PEO-b-PPO star-shaped polymers enhance the structural stability of electrostatically coupled liposome/polyelectrolyte complexes.

We propose a strategy to counteract the salt-driven disassembly of multiliposomal complexes made by electrostatic co-assembly of anionic small unilamellar liposomes and cationic star-shaped polyelectrolytes (made of quaternized poly(dimethylaminoethyl methacrylate) (qPDMAEMA100)3.1). The combined action of (qPDMAEMA100)3.1 and a nonionic star-shaped polymer (PEO12-b-PPO45)4, which comprises diblock copolymer arms uniting a poly(ethylene oxide) PEO inner block and a poly(propylene oxide) PPO terminal block, leads to a stabilization of these complexes against disintegration in saline solutions. Hereby, the anchoring of the PPO terminal blocks to the lipid bilayer and the bridging between several liposomes are at the origin of the promoted structural stability. Two-focus fluorescence correlation spectroscopy verifies the formation of multiliposomal complexes with (PEO12-b-PPO45)4. The polyelectrolyte and the amphiphilic polymer work synergistically, as the joint action still assures some membrane integrity, which is not seen for the mere (PEO12-b-PPO45)4-liposome interaction alone.

Stimulated Transitions of Directed Nonequilibrium Self-Assemblies.

Near-equilibrium stimulus-responsive polymers have been used extensively to introduce morphological variations in dependence of adaptable conditions. Far-less-well studied are triggered transformations at constant conditions. These require the involvement of metastable states, which are either able to approach the equilibrium state after deviation from metastability or can be frozen on returning from nonequilibrium to equilibrium. Such functional nonequilibrium macromolecular systems hold great promise for on-demand transformations, which result in substantial changes in their material properties, as seen for triggered gelations. Herein, a diblock copolymer system consisting of a hydrophilic block and a block that is responsive to both pressure and temperature, is introduced. This species demonstrates various micellar transformations upon leaving equilibrium/nonequilibrium states, which are triggered by a temperature deflection or a temporary application of hydrostatic pressure.

Balancing Segregation and Complexation in Amphiphilic Copolymers by Architecture and Confinement.

Segregation is a well-known principle for micellization, as solvophobic components try to minimize interactions with other entities (such as solvent) by self-assembly. An opposite principle is based on complexation (or coacervation), leading to the coassembly/association of different components. Most cases in the literature rely on only one of these modes, though the classical micellization scheme (such as spherical micelles, wormlike micelles, and vesicles) can be enriched by a subtle balance of segregation and complexation. Because of their counteraction, micellar constructs with unprecedented structure and behavior could be obtained. In this feature, systems are highlighted, which are between both mechanisms, and we study concentration, architecture, and confinement effects. Systems with inter- and intramolecular interactions are presented, and the effects of polymer topology and monomer sequence on the resulting structures are discussed. It is shown that complexation can lead to altered micellization behavior as the complex of one hydrophobic and one hydrophilic component can have a very low surface tension toward the solvent. Then, the more soluble component is enriched at the surface of the complex and acts as a microsurfactant. Although segregation dominates for amphiphilic copolymers in solution, the effect of the complexation can be enhanced by branching (change of architecture). Another possibility to enhance the complexation is by confining copolymers in a (pseudo-) 2D environment (like the one available at liquid-liquid interfaces). These observations show how new structural features can be achieved by tuning the subtle balance between segregation and complexation/solubilization.

Facile Screening of Various Micellar Morphologies by Blending Miktoarm Stars and Diblock Copolymers.

A time-saving phase-diagram screening is introduced for the self-assembly of miktoarm star polymers with different arm numbers for the insoluble part. Agreeing with theory, all conventional micellar morphologies (spherical star-like micelles, cylindrical micelles and vesicles) can be accessed by adjusting the average arm number when blending miktoarm stars with diblock copolymers (at constant arm/block lengths). Additionally, a rare clustered vesicle phase is detected. Hence, this approach permits an easy tuning of the equilibrium morphology and the size of the solvophobic domain. Such screening by scattering, ultracentrifugation, and electron microscopy techniques assists the targeted synthesis of miktoarm stars with a well-defined arm number, aimed at the morphology control of the nanostructures without blending. Specifically, we demonstrate a systematic variation of all classical micellar morphologies based on interpolyelectrolyte complexes (IPECs), consisting of a water-insoluble part formed by electrostatically coupled poly(styrenesulfonate) chains/quaternized poly(2-(dimethylamino)ethyl methacrylate) blocks, being stabilized by hydrophilic poly(ethylene oxide) blocks.

