Hydrogel nanocomposites: a potential UV/blue light filtering material for ophthalmic lenses.

Poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (poly(HEMA-co-MMA)) and ZnS hydrogel nanocomposites were prepared and characterized. The chemical composition of the inorganic nanoparticles was confirmed by X-ray diffraction, and the homogeneity of their distribution within the hydrogel was assessed by transmission electron microscopy. The influence of the content of ZnS nanoparticles on the optical performances of the nanocomposites was investigated by UV-Vis spectroscopy. The ability of the hydrogel nanocomposites to filter the hazardous UV light and part of the blue light was reported, which makes them valuable candidates for ophthalmic lens application. In contrast to the optical properties, the thermo-mechanical properties of neat poly(HEMA-co-MMA) hydrogels were found to be largely independent of filling by ZnS nanoparticles (≤2 mg/ml co-monomer mixture). Finally, in vitro cell adhesion test with lens epithelial cells (LECs), extracted from porcine lens crystalline capsule, showed that ZnS had no deleterious effect on the biocompatibility of neat hydrogels, at least at low content.

Synthesis of poly(vinyl alcohol)/C(60) and poly(N-vinylpyrrolidone)/C(60) nanohybrids as potential photodynamic cancer therapy agents.

Well-defined poly(vinyl acetate) (PVAc) and poly(N-vinylpyrrolidone)-co-poly(vinyl acetate) (PNVP-co-PVAc) chains end-capped by Co(acac)(2) (acac=acetylacetonate) and prepared by cobalt-mediated radical polymerization (CMRP) are grafted onto a fullerene. Homolytic Co-C bond cleavage of the polymer chain ends at 30 degrees C releases the polymeric radicals that add onto C(60), thereby leading to the corresponding PVAc/C(60) and PNVP-co-PVAc/C(60) nanohybrids. The [polymer-Co(acac)(2)]/[C(60)] molar ratio was varied to adjust the structure of the nanohybrids, and more particularly the number of grafted arms. Finally, the potential of the hydrosoluble PVOH/C(60) nanohybrids, which result from the methanolysis of the ester groups of PVAc/C(60), and of the PNVP-co-PVAc/C(60) nanohybrids as photosensitizers for photodynamic therapy (PDT), was approached. First, photobleaching tests demonstrated the ability of these nanohybrids to produce singlet oxygen upon irradiation, which can play a role in cell damage. Second, cell viability assays demonstrated that both types of nanohybrids are deprived of intrinsic cytotoxicity in the dark, whereas they promoted significant cell mortality when subjected to light treatment. The selective response of these materials to irradiation makes them promising compounds for PDT.

Gold-loaded carbon nanoparticles from poly(vinyl alcohol)-b-poly(acrylonitrile) non-shell-cross-linked micelles.

Herein we show that a new amphiphilic poly(vinyl alcohol)-b-poly(acrylonitrile) block copolymer dispersed in water can be easily loaded with gold nanoparticles by addition of chlorauric acid followed by reduction by sodium borohydride. After deposition of the so-loaded micelles onto a silicon wafer, followed by an appropriate thermal treatment, the poly(acrylonitrile) core of the micelles is carbonized, while the poly(vinyl alcohol) shell is completely decomposed and volatilized, leading to gold encapsulated in carbon nanoparticles. The morphology of the micelles is maintained during thermal treatment without requiring shell-cross-linking of the micelles prior to pyrolysis.

Stabilized mixed micelles with a temperature-responsive core and a functional shell.

Formation and stabilization of multiresponsive micelles with a mixed poly(ethylene oxide)/polyelectrolyte shell and a temperature-responsive poly(propylene oxide) core were studied. Various poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers were mixed with poly(acrylic acid)-block-poly(propylene oxide)-block-poly(acrylic acid) (PAA-PPO-PAA) or poly(dimethylaminoethyl methacrylate)-block-poly(propylene oxide)-block-poly(dimethylaminoethyl methacrylate) (PDMAEMA-PPO-PDMAEMA) triblock copolymers. The micelles formed by binary mixtures of well-defined compositions at a specific pH were additionally stabilized by loading with pentaerythritol tetraacrylate (PETA), that was polymerized and cross-linked "in situ" with UV assistance. Depending on both the composition of the copolymers and the experimental conditions, either spherical or wormlike "stabilized polymeric micelles with a mixed shell" (SPMMS) were observed by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The SPMMS that contained PAA blocks in the shell were pH-sensitive, such that a reversible transition from well-dispersed SPMMS to precipitate could be promoted. In contrast, the SPMMS with a PEO/PDMAEMA mixed shell remained well-dispersed in the 2-11 pH range. Finally, SPMMS were successfully exploited as templates for the preparation of Ag nanoparticles (Ag NPs).

