Self-assembly of defined core-shell ellipsoidal particles at liquid interfaces.

Hypothesis: Ellipsoidal particles confined at liquid interfaces exhibit complex self-assembly due to quadrupolar capillary interactions, favouring either tip-to-tip or side-to-side configurations. However, predicting and controlling which structure forms remains challenging. We hypothesize that introducing a polymer-based soft shell around the particles will modulate these capillary interactions, providing a means to tune the preferred self-assembly configuration based on particle geometry and shell properties.

Capillary Assembly of Anisotropic Particles at Cylindrical Fluid-Fluid Interfaces.

The unique behavior of colloids at liquid interfaces provides exciting opportunities for engineering the assembly of colloidal particles into functional materials. The deformable nature of fluid-fluid interfaces means that we can use the interfacial curvature, in addition to particle properties, to direct self-assembly. To this end, we use a finite element method (Surface Evolver) to study the self-assembly of rod-shaped particles adsorbed at a simple curved fluid-fluid interface formed by a sessile liquid drop with cylindrical geometry.

Using adsorption kinetics to assemble vertically aligned nanorods at liquid interfaces for metamaterial applications.

Vertically aligned monolayers of metallic nanorods have a wide range of applications as metamaterials or in surface enhanced Raman spectroscopy. However the fabrication of such structures using current top-down methods or through assembly on solid substrates is either difficult to scale up or have limited possibilities for further modification after assembly. The aim of this paper is to use the adsorption kinetics of cylindrical nanorods at a liquid interface as a novel route for assembling vertically aligned nanorod arrays that overcomes these problems.

Defined core-shell particles as the key to complex interfacial self-assembly.

The two-dimensional self-assembly of colloidal particles serves as a model system for fundamental studies of structure formation and as a powerful tool to fabricate functional materials and surfaces. However, the prevalence of hexagonal symmetries in such self-assembling systems limits its structural versatility. More than two decades ago, Jagla demonstrated that core-shell particles with two interaction length scales can form complex, nonhexagonal minimum energy configurations.

Adsorption trajectories of nonspherical particles at liquid interfaces.

The adsorption of colloidal particles at liquid interfaces is of great importance scientifically and industrially, but the dynamics of the adsorption process is still poorly understood. In this paper we use a Langevin model to study the adsorption dynamics of ellipsoidal colloids at a liquid interface. Interfacial deformations are included by coupling our Langevin dynamics to a finite element model while transient contact line pinning due to nanoscale defects on the particle surface is encoded into our model by renormalizing particle friction coefficients and using dynamic contact angles relevant to the adsorption timescale.

Pattern formation in two-dimensional hard-core/soft-shell systems with variable soft shell profiles.

Hard-core/soft shell (HCSS) particles have been shown to self-assemble into a remarkably rich variety of structures under compression due to the simple interplay between the hard-core and soft-shoulder length scales in their interactions. Most studies in this area model the soft shell interaction as a square shoulder potential. Although appealing from a theoretical point of view, the potential is physically unrealistic because there is no repulsive force in the soft shell regime, unlike in experimental HCSS systems.

Correction to "Capillary Interaction and Self-Assembly of Tilted Magnetic Ellipsoidal Particles at Liquid Interfaces".

[This corrects the article DOI: 10.1021/acsomega.8b01818.

Capillary Interaction and Self-Assembly of Tilted Magnetic Ellipsoidal Particles at Liquid Interfaces.

Magnetic ellipsoidal particles adsorbed at a liquid interface provide exciting opportunities for creating switchable functional materials, where self-assembly can be switched on and off using an external field [Davies et al., ., , , 6715].

Density functional theory for the crystallization of two-dimensional dipolar colloidal alloys.

Two-dimensional mixtures of dipolar colloidal particles with different dipole moments exhibit extremely rich self-assembly behaviour and are relevant to a wide range of experimental systems, including charged and super-paramagnetic colloids at liquid interfaces. However, there is a gap in our understanding of the crystallization of these systems because existing theories such as integral equation theory and lattice sum methods can only be used to study the high temperature fluid phase and the zero-temperature crystal phase, respectively. In this paper we bridge this gap by developing a density functional theory (DFT), valid at intermediate temperatures, in order to study the crystallization of one and two-component dipolar colloidal monolayers.

Amphiphile-Induced Anisotropic Colloidal Self-Assembly.

Spherical colloidal particles typically self-assemble into hexagonal lattices when adsorbed at liquid interfaces. More complex assembly structures, including particle chains and phases with square symmetry, were theoretically predicted almost two decades ago for spherical particles interacting via a soft repulsive shoulder. Here, we demonstrate that such complex assembly phases can be experimentally realized with spherical colloidal particles assembled at the air/water interface in the presence of molecular amphiphiles.

Anisotropic Self-Assembly from Isotropic Colloidal Building Blocks.

Spherical colloidal particles generally self-assemble into hexagonal lattices in two dimensions. However, more complex, non-hexagonal phases have been predicted theoretically for isotropic particles with a soft repulsive shoulder but have not been experimentally realized. We study the phase behavior of microspheres in the presence of poly(N-isopropylacrylamide) (PNiPAm) microgels at the air/water interface.

Magnetic cylindrical colloids at liquid interfaces exhibit non-volatile switching of their orientation in an external field.

We study the orientation of magnetic cylindrical particles adsorbed at a liquid interface in an external field using analytical theory and high resolution finite element simulations. Cylindrical particles are interesting since they possess multiple locally stable orientations at the liquid interface so that the orientational transitions induced by an external field will not disappear when the external field is removed, i.e.

