Anisotropic mesoporous silica/microgel core-shell responsive particles.

Hybrid anisotropic microgels were synthesised using mesoporous silica as core particles. By finely controlling the synthesis conditions, the latter can be obtained with different shapes such as platelets, primary particles or rods. Using the core particles as seeds for precipitation polymerisation, a crosslinked poly(N-isopropylacrylamide) (PNIPAM) microgel shell could be grown at the surface, conferring additional thermo-responsive properties. The different particles were characterised using scattering and imaging techniques. Small angle X-ray scattering (SAXS) was employed to identify the shape and porous organisation of the core particles and dynamic light scattering (DLS) to determine the swelling behaviour of the hybrid microgels. In addition, cryogenic transmission electron microscopy (cryo-TEM) imaging of the hybrids confirms the different morphologies as well as the presence of the microgel network and the core-shell conformation. Finally, the response of the particles to an alternating electric field is demonstrated for hybrid rod-shaped microgels in situ using confocal laser scanning microscopy (CLSM).

Assembling responsive microgels at responsive lipid membranes.

Directed colloidal self-assembly at fluid interfaces can have a large impact in the fields of nanotechnology, materials, and biomedical sciences. The ability to control interfacial self-assembly relies on the fine interplay between bulk and surface interactions. Here, we investigate the interfacial assembly of thermoresponsive microgels and lipogels at the surface of giant unilamellar vesicles (GUVs) consisting of phospholipids bilayers with different compositions. By altering the properties of the lipid membrane and the microgel particles, it is possible to control the adsorption/desorption processes as well as the organization and dynamics of the colloids at the vesicle surface. No translocation of the microgels and lipogels through the membrane was observed for any of the membrane compositions and temperatures investigated. The lipid membranes with fluid chains provide highly dynamic interfaces that can host and mediate long-range ordering into 2D hexagonal crystals. This is in clear contrast to the conditions when the membranes are composed of lipids with solid chains, where there is no crystalline arrangement, and most of the particles desorb from the membrane. Likewise, we show that in segregated membranes, the soft microgel colloids form closely packed 2D crystals on the fluid bilayer domains, while hardly any particles adhere to the more solid bilayer domains. These findings thus present an approach for selective and controlled colloidal assembly at lipid membranes, opening routes toward the development of tunable soft materials.

Directed Self-Assembly of Polarizable Ellipsoids in an External Electric Field.

The interplay between shape anisotropy and directed long-range interactions enables the self-assembly of complex colloidal structures. As a recent highlight, ellipsoidal particles polarized in an external electric field were observed to associate into well-defined tubular structures. In this study, we systematically investigate such directed self-assembly using Monte Carlo simulations of a two-point-charge model of polarizable prolate ellipsoids. In spite of its simplicity and computational efficiency, we demonstrate that the model is capable of capturing the complex structures observed in experiments on ellipsoidal colloids at low volume fractions. We show that, at sufficiently high electric field strength, the anisotropy in shape and electrostatic interactions causes a transition from three-dimensional crystal structures observed at low aspect ratios to two-dimensional sheets and tubes at higher aspect ratios. Our work thus illustrates the rich self-assembly behavior accessible when exploiting the interplay between competing long- and short-range anisotropic interactions in colloidal systems.

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.

Anisotropic magnetic particles in a magnetic field.

We characterize the structural properties of magnetic ellipsoidal hematite colloids with an aspect ratio ρ ≈ 2.3 using a combination of small-angle X-ray scattering and computer simulations. The evolution of the phase diagram with packing fraction ϕ and the strength of an applied magnetic field B is described, and the coupling between orientational order of magnetic ellipsoids and the bulk magnetic behavior of their suspension addressed. We establish quantitative structural criteria for the different phase and arrest transitions and map distinct isotropic, polarized non-nematic, and nematic phases over an extended range in the ϕ-B coordinates. We show that upon a rotational arrest of the ellipsoids around ϕ = 0.59, the bulk magnetic behavior of their suspension switches from superparamagnetic to ordered weakly ferromagnetic. If densely packed and arrested, these magnetic particles thus provide persisting remanent magnetization of the suspension. By exploring structural and magnetic properties together, we extend the often used colloid-atom analogy to the case of magnetic spins.

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.

Field-induced assembly of colloidal ellipsoids into well-defined microtubules.

