Giant hollow fiber formation through self-assembly of oppositely charged polyelectrolyte brushes and gold nanoparticles

We report on the use of binary mixtures of oppositely charged gold nanoparticles (AuNPs) and spherical polyelectrolyte brushes (SPBs), consisting of a polystyrene core onto which long polystyrene sulfonate chains are grafted, as a simple model system to investigate the influence of directional interactions on self-assembly. We demonstrate that the mixing ratio, i.e., the number of AuNPs per SPB, has a profound influence on self-assembly. In particular we report on the formation of giant hollow fibers, and present a thorough characterization of these nanostructures. We speculate that the adsorption of a few AuNPs on the SPBs appears to direct the tubular self-assembly, and discuss the analogy to the case of modified proteins such as tubulin under the action of nucleotides

Crystallization-induced aggregation of block copolymer micelles: influence of crystallization kinetics on morphology

We present a systematic investigation of the crystallization and aggregation behavior of a poly(1,2-butadiene)-block-poly(ethylene oxide) diblock copolymer (PB-b-PEO) in n-heptane. n-Heptane is a poor solvent for PEO and at 70°C the block copolymer self-assembles into spherical micelles composed of a liquid PEO core and a soluble PB corona. Time- and temperature-dependent light scattering experiments revealed that when crystallization of the PEO cores is induced by cooling, the crystal morphology depends on the crystallization temperature (T c ): Below 30°C, the high nucleation rate of the PEO core dictates the growth of the crystals by a fast aggregation of the micelles into meander-like (branched) structures due to a depletion of the micelles at the growth front. Above 30°C the nucleation rate is diminished and a relatively small crystal growth rate leads to the formation of twisted lamellae as imaged by scanning force microscopy. All data demonstrate that the formation mechanism of the crystals through micellar aggregation is dictated by two competitive effects, namely, by the nucleation and growth of the PEO core

Anisotropic responsive microgels with tuneable shape and interactions

Highly monodisperse polystyrene/poly(N-isopropylmethacrylamide) (PS-PNIPMAM) core-shell composite microgels were synthesized and further nanoengineered in either ellipsoidal, faceted or bowl-shaped particles. Beside their anisotropy in shape, the microgel design enables an exquisite control of the particle conformation, size and interactions from swollen and hydrophilic to collapsed and hydrophobic using temperature as an external control variable. The post-processing procedures and the characterization of the different particles are first presented. Their potential as model systems for the investigation of the effects of anisotropic shape and interactions on the phase behavior is further demonstrated. Finally, the self-assembly of bowl-shaped composite microgel particles is discussed, where the temperature and an external AC electric field are employed to control the interactions from repulsive to attractive and from soft repulsive to dipolar, respectively

A new route towards colloidal molecules with externally tunable interaction sites.

We describe a route towards self-assembled colloidal molecules, where thermoresponsive microgels serve as discrete, externally tunable interaction sites. The ability of poly(N-isopropylacrylamide) (PNIPAM) and poly(N-isopropylmethacrylamide) (PNIPMAM) microgels to adsorb to the oil/water (O/W) interface and create Pickering-stabilized mini-emulsions was first tested using the controlled addition of sub-micron-sized polydimethylsiloxane (PDMS) oil droplets to a microgel suspension. The use of a mixture of PNIPAM and PNIPMAM microgels differing in size and fluorescent labeling then resulted in the formation of thermosensitive patchy particles, where the patches can be visualised using fluorescence confocal laser scanning microscopy. The size of the assembled decorated droplets and the number of adsorbed microgels was further reduced using an in situ synthesis approach, where the oil droplets are directly synthesised in the presence of microgels. This results in the formation of highly monodisperse microgel-decorated PDMS oil droplets with a small number of microgels adsorbed to the droplet interface. We demonstrate that we can use temperature to change the interaction potential between these interaction sites and thus trigger a reversible association of the individual decorated droplets at temperatures above the volume phase transition temperature TVPT of the microgels. Finally, we investigated the temporal evolution of the decorated droplets and found that small and well-defined clusters of microgels form in the early stages of the process primarily through the action of capillary forces. These clusters mimic colloidal molecules with a small number of discrete and thermosensitive binding sites

Tunable Adsorption of Soft Colloids on Model Biomembranes.

A simple procedure is developed to probe in situ the association between lipid bilayers and colloidal particles. Here, a one-step method is applied to generate giant unilamellar 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) vesicles (GUVs) by application of an alternating electric field directly in the presence of thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) microgels. We demonstrate that the soft PNIPAM microgel particles act as switchable stabilizers for lipid membranes. The change of the particle conformation from the swollen to the collapsed state enables the reversible control of the microgel adsorption as a function of temperature. At 20 °C, the swollen and hydrophilic soft microgel particles adsorb evenly and densely pack in 2D hexagonal arrays at the DOPC GUV surfaces. In contrast, at 40 °C, that is, above the volume phase transition temperature (TVPT = 32 °C) of the PNIPAM microgels, the collapsed and more hydrophobic particles partially desorb and self-organize into domains at the GUV/GUV interfaces. This study shows that thermoresponsive PNIPAM microgels can be used to increase and control the stability of lipid vesicles where the softness and deformability of these types of particles play a major role. The observed self-assembly, where the organization and position of the particles on the GUV surface can be controlled "on demand", opens new routes for the design of nanostructured materials

Assembling oppositely charged lock and key responsive colloids: A mesoscale analog of adaptive chemistry

We have seen a considerable effort in colloid sciences to copy Nature’s successful strategies to fabricate complex functional structures through self-assembly. This includes attempts to design colloidal building blocks and their intermolecular interactions, such as creating the colloidal analogs of directional molecular interactions, molecular recognition, host-guest systems, and specific binding. We show that we can use oppositely charged thermoresponsive particles with complementary shapes, such as spherical and bowl-shaped particles, to implement an externally controllable lock-and-key self-assembly mechanism. The use of tunable electrostatic interactions combined with the temperature-dependent size and shape and van der Waals interactions of these building blocks provides an exquisite control over the selectivity and specificity of the interactions and self-assembly process. The dynamic nature of the mechanism allows for reversibly cycling through various structures that range from weakly structured dense liquids to well-defined molecule-shaped clusters with different configurations through variations in temperature and ionic strength. We link this complex and dynamic self-assembly behavior to the relevant molecular interactions, such as screened Coulomb and van der Waals forces and the geometrical complementarity of the two building blocks, and discuss our findings in the context of the concepts of adaptive chemistry recently introduced to molecular systems