Stainless steel grafting of hyperbranched polymer brushes with an antibacterial activity: synthesis, characterization, and properties.

Two strategies were used for the preparation of hyperbranched polymer brushes with a high density of functional groups: (a) the cathodic electrografting of stainless steel by poly[2-(2-chloropropionate)ethyl acrylate] [poly(cPEA)], which was used as a macroinitiator for the atom transfer radical polymerization of an inimer, 2-(2-bromopropionate)ethyl acrylate in the presence or absence of heptadecafluorodecyl acrylate, (b) the grafting of preformed hyperbranched poly(ethyleneimine) onto poly(N-succinimidyl acrylate) previously electrografted onto stainless steel. The hyperbranched polymer, which contained either bromides or amines, was quaternized because the accordingly formed quaternary ammonium or pyridinium groups are known for antibacterial properties. The structure, chemical composition, and morphology of the quaternized and nonquaternized hyperbranched polymer brushes were characterized by ATR-FTIR reflectance, Raman spectroscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. The peeling test confirmed that the grafted hyperbranched polymer films adhered much more strongly to stainless steel than the nongrafted solvent-cast films. The quaternized hyperbranched polymer brushes were more effective in preventing both protein adsorption and bacterial adhesion than quaternary ammonium containing poly(cPEA) primary films, more likely because of the higher hydrophilicity and density of cationic groups.

Synthesis of biodegradable poly-epsilon-caprolactone microspheres by dispersion ring-opening polymerization in supercritical carbon dioxide.

A series of fluorinated diblock and triblock copolymers of poly(epsilon-caprolactone) and poly(heptadecafluorodecylacrylate) were prepared by combining ring-opening polymerization of epsilon-CL and atom transfer radical polymerization of the acrylate. These copolymers with well-controlled molecular weight and composition were characterized by (1)H NMR spectroscopy and used as stabilizers for the dispersion ring-opening polymerization of epsilon-CL in supercritical carbon dioxide. The effect of composition and architecture of the polymeric stabilizers on the stabilization of PCL microspheres was investigated. Finally, purification of PCL was successfully implemented by reactive supercritical fluid extraction of the tin catalyst.

Cobalt-mediated radical polymerization of acrylonitrile: kinetics investigations and DFT calculations.

The successful controlled homopolymerization of acrylonitrile (AN) by cobalt-mediated radical polymerization (CMRP) is reported for the first time. As a rule, initiation of the polymerization was carried out starting from a conventional azo-initiator (V-70) in the presence of bis(acetylacetonato)cobalt(II) ([Co(acac)(2)]) but also by using organocobalt(III) adducts. Molar concentration ratios of the reactants, the temperature, and the solvent were tuned, and the effect of these parameters on the course of the polymerization is discussed in detail. The best level of control was observed when the AN polymerization was initiated by an organocobalt(III) adduct at 0 degrees C in dimethyl sulfoxide. Under these conditions, poly(acrylonitrile) with a predictable molar mass and molar mass distribution as low as 1.1 was prepared. A combination of kinetic data, X-ray analyses, and DFT calculations were used to rationalize the results and to draw conclusions on the key role played by the solvent molecules in the process. These important mechanistic insights also permit an explanation of the unexpected "solvent effect" that allows the preparation of well-defined poly(vinyl acetate)-b-poly(acrylonitrile) by CMRP.

Normal and frictional forces between surfaces bearing polyelectrolyte brushes.

Normal and shear forces were measured as a function of surface separation, D, between hydrophobized mica surfaces bearing layers of a hydrophobic-polyelectrolytic diblock copolymer, poly(methyl methacrylate)- block-poly(sodium sulfonated glycidyl methacrylate) copolymer (PMMA- b-PSGMA). The copolymers were attached to each hydrophobized surface by their hydrophobic PMMA moieties with the nonadsorbing polyelectrolytic PSGMA tails extending into the aqueous medium to form a polyelectrolyte brush. Following overnight incubation in 10 (-4) w/v aqueous solution of the copolymer, the strong hydrophobic attraction between the hydrophobized mica surfaces across water was replaced by strongly repulsive normal forces between them. These were attributed to the osmotic repulsion arising from the confined counterions at long-range, together with steric repulsion between the compressed brush layers at shorter range. The corresponding shear forces on sliding the surfaces were extremely low and below our detection limit (+/-20-30 nN), even when compressed down to a volume fraction close to unity. On further compression, very weak shear forces (130 +/- 30 nN) were measured due to the increase in the effective viscous drag experienced by the compressed, sliding layers. At separations corresponding to pressures of a few atmospheres, the shearing motion led to abrupt removal of most of the chains out of the gap, and the surfaces jumped into adhesive contact. The extremely low frictional forces between the charged brushes (prior to their removal) is attributed to the exceptional resistance to mutual interpenetration displayed by the compressed, counterion-swollen brushes, together with the fluidity of the hydration layers surrounding the charged, rubbing polymer segments.