Current theoretical attempts to understand the reversible formation of stable microtubules and virus shells are generally based on shape-specific building blocks or monomers, where the local curvature of the resulting structure is explicitly built-in via the monomer geometry. Here we demonstrate that even simple ellipsoidal colloids can reversibly self-assemble into regular tubular structures when subjected to an alternating electric field. Supported by model calculations, we discuss the combined effects of anisotropic shape and field-induced dipolar interactions on the reversible formation of self-assembled structures. Our observations show that the formation of tubular structures through self-assembly requires much less geometrical and interaction specificity than previously thought, and advance our current understanding of the minimal requirements for self-assembly into regular virus-like structures.

Advanced multiresponsive comploids: from design to possible applications.

We extend the commonly used synthesis strategies for responsive microgels to the design of novel multiresponsive and multifunctional nanoparticles that combine inorganic magnetic, metallic/catalytic and thermoresponsive organic moieties. Magnetic responsiveness is implemented through the integration of silica-coated maghemite nanoparticles into fluorescently labeled crosslinked poly(N-isopropylmethacrylamide) microgels. These particles are then employed as templates for the in situ reduction of catalytically active gold nanoparticles. In order to tune the reactivity of the catalyst through a thermally controlled barrier, an additional layer of crosslinked poly(N-isopropylacrylamide) is added in the final step. We subsequently demonstrate that these particles can be employed as smart catalysts. We show that the thermoresponsive nature of the outer particle shell not only provides control over the catalytic activity, but when combined with a magnetic core allows for very efficient removal of the catalytic system through temperature-controlled reversible coagulation and subsequent magnetophoresis in an applied magnetic field gradient. We finally discuss the use of this design principle for the synthesis of complex hybrid particles for various applications that would all profit from their multiresponsive and multifunctional nature.

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.

Strain-induced macroscopic magnetic anisotropy from smectic liquid-crystalline elastomer-maghemite nanoparticle hybrid nanocomposites.

We combine tensile strength analysis and X-ray scattering experiments to establish a detailed understanding of the microstructural coupling between liquid-crystalline elastomer (LCE) networks and embedded magnetic core-shell ellipsoidal nanoparticles (NPs). We study the structural and magnetic re-organization at different deformations and NP loadings, and the associated shape and magnetic memory features. In the quantitative analysis of a stretching process, the effect of the incorporated NPs on the smectic LCE is found to be prominent during the reorientation of the smectic domains and the softening of the nanocomposite. Under deformation, the soft response of the nanocomposite material allows the organization of the nanoparticles to yield a permanent macroscopically anisotropic magnetic material. Independent of the particle loading, the shape-memory properties and the smectic phase of the LCEs are preserved. Detailed studies on the magnetic properties demonstrate that the collective ensemble of individual particles is responsible for the macroscopic magnetic features of the nanocomposite.

Liquid-crystalline elastomer-nanoparticle hybrids with reversible switch of magnetic memory.

A stimuli-responsive material is synthesized that combines the actuation potential of liquid-crystalline elastomers with the anisotropic magnetic properties of ellipsoidal iron oxide nanoparticles. The resulting nanocomposite exhibits unique shape-memory features with magnetic information, which can be reversibly stored and erased via parameters typical of soft materials, such as high deformations, low stresses, and liquid-crystalline smectic-isotropic transition temperatures.

Sphere-to-Rod Transition of Micelles formed by the Semicrystalline Polybutadiene-block-Poly(ethylene oxide) Block Copolymer in a Selective Solvent.

We present a morphological study of the micellization of an asymmetric semicrystalline block copolymer, poly(butadiene)-block-poly(ethylene oxide), in the selective solvent n-heptane. The molecular weights of the poly(butadiene) (PB) and poly(ethylene oxide) (PEO) blocks are 26 and 3.5 kg · mol(-1) , respectively. In this solvent, micellization into a liquid PEO-core and a corona of PB-chains takes place at room temperature. Through a thermally controlled crystallization of the PEO core at -30 °C, spherical micelles with a crystalline PEO core and a PB corona are obtained. However, crystallization at much lower temperatures (-196 °C; liquid nitrogen) leads to the transition from spherical to rod-like micelles. With time these rod-like micelles aggregate and form long needles. Concomitantly, the degree of crystallinity of the PEO-cores of the rod-like micelles increases. The transition from a spherical to a rod-like morphology can be explained by a decrease of solvent power of the solvent n-heptane for the PB-corona chains: n-Heptane becomes a poor solvent at very low temperatures leading to a shrinking of the coronar chains. This favors the transition from spheres to a morphology with a smaller mean curvature, that is, to a cylindrical morphology.