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We report a nanocarrier based on A(2)B type miktoarm polymers (A=polyethylene glycol (PEG); B=polycaprolactone (PCL)) for nimodipine (NIM), a hydrophobic drug with very poor aqueous solubility that is commonly prescribed for the prevention and treatment of delayed ischemic neurological disorders. The A(2)B star polymers were constructed on a core with orthogonal functionalities that facilitated the performance of "click" chemistry followed by ring-opening polymerization. These star polymers assemble into spherical micelles into which NIM can be easily loaded by the co-solvent evaporation method. The micelles obtained from the star polymer PEG775(2)-PCL5800 showed NIM encapsulation efficiency of up to 78 wt% at a feed weight ratio of 5.0%. The loading efficiency of the micelles was dependent on the length of the PCL arm in the A(2)B miktoarm polymers. Aqueous solubility of NIM was increased by approximately 200 fold via micellar encapsulation. The in vitro release of NIM from the micelles was found to occur at a much slower rate than from its solution. Lipopolysaccharide induced nitric oxide production in N9 microglia cells was reduced in the presence of micelle-encapsulated NIM, as well as in the presence of micelles alone. The treatment of microglia with micelle-encapsulated NIM reduced the release of TNF-alpha, a pro-inflammatory cytokine. These results suggest that NIM-loaded miktoarm micelles could be useful in the treatment of neuroinflammation.

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Polylactide (DL)/polyethylene glycol/silicate nanocomposite blended biodegradable films have been prepared by solvent casting method. Rheological and thermal properties were investigated for both neat amorphous polylactide (PLA-DL form) and blend of montmorillonite (clay) and poly (ethylene glycol) (PEG). Melt rheology of the PLA individually and blends (PLA/clay; PLA/PEG; PLA/PEG/clay) were performed by small amplitude oscillation shear (SAOS) measurement. Individually, PLA showed an improvement in the viscoelastic properties in the temperature range from 180 to 190 degrees C. Incorporation of nanoclay (3% to 9% wt) was attributed by significant improvements in the elastic modulus (G') of PLA/clay blend due to intercalation at higher temperature. Both dynamic modulii of PLA/PEG blend were significantly reduced with addition of 10% PEG. Rheometric measurement could not be conducted while PLA/PEG blends containing 25% PEG. A blend of PLA/PEG/clay (68/23/9) showed liquid-like properties with excellent flexibility. Thermal analysis of different clay loading films indicated that the glass transition temperatures (T(g)) remained unaffected irrespective of clay concentration due to immobilization of polymer chain in the clay nanocomposite. PEG incorporation reduced the T(g) of the blend (PLA/PEG and PLA/PEG/clay) significantly. Both rheological and thermal analysis data supported plasticization and flexibility of the blended films. It is also interesting to study competition between PLA and PEG for the intercalation into the interlayer spacing of the clay. This study indicates that PLA/montmorillonite blend could serve as effective nano-composite for packaging and other applications.

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The melt rheology and thermal properties of polylactide (PLA)-based nanocomposite films that were prepared by solvent casting method with L-PLA, polyethylene glycol (PEG), and montmorillonite clay were studied. The neat PLA showed predominantly solid-like behavior (G' > G″) and the complex viscosity (η*) decreased systematically as the temperature increased from 184 to 196 °C. The elastic modulus (G') of PLA/clay blend showed a significant improvement in the magnitude in the melt, while clay concentration was at 6% wt or higher. At similar condition, PEG dramatically reduced dynamic modulii and complex viscosity of PLA/PEG blend as function of concentration. A nanocomposite blend of PLA/PEG/clay (74/20/6) when compared to the neat polymer and PLA/PEG blend exhibited intermediate values of elastic modulus (G') and complex viscosity (η*) with excellent flexibility. Thermal analysis of different clay loading blends indicated that the melting temperature (T(m)) and glass transition temperature (T(g)) remained unaffected irrespective of clay concentration due to immobilization of polymer chain in the clay nanocomposite. PEG incorporation reduced the T(g) and the T(m) of the blends (PLA/PEG and PLA/PEG/clay) significantly, however, crystallinity increased in the similar condition. The transmission electron microscopy (TEM) image of nanocomposite films indicated good compatibility between PLA and PEG, whereas clay was not thoroughly distributed in the PLA matrix and remained as clusters. The percent crystallinity obtained by X-ray was significantly higher than that of differential scanning calorimeter (DSC) data for PLA.

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It is now well established that amphiphilic PS-b-P2VP-b-PEO linear triblock copolymers can form multilayered assemblies, thus core-shell-corona (CSC) micelles, in water. Micellization is triggered by addition of a small amount of water into a dilute solution of the PS-b-P2VP-b-PEO copolymer in a non-selective organic solvent. However, the phenomena that take place at the very beginning of this process are poorly documented. How these copolymer chains are perturbed by addition of water was investigated in this work by light and neutron scattering techniques and transmission electron microscopy. It was accordingly possible to determine the critical water concentration (CWC), the compactness of the nano-objects in solution, their number of aggregation, and their hydrodynamic diameter at each step of the micellization process.

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Metastable spherical micelles have been obtained by mixing in chloroform poly(styrene)-block-poly(4-vinylpyridine) diblock copolymers with perfluorinated surfactants bearing a carboxylic acid head. Dilution of these initial micelles triggers a morphological reorganization resulting in the formation of more stable vesicles. This transition can be advantageously used to encapsulate molecules of interest.

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This work describes studying the permanent grafting of carboxylic acid end-functionalized poly(ethylene glycol) methyl ether (PEG) chains of different molecular weights from the melt onto a surface employing poly(glycidyl methacrylate) ultrathin film as an anchoring layer. The grafting led to the synthesis of the complete PEG brushes possessing exceptionally high grafting density. The maximum thickness of the attached PEG films was strongly dependent on the length of the polymer chains being grafted. The maximum grafting efficiency was close to the critical entanglement molecular weight region for PEG. All grafted PEG layers were in the "brush regime", since the distance between grafting sites for the layers was lower than the end-to-end distance for the anchored macromolecules. Scanning probe microscopy revealed that the grafting process led to complete PEG layers with surface smoothness on a nanometric scale. Practically all samples were partly or fully covered with crystalline domains that disappeared when samples were scanned under water. Due to the PEG hydrophilic nature, the surface with the grafted layer exhibited a low (up to 21 degrees ) water contact angle.

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A reactor for the synthesis of gold nanoparticles is one of the uses of a poly(styrene)-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) triblock copolymer (PS-b-P2VP-b-PEO) which forms core-shell-corona micelles in water. Very low polydispersity spherical micelles are observed that consist of a PS core surrounded by a pH-sensitive P2VP shell and a corona of PEO chains end-capped by a hydroxyl group. The corona can act as a site for attaching responsive or sensing molecules.