Polyelectrolyte Multilayers as Nanocontainers for Functional Hydrophilic Molecules

We report on the introduction of small organic hydrophilic molecules (fluorescein, rhodamine B, and two coumarin-based dyes) in multilayers of strong polyelectrolytes, studied by X-ray reflectometry, UV/visible spectroscopy, and fluorescence measurements. Very low diffusion coefficients (about 10-17 cm2·s-1) were found for the inward diffusion of fluorescein in preformed multilayers. In addition, diffusion was accompanied by substantial variations of the thickness of the multilayer (up to 300%), ruling out the practical significance of inward diffusion as a tool to dope multilayers. We then attempted to coadsorb the fluorophores simultaneously with the polyions during the construction of the multilayer. However, displacement of small molecules by polyions of identical charge and outward diffusion of the fluorophores during the rinsing step resulted in very limited inclusion of the dye by this procedure. This issue was solved by introducing the fluorophore in all baths, including the rinsing ones. Then, the concentration of the multilayers in dye is directly related to the concentration of the dipping solutions and is dependent on the nature of the dye and of the multilayer. The outward diffusion of the fluorophores from these multilayers was studied, and very low diffusion coefficients were again determined, depending on the net charge of the dye. The ability to load rapidly polyelectrolyte multilayers with a variety of hydrophilic organic molecules of small molar mass, in tunable concentration, is a major outcome of the present study. It offers new opportunities to use these multilayers as templates for the confinement of active molecules in functional devices

Photo-Cross-Linked Self-Assembled Poly(ethylene oxide)-Based Hydrogels Containing Hybrid Junctions with Dynamic and Permanent Cross-Links

Homogeneous hydrogels were formed by self-assembly of triblock copolymers via association of small hydrophobic end blocks into micelles bridged by large poly­(ethylene oxide) central blocks. A fraction of the end blocks were photo-cross-linkable and could be rapidly cross-linked covalently by in situ UV irradiation. In this manner networks were formed with well-defined chain lengths between homogeneously distributed hybrid micelles that contained both permanent and dynamically cross-linked end blocks. Linear rheology showed a single relaxation mode before in situ irradiation intermediate between those of the individual networks. The presence of transient cross-links decreased the percolation threshold of the network rendered permanent by irradiation and caused a strong increase of the elastic modulus at lower polymer concentrations. Large amplitude oscillation and tensile tests showed significant increase of the fracture strain caused by the dynamic cross-links

Effect of Arm Exchange on the Liquid–Solid Transition of Dense Suspensions of Star Polymers

Star polymers with dynamic arm exchange are formed in water by self-assembly of amphiphilic diblock copolymers based on poly­(ethylene oxide) end capped with a small hydrophobic block. The arm exchange was arrested <i>in situ</i> by photo-cross-linking of the core. The effect of dynamic arm exchange on the osmotic compressibility and viscosity was investigated systematically as a function of the concentration and temperature. The discontinuous liquid–solid transition reported for dense polymeric micelle suspensions was found to be preserved after dynamic arm exchange was arrested <i>in situ</i>. The effect of cross-linking and aggregation number on the liquid–solid transition was investigated

Poly(ethylene oxide)/Gelatin-Based Biphasic Photocrosslinkable Hydrogels of Tunable Morphology for Hepatic Progenitor Cell Encapsulation

Macroporous hydrogels have great potential for biomedical applications. Liquid or gel-like pores were created in a photopolymerizable hydrogel by forming water-in-water emulsions upon mixing aqueous solutions of gelatin and a poly(ethylene oxide) (PEO)-based triblock copolymer. The copolymer constituted the continuous matrix, which dominated the mechanical properties of the hydrogel once photopolymerized. The gelatin constituted the dispersed phase, which created macropores in the hydrogel. The microstructures of the porous hydrogel were determined by the volume fraction of the gelatin phase. When volume fractions were close to 50 v%, free-standing hydrogels with interpenetrated morphology can be obtained thanks to the addition of a small amount of xanthan. The hydrogels displayed Young’s moduli ranging from 5 to 30 kPa. They have been found to be non-swellable and non-degradable in physiological conditions. Preliminary viability tests with hepatic progenitor cells embedded in monophasic PEO-based hydrogels showed rapid mortality of the cells, whereas encouraging viability was observed in PEO-based triblock copolymer/gelatin macroporous hydrogels. The latter has the potential to be used in cell therapy

Effect of Connectivity on the Structure and the Liquid–Solid Transition of Dense Suspensions of Soft Colloids