Imparting antifouling properties of poly(2-hydroxyethyl methacrylate) hydrogels by grafting poly(oligoethylene glycol methyl ether acrylate).

The antifouling properties of poly(2-hydroxyethyl methacrylate- co-methyl methacrylate) hydrogels were improved by the surface grafting of a brush of poly(oligoethylene glycol methyl ether acrylate) [poly(OEGA)]. The atom-transfer radical polymerization (ATRP) of OEGA (degree of polymerization = 8) was initiated from the preactivated surface of the hydrogel under mild conditions, thus in water at 25 degrees C. The catalytic system was optimized on the basis of two ligands [1,1,4,7,10,10-hexamethyl-triethylenetetramine (HMTETA) or tris[2-(dimethylamino)ethyl]amine (Me6TREN)] and two copper salts (CuIBr or CuICl). Faster polymerization was observed for the Me 6TREN/CuIBr combination. The chemical composition and morphology of the coated surface were analyzed by X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy, contact angle measurements by the water droplet and captive bubble methods, scanning electron microscopy, and environmental scanning electron microscopy. The hydrophilicity of the surface increased with the molar mass of the grafted poly(OEGA) chains, and the surface modifications were reported in parallel. The antifouling properties of the coatings were tested by in vitro protein adsorption and cell adhesion tests, with green fluorescent protein, beta-lactamase, and lens epithelial cells, as model proteins and model cells, respectively. The grafted poly(OEGA) brush decreased the nonspecific protein adsorption and imparted high cell repellency to the hydrogel surface.

Copper bromide complexed by fluorinated macroligands: towards microspheres by ATRP of vinyl monomers in scCO2.

We report the successful synthesis of poly(methyl methacrylate) (PMMA) by atom transfer radical polymerization using a catalyst ligated to a polymeric ligand having a dual role, i.e., the complexation of the copper salt and the stabilization of the growing PMMA particles; at the end of the polymerization, the catalyst is removed by supercritical fluid extraction leading to PMMA microspheres with low residual catalyst content.

Core-shell-corona micelles by PS-b-P2VP-b-PEO copolymers: focus on the water-induced micellization process.

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.

Mechanistic insights into the cobalt-mediated radical polymerization (CMRP) of vinyl acetate with cobalt(III) adducts as initiators.

Over the past few years, cobalt-mediated radical polymerization (CMRP) has proved efficient in controlling the radical polymerization of very reactive monomers, such as vinyl acetate (VAc). However, the reason for this success and the intimate mechanism remained basically speculative. Herein, two mechanisms are shown to coexist: the reversible termination of the growing poly(vinyl acetate) chains by the Co(acac)2 complex (acac: acetylacetonato), and a degenerative chain-transfer process. The importance of one contribution over the other strongly depends on the polymerization conditions, including complexation of cobalt by ligands, such as water and pyridine. This significant progress in the CMRP mechanism relies on the isolation and characterization of the very first cobalt adducts formed in the polymerization medium and their use as CMRP initiators. The structure proposed for these adducts was supported by DFT calculations. Beyond the control of the VAc polymerization, which is the best ever achieved by CMRP, extension to other monomers and substantial progress in macromolecular engineering are now realistic forecasts.

Synthesis of eight- and star-shaped poly(epsilon-caprolactone)s and their amphiphilic derivatives.

Spirocyclic tin dialkoxides are unique initiators for the ring-expansion polymerization of lactones leading to complex, but well-defined macromolecular architectures. In a first example, epsilon-caprolactone (epsilon CL) was polymerized, followed by the resumption of polymerization of a mixture of epsilon CL and epsilon CL alpha-substituted by a chloride (alpha Cl epsilon CL), so leading to "living" eight-shaped chains. Upon hydrolysis of the alkoxides, a four-arm star-shaped copolyester was formed, whose each arm was grafted by conversion of the chloride units into azides, followed by the Huisgen's [3+2] cycloaddition of alkyne end-capped poly(ethylene oxide) (PEO) onto the azide substituents. The complexity of this novel amphiphilic architecture was increased further by substituting the four-arm interconnecting PCL by an eight-shaped PCL. In a preliminary step, epsilon CL was polymerized followed by a few units of epsilon CL alpha-substituted by an acrylate. The intramolecular photo-crosslinking of the acrylates adjacent to the tin dialkoxides was effective in stabilizing the eight-shaped polyester while preserving the chain growth sites. This quite unusual tetrafunctional macroinitiator was used to copolymerize epsilon CL and alpha Cl epsilon CL, followed by hydrolysis of the alkoxides, conversion of the chloride units into azides and grafting of the four arms by PEO (see above). This architecture reported for the very first time is nothing but a symmetrical four-tail eight-shaped copolyester macromolecule.

