What is the role of PEO chains in the assembly of core-corona supraparticles in aqueous dispersions?

Hypothesis The assembly of core-corona supraparticles in aqueous dispersions has been regularly assisted by auxiliary monomers/oligomers which modify the individual particles with, e.g., surface grafting of polyethylene oxide (PEO) chains or other hydrophilic monomers. However, this modification complicates the preparation and purification procedures and increases potential upscaling efforts. Hybrid polymer-silica core-corona supracolloids could be more simply assembled if the PEO chains from surfactants, typically used by default as polymer stabilizers, concomitantly act as assembly promotors. The supracolloids assembly could therefore be more easily achieved without requiring particles functionalization or post-purification steps. Methods The self-assembly of supracolloidal particles prepared with PEO-surfactant stabilized (Triton X-405) and/or PEO-grafted polymer particles is compared to differentiate the roles of the PEO chains in the assembly of core-corona supraparticles. Using time-resolved dynamic light scattering (DLS) and cryogenic transmission electron microscopy(cryo-TEM), the effect of concentration of PEO chains (from surfactant) on the kinetics and dynamics of supracolloids assembly is investigated. Self-consistent field (SCF) lattice theory was used to numerically study the distribution of PEO chains at the interfaces present in the supracolloidal dispersions. Findings The PEO based surfactant can be used as assembly promoter of core-corona hybrid supracolloids due to its amphiphilic nature and via establishing hydrophobic interactions. The concentration of the PEO surfactant, and especially the PEO chains distribution over the different interfaces, crucially affect the supracolloids assembly. A simplified pathway for preparing hybrid supracolloidal particles with a well-controlled corona coverage over polymer cores is presented.

Competition between deformation and free volume quantified by 3D image analysis of red blood cell.

Cells in living organisms are subjected to mechanical strains caused by external forces like overcrowding, resulting in strong deformations that affect cell function. We study the interplay between deformation and crowding of red blood cells (RBCs) in dispersions of nonabsorbing rod-like viruses. We identify a sequence of configurational transitions of RBC doublets, including configurations that can only be induced by long-ranged attraction: highly fluctuating T-shaped and face-to-face configurations at low, and doublets approaching a complete spherical configuration at high, rod concentrations. Complementary simulations are used to explore different energy contributions to deformation as well as the stability of RBC doublet configurations. Our advanced analysis of 3D reconstructed confocal images of RBC doublets quantifies the depletion interaction and the resulting deformation energy. Thus, we introduce a noninvasive, high-throughput platform that is generally applicable to investigate the mechanical response of biological cells to external forces and characterize their mechanical properties.

Excluded volume interactions and phase stability in mixtures of hard spheres and hard rods.

In this paper we study excluded volume interactions, the free volume fraction available, and the phase behaviour, in mixtures of hard spheres (HS) and hard rods, modeled as spherocylinders. We use free volume theory (FVT) to predict various physical properties and compare to Monte Carlo computer simulations. FVT is used at two levels. We use the original FVT approach in which it is assumed that the correlations of the HS are not affected by the rods. This is compared to a recent, more rigorous, FVT approach which includes excluded volume interactions between the different components at all levels. We find that the novel rigorous FVT approach agrees well with computer simulation results at the level of free volume available, as well as for the phase stability. The FVT predictions show significant quantitative and qualitative deviations with respect to the original FVT approach. The phase transition curves are systematically at higher rod concentrations than previously predicted. Furthermore, the calculations revealed that a certain asphericity is required to induce isostructural fluid-fluid coexistence and the stability region is highly dependent on the size ratio between the rods and the spheres.

Distribution of block copolymers in drying polymer films.

HYPOTHESIS: Block copolymers (BCP) consisting of a polar block and a surface active apolar block are widely used for surface functionalization of polymer films. The characteristics of the copolymer blocks determine whether surface segregation and/or phase separation occurs, for a given bulk mixture. This data can be used to find the optimal BCP composition where high surface enrichment is obtained without accumulation of phase separated BCP in the bulk. METHODS: The distribution of poly(ethylene oxide)-polydimethylsiloxane (PEO-PDMS) BCP in a polymer formulation relevant for coating applications is systematically investigated. The surface segregation is studied in liquid formulations with surface tension measurements and dried films with X-ray photoelectron spectroscopy (XPS), whereas phase separation is quantified using turbidity measurements. The results are compared with Scheutjens-Fleer self-consistent field (SF-SCF) computations, which are also applied to determine the effect of film drying on BCP phase stability and surface segregation. FINDINGS: Longer PDMS blocks result in lower interfacial tension of the liquid polymer mixture, whereas for the cured films, the largest PDMS concentration at the interface was obtained for intermediate PDMS block lengths. This is explained by the observation that phase separation already occurs at very low BCP concentrations for long PDMS blocks. The SCF predictions qualitatively agree with the experimental results and reveal that the BCP distribution changes significantly during film drying.

Selective colloidal bonds via polymer-mediated interactions.

Regioselectivity in colloidal self-assembly typically requires specific chemical interactions to guide particle binding. In this paper, we describe a new method to form selective colloidal bonds that relies solely on polymer adsorption. Mixtures of polymer-coated and bare particles are initially stable due to long-ranged electrostatic repulsion. When their charge is screened, the two species can approach each other close enough for polymer bridges to form, binding the particles together. By utilizing colloidal dumbbells, where each lobe is coated with polymer brushes of differing lengths, we demonstrate that the Debye screening length serves as a selective switch for the assembly of bare tracer particles onto the two lobes. We model the interaction using numerical self-consistent field lattice computations and show how regioselectivity arises from just a few nanometers difference in polymer brush length.

Phase behaviour of colloidal superballs mixed with non-adsorbing polymers.

Inspired by experimental work on colloidal cuboid-polymer dispersions (Rossi et al., Soft Matter, 7, 4139 (2011)) we have theoretically studied the phase behaviour of such mixtures. To that end, free volume theory (FVT) was applied to predict the phase behaviour of mixtures of superballs and non-adsorbing polymer chains in a common solvent. Closed expressions for the thermodynamic properties of a suspension of hard colloidal superballs have been derived, accounting for fluid (F), face-centred cubic (FCC) and simple cubic (SC) phase states. Even though the considered solid phases are approximate, the hard superballs phase diagram semi-quantitatively matches with more evolved methods. The theory developed for the cuboid-polymer mixture reveals a rich phase behaviour, which includes not only isostructural F1-F2 coexistence, but also SC1-SC2 coexistence, several triple coexistences, and even a quadruple-phase coexistence region (F1-F2-SC-FCC). The model proposed offers a tool to asses the stability of cuboid-polymer mixtures in terms of the colloid-to-polymer size ratio.

Water-in-Water Emulsions Stabilized by Nanoplates.

Ultrathin plate-like colloidal particles are effective candidates for Pickering stabilization of water-in-water emulsions, a stabilization that is complicated by the thickness and ultralow tension of the water-water interface. Plate-like particles have the advantage of blocking much of the interface while simultaneously having a low mass. Additionally, the amount of blocked interface is practically independent of the equilibrium contact angle θ at which the water-water interface contacts the nanoplates. As a result, the adsorption of nanoplates is stronger than for spheres with the same maximal cross section, except if θ = 90°.