Aqueous solutions of multiarm flower-like poly­(ethylene oxide) (PEO) were formed and connected to various degrees by self-assembly. The structure was rendered permanent by <i>in situ</i> UV-irradiation. Dense suspensions of these single and connected soft colloids were studied by static and dynamic light scattering and viscosity measurements. The concentration dependence of the osmotic compressibility, the dynamic correlation length, and the viscosity of single flowers was shown to be close to that of equivalent PEO star-like polymers demonstrating that the effect of forming loops on the interaction is small. It was found that the osmotic compressibility and the dynamic correlation length of dense suspensions are not influenced by the bridging. However, when flower polymers are connected into clusters, motion in dense suspensions needs to be collective over larger length scales. This causes a much stronger increase of the viscosity for dense suspensions of interpenetrated clusters compared to single-flower polymers

Patchy Supramolecular Bottle-Brushes Formed by Solution Self-Assembly of Bis(urea)s and Tris(urea)s Decorated by Two Incompatible Polymer Arms

In an attempt to design urea-based Janus nanocylinders through a supramolecular approach, nonsymmetrical bis­(urea)­s and tris­(urea)­s decorated by two incompatible polymer arms, namely, poly­(styrene) (PS) and poly­(isobutylene) (PIB), were synthesized using rather straightforward organic and polymer chemistry techniques. Light scattering experiments revealed that these molecules self-assembled in cyclohexane by cooperative hydrogen bonds. The extent of self-assembly was limited for the bis­(urea)­s. On the contrary, reasonably anisotropic 1D structures (small nanocylinders) could be obtained with the tris­(urea)­s (<i>N</i>_agg ∼ 50) which developed six cooperative hydrogen bonds per molecule. ¹H transverse relaxation measurements and NOESY NMR experiments in cyclohexane revealed that perfect Janus nanocylinders with one face consisting of only PS and the other of PIB were not obtained. Nevertheless, phase segregation between the PS and PIB chains occurred to a large extent, resulting in patchy cylinders containing well separated domains of PIB and PS chains. Reasons for this behavior were proposed, paving the way to improve the proposed strategy toward true urea-based supramolecular Janus nanocylinders

Competition Between Steric Hindrance and Hydrogen Bonding in the Formation of Supramolecular Bottle Brush Polymers

The formation of supramolecular bottle-brush polymers consisting of a noncovalent backbone assembled through directional hydrogen bonds and of poly­(isobutylene) (PIB) side-chains was investigated in cyclohexane by light scattering. Two limiting cases were observed depending on the balance between the favorable formation of hydrogen bonds and the unfavorable stretching of the PIB chains within the supramolecular bottle-brushes, in agreement with a theoretical model developed by Wang et al. On one hand, a bisurea self-assembling unit able to form four cooperative hydrogen bonds per molecule led to relatively short supramolecular bottle-brushes, the length of which could be varied by modifying steric hindrance or by using solvent mixtures. On the other hand, supramolecular bottle-brush polymers exhibiting persistent lengths of more than 300 nm could be obtained by using trisureas that are able to form six hydrogen bonds per molecule. Their easy synthesis and the fact that it is possible to control their self-assembly into long supramolecular bottle-brush polymers make polymer-decorated bisureas and trisureas an attractive alternative to cyclopeptides and shape-persistent rings for the creation of supramolecular nanostructures

Polymersomes from Amphiphilic Glycopolymers Containing Polymeric Liquid Crystal Grafts

For the first time, polymersomes were obtained by self-assembly in water of amphiphilic grafted glycopolymers based on dextran polysaccharidic backbone and polymeric liquid crystal grafts (poly­(diethylene glycol cholesteryl ether acrylate), PDEGCholA). After measuring the properties of these glycopolymers in term of surfactancy, the influence of their structural parameters on their self-assemblies once dispersed in water was investigated by static and dynamic light scattering and by cryogenic transmission electron microscopy (cryo-TEM). Based on the results, a proper design of Dex-g^N-PDEGCholA^F leads to hollow vesicular structure formulation known as polymersome

Self-Assembly and Critical Solubility Temperature of Supramolecular Polystyrene Bottle-Brushes in Cyclohexane

The formation of polystyrene (PS) supramolecular bottle-brushes by self-assembly in cyclohexane of hydrogen-bonding tris­(urea) units decorated by PS chains was investigated using light and neutron scattering. Atom transfer radical polymerization (ATRP) was used to control the length of the PS side-chains and allowed the straightforward synthesis of the targeted tris­(urea)­s. It was shown that their extent of self-assembly strongly depended on the degree of polymerization and chemical nature of the polymer side chains, in contrast with what was previously observed with cyclic oligopeptides, another type of self-assembling units. With sufficiently short PS side-chains, anisotropic supramolecular bottle-brushes could be obtained. Their critical solubility temperature, <i>T</i>_c, was measured in cyclohexane, proving experimentally for the first time that densely grafted PS bottle-brushes exhibit a much lower <i>T</i>_c than linear PS or even star-shaped PS of similar molecular weight