Combination of electrografting and layer-by-layer deposition: an efficient way to tailor polymer coatings of (semi)-conductors.

This communication reports on a novel, simple and highly versatile concept, which consists in combining the advantages of two complementary and relevant techniques (i) electrografting and (ii) layer-by-layer deposition process with the goal to tailor strongly adhering coatings to (semi)-conducting surfaces imparting them with tunable specific properties.

Atomic force microscopy investigation of the morphology and the biological activity of protein-modified surfaces for bio- and immunosensors.

With the purpose of developing biosensors, the reliable proof of the biological activity of two new sensor systems was obtained by atomic force microscopy (AFM) in both the imaging and the single-molecule force spectroscopy modes. Antigens or antibodies of pharmacological interest were grafted onto self-assembled monolayers of thiols on gold, and AFM imaging demonstrated that the grafting process produced homogeneous submonolayers of isolated proteins. The analysis of the morphology of the surfaces at the different functionalization steps allowed evaluating the protein grafting density and showed that the recognition of complementary species present in the surrounding solution occurred. Single-molecule force spectroscopy experiments between the sensing surfaces and AFM probes, onto which the complementary species were grafted, enabled a direct and rapid test of the biological activity of the sensors by investigating the interaction occurring at the level of one single ligand-receptor bond. Ellipsometry and surface plasmon resonance allowed further characterization of the sensor surfaces and confirmed that the biological recognition took place.

PEGylated quaternized copolymer/DNA complexes for gene delivery.

The aim of this study was to improve the colloidal stability, decrease unspecific interactions with cells and blood components of a novel gene delivery system composed of epsilon-caprolactone and quaternized epsilon-caprolactone. For this purpose, diblock 50/50 copolymer was used to generate complexes with DNA by either the solvent evaporation technique and by dialysis. The size, surface charge and degree of interaction of the plasmid-loaded formulations were measured. Then, polyplexes were combined with a poly(CL)-b-PEG copolymer to create a hydrophilic corona on the surface of the complexes. The cytotoxicity, transfection efficiency and cellular uptake of polyplexes and their association with PEG were evaluated on HeLa cells. The dialysis method did not allow to reduce the size of complexes as compared to the solvent evaporation method. The zeta potential of polyplexes became positive from a charge ratio of 4. The degree of interaction of copolymer with plasmid DNA was very high. Cytotoxicity and transfection efficiency were found to be comparable to polyethylenimine 50 kDa. Association of polyplexes with poly(CL)-b-PEG copolymer led to a small increase in particle size and a sharp decrease of charge surface. Cytotoxicity, transfection efficiency and cellular uptake were significantly reduced relative to unshielded copolymer/DNA complexes. The PEGylated formulations may be an attractive approach for an in vivo application.

Mannosylated poly(ethylene oxide)-b-poly(epsilon-caprolactone) diblock copolymers: synthesis, characterization, and interaction with a bacterial lectin.

A novel bioeliminable amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) (PEO-b-PCL) diblock copolymer end-capped by a mannose residue was synthesized by sequential controlled polymerization of ethylene oxide and epsilon-caprolactone, followed by the coupling of a reactive mannose derivative to the PEO chain end. The anionic polymerization of ethylene oxide was first initiated by potassium 2-dimethylaminoethanolate. The ring-opening polymerization of epsilon-caprolactone was then initiated by the omega-hydroxy end-group of PEO previously converted into an Al alkoxide. Finally, the saccharidic end-group was attached by quaternization of the tertiary amine alpha-end-group of the PEO-b-PCL with a brominated mannose derivative. The copolymer was fully characterized in terms of chemical composition and purity by high-resolution NMR spectroscopy and size exclusion chromatography. Furthermore, measurements with a pendant drop tensiometer showed that both the mannosylated copolymer and the non-mannosylated counterpart significantly decreased the dichloromethane/water interfacial tension. Moreover, these amphiphilic copolymers formed monodisperse spherical micelles in water with an average diameter of approximately 11 nm as measured by dynamic light scattering and cryo-transmission electron microscopy. The availability of mannose as a specific recognition site at the surface of the micelles was proved by isothermal titration microcalorimetry (ITC), using the BclA lectin (from Burkholderia cenocepacia), which interacts selectively with alpha-D-mannopyranoside derivatives. The thermodynamic parameters of the lectin/mannose interaction were extracted from the ITC data. These colloidal systems have great potential for drug targeting and vaccine delivery systems.