Interface-enforced complexation between copolymer blocks.

Binary diblock copolymers and corresponding ternary miktoarm stars are studied at oil-water interfaces. All polymers contain oil-soluble poly(propylene oxide) PPO, water-soluble poly(dimethylaminoethyl methacrylate) PDMAEMA and/or poly(ethylene oxide) PEO. The features of their Langmuir compression isotherms are well related to the ones of the corresponding homopolymers. Within the Langmuir-trough, PEO-b-PPO acts as the most effective amphiphile compared to the other PPO-containing copolymers. In contrast, the compression isotherms show a complexation of PPO and PDMAEMA for PPO-b-PDMAEMA and the star, reducing their overall amphiphilicity. Such complex formation between the blocks of PPO-b-PDMAEMA is prevented in bulk water but facilitated at the interface. The weakly-interacting blocks of PPO-b-PDMAEMA form a complex due to their enhanced proximity in such confined environments. Scanning force microscopy and Monte Carlo simulations with varying confinement support our results, which are regarded as compliant with the mathematical random walk theorem by Pólya. Finally, the results are expected to be of relevance for e.g. emulsion formulation and macromolecular engineering.

Effects of architecture on the stability of thermosensitive unimolecular micelles.

The influence of architecture on polymer interactions is investigated and differences between branched and linear copolymers are found. A comprehensive picture is drawn with the help of a fluorescence approach (using pyrene and 4HP as probe molecules) together with IR or NMR spectroscopy and X-ray/light scattering measurements. Five key aspects are addressed: (1) synergistic intramolecular complexation within miktoarm stars. The proximity of thermoresponsive poly(propylene oxide) (PPO) and poly(dimethylaminoethyl methacrylate) (PDMAEMA) within a miktoarm star leads to complexation between these weakly interacting partners. Consequently, the original properties of the constituents are lost, showing hydrophobic domains even at low temperatures, at which all homopolymers are water soluble. (2) Unimolecular micelles for miktoarm stars. The star does not exhibit intermolecular self-assembly in a large temperature range, showing unimers up to 55 °C. This behavior was traced back to a reduced interfacial tension between the PPO-PDMAEMA complex and water (PDMAEMA acts as a "microsurfactant"). (3) Unimolecular to multimolecular micelle transition for stars. The otherwise stable unimolecular micelles self-assemble above 55 °C. This aggregation is not driven by PPO segregation, but by collapse of residual PDMAEMA. This leads to micrometer-sized multilamellar vesicles stabilized by poly(ethylene oxide) (PEO). (4) Prevention of pronounced complexation within diblock copolymers. In contrast to the star copolymers, PPO and PDMAEMA adapt rather their homopolymer behavior within the diblock copolymers. Then they show their immanent LCST properties, as PDMAEMA turns insoluble at elevated temperatures, whereas PPO becomes hydrophobic below room temperature. (5) Two-step micellization for diblock copolymers. Upon heating of linear copolymers, the dehydration of PPO is followed by self-assembly into spherical micelles. An intermediate prevalence of unimolecular micelles is revealed in a small temperature window between PPO collapse and self-assembly of PEO-b-PPO. Also for PPO-b-PDMAEMA, PPO segregation prevails after initial weak complexation, leading to micelles with a PPO core. Considerable amounts of water are entrapped within the collapsed PDMAEMA domains above 55 °C (skin effect), preventing PPO-PDMAEMA complexation within precipitating PPO-b-PDMAEMA. Further, collapsed PDMAEMA is rather polar as sensed by pyrene and 4HP. In summary, advanced macromolecular architectures can lead to an unprecedented intramolecular self-assembly behavior, where internal complexation prevents intermolecular aggregation.

Unimolecular Janus Micelles by Microenvironment-Induced, Internal Complexation.

A noncentrosymmetric, star-shaped polymeric system is presented, which forms unimolecular micelles upon complexation of poly(propylene oxide) (PPO) with poly(dimethylaminoethyl methacrylate) (PDMAEMA). The influence of macromolecular architecture on the hydrophobicity of PPO and its interaction with PDMAEMA is investigated. Within stars, a complex between PPO and PDMAEMA is formed, lowering the interfacial tension of the hydrophobic domain (PDMAEMA acts as a "microsurfactant" for PPO). This leads to a pronounced drop in aggregation number compared to similar diblock copolymers, as corroborated by a scaling approach.