blends, and the PEO spherulites in the blends are always completely volume-filling. Real-time small-angle X-ray scattering (SAXS) experiments reveal that the long period L increases drastically with increasing ER content at the same temperatures. The amorphous cured ER component segregates interlamellarly during the crystallization process of PEO because of the low chain mobility of the cured ER. A model describing the semicrystalline morphology of MCDEA-cured ER/PEO blends is proposed based on the SAXS results. The semicrystalline morphology is a stack of crystalline lamellae; the amorphous fraction of PEO, the branched ER chains and imperfect ER network are located between PEO lamellae.

Nanostructures and nanoporosity in thermoset epoxy blends with an amphiphilic polyisoprene-block-poly(4-vinyl pyridine) reactive diblock copolymer

Nanostructured thermoset blends were prepared based on a bisphenol A-type epoxy resin and an amphiphilic reactive diblock copolymer, namely polyisoprene-block-poly(4-vinyl pyridine) (PI-P4VP). Infrared spectra revealed that the P4VP block of the diblock copolymer reacted with the epoxy monomer. However, the non-reactive hydrophobic PI block of the diblock copolymer formed a separate microphase on the nanoscale. Ozone treatment was used to create nanoporosity in nanostructured epoxy/PI-P4VP blends via selective removal of the PI microphase and lead to nanoporous epoxy thermosets; disordered nanopores with the average diameter of about 60 nm were uniformly distributed in the blend with 50 wt% PI-P4VP. Multi-scale phase separation with a distinctly different morphology was observed at the air/sample interface due to the interfacial effects, whereas only uniform microphase separated morphology at the nanoscale was found in the bulk of the blend.

Heterotrimeric G proteins-mediated resistance to necrotrophic pathogens includes mechanisms independent of salicylic acid-, jasmonic acid/ethylene- and abscisic acid-mediated defense signaling

Heterotrimeric G proteins are involved in the defense response against necrotrophic fungi in Arabidopsis. In order to elucidate the resistance mechanisms involving heterotrimeric G proteins, we analyzed the effects of the Gβ (subunit deficiency in the mutant agb1-2 on pathogenesis-related gene expression, as well as the genetic interaction between agb1-2 and a number of mutants of established defense pathways. Gβ-mediated signaling suppresses the induction of salicylic acid (SA)-, jasmonic acid (JA)-, ethylene (ET)- and abscisic acid (ABA)-dependent genes during the initial phase of the infection with Fusarium oxysporum (up to 48 h after inoculation). However, at a later phase it enhances JA/ET-dependent genes such as PDF1.2 and PR4. Quantification of the Fusarium wilt symptoms revealed that Gβ- and SA-deficient mutants were more susceptible than wild-type plants, whereas JA- and ET-insensitive and ABA-deficient mutants demonstrated various levels of resistance. Analysis of the double mutants showed that the Gβ-mediated resistance to F. oxysporum and Alternaria brassicicola was mostly independent of all of the previously mentioned pathways. However, the progressive decay of agb1-2 mutants was compensated by coi1-21 and jin1-9 mutations, suggesting that at this stage of F. oxysporum infection Gβ acts upstream of COI1 and ATMYC2 in JA signaling.

Preparation of cross-linked nanoporous poly(ethylene glycol) diacrylate membrane in hexagonal lyotropic liquid crystal phases

Cross-linked poly(ethylene glycol) diacrylate (PEGDA) membranes were prepared by polymerization in periodic nanostructured lyotropic liquid crystals (LLC) hexagonal phases under UV light. A series of membranes were prepared under different purification treatment conditions. Polarized light microscope was employed to determine the LLC phase texture of LLC system before and after polymerization. It is found that the LLC hexagonal structure retained to some degree after polymerization. The interior structures of final membranes were investigated with scanning electron microscope (SEM). The results suggested that purification process affect the structure retention.

Superhydrophobic electrospun POSS-PMMA copolymer fibres with highly ordered nanofibrillar and surface structures

A POSS-PMMA copolymer has been synthesised by conventional free-radical polymerisation reaction. Uniform electrospun fibres from this copolymer showed a water contact angle as high as 1651 with a sliding angle as low as 61. For the first time, we found that the electrospun fibres had a bundled nanofibril secondary structure with an ordered POSS morphology on the fibre surface.