Interaction between colloidal particles on an oil-water interface in dilute and dense phases.

The interaction between micron-sized charged colloidal particles at polar/non-polar liquid interfaces remains surprisingly poorly understood for a relatively simple physical chemistry system. By measuring the pair correlation function g(r) for different densities of polystyrene particles at the decane-water interface, and using a powerful predictor-corrector inversion scheme, effective pair-interaction potentials can be obtained up to fairly high densities, and these reproduce the experimental g(r) in forward simulations, so are self consistent. While at low densities these potentials agree with published dipole-dipole repulsion, measured by various methods, an apparent density dependence and long range attraction are obtained when the density is higher.

ABC triblock copolymer micelles: spherical versus worm-like micelles depending on the preparation method.

Well-defined ABC triblock copolymers based on two hydrophilic blocks, A and C, and a hydrophobic block B are synthesized and their self-assembly behavior is investigated. Interestingly, at the same solvent, concentration, pH, and temperature, different shape micelles are observed, spherical and worm-like micelles, depending on the preparation method. Specifically, spherical micelles are observed with bulk rehydration while both spherical and worm-like micelles are observed with film rehydration.

Influence of magnetic field on the orientation of anisotropic magnetic particles at liquid interfaces.

We study theoretically the influence of an external magnetic field on the orientation of an ellipsoidal magnetic particle adsorbed at a liquid interface. Using the finite element program Surface Evolver, we calculate the equilibrium meniscus shape around the ellipsoidal particle and its equilibrium tilt angle with respect to the undeformed interface θt when a magnetic field B is applied perpendicular to the interface. We find that as we increase field strength, θt increases and at a critical magnetic field Bc1 and tilt angle θc1, the particle undergoes a discontinuous transition to the 'perpendicular' orientation (θt = 90°).

Water-in-water emulsions based on incompatible polymers and stabilized by triblock copolymers-templated polymersomes.

Aqueous solutions containing a mixture of polyethylene glycol (PEG) and dextran homopolymers form an aqueous two-phase system which can be emulsified to give a water-in-water emulsion. We show how these emulsions can be stabilized using triblock polymers containing poly[poly(ethylene glycol) methyl ether methacrylate] (PEGMA), poly (n-butyl methacrylate) (BuMA), and poly[2-(dimethylamino) ethyl methacrylate] (DMAEMA) blocks of general structure Pp-Bb-Dd, in which the middle BuMA block is hydrophobic. Low-energy input stirring of mixtures containing equal volumes of PEG- and dex-rich aqueous phases plus 1 wt % of Pp-Bb-Dd stabilizer all form dex-in-PEG emulsions (for the range of Pp-Bb-Dd triblock polymers used here) which have a polymersome-like structure.

Self-assembly of two-dimensional colloidal clusters by tuning the hydrophobicity, composition, and packing geometry.

We study the structure of binary monolayers of large (3  μm diameter) very hydrophobic (A) and large (3  μm diameter) hydrophilic (B) or small (1  μm diameter) hydrophilic (C) silica particles at an octane-water interface. By tuning the composition and packing geometry of the mixed monolayer, we find that a rich variety of two-dimensional hexagonal superlattices of mixed A/B or A/C clusters are formed, stabilized by short-ranged electrostatic induced dipole interactions. The cluster structures obtained are in excellent agreement with zero temperature calculations, indicating that the self-assembly process can be effectively controlled.

Effect of particulate contamination on adhesive ability and repellence in two species of ant (Hymenoptera; Formicidae).

Tarsal adhesive pads are crucial for the ability of insects to traverse their natural environment. Previous studies have demonstrated that for both hairy and smooth adhesive pads, significant reduction in adhesion can occur because of contamination of these pads by wax crystals present on plant surfaces or synthetic microspheres. In this paper, we focus on the smooth adhesive pads of ants and study systematically how particulate contamination and the subsequent loss of adhesion depends on particle size, particle surface energy, humidity and species size.

Two-dimensional colloidal alloys.

We study the structure of mixed monolayers of large (3 μm diameter) and small (1 μm diameter) very hydrophobic silica particles at an octane-water interface as a function of the number fraction of small particles ξ. We find that a rich variety of two-dimensional hexagonal super-lattices of large (A) and small (B) particles can be obtained in this system due to strong and long-range electrostatic repulsions through the nonpolar octane phase. The structures obtained for the different compositions are in good agreement with zero temperature calculations and finite temperature computer simulations.

Obtaining effective pair potentials in colloidal monolayers using a thermodynamically consistent inversion scheme.

The structure and stability of colloidal monolayers depends crucially on the effective pair interaction potential u(r) between colloidal particles. In this study, we construct a novel method for extracting u(r) from the two-dimensional (2D) radial distribution function g(r) of dense colloidal monolayers. The method is based on the Ornstein-Zernike relation and the HMSA closure first proposed by Zerah and Hansen (Zerah, G.

Determination of interaction potentials of colloidal monolayers from the inversion of pair correlation functions: a two-dimensional predictor-corrector method.

The structure and stability of colloidal monolayers depend crucially on the effective pair potential u(r) between colloidal particles. In this paper, we develop a two-dimensional (2D) predictor-corrector method for extracting u(r) from the pair correlation function g(r) of dense colloidal monolayers. The method is based on an extension of the three-dimensional scheme of Rajagopalan and Rao [Phys.

Micelle shape transitions in block copolymer/homopolymer blends: comparison of self-consistent field theory with experiment.

Diblock copolymers blended with homopolymer may self-assemble into spherical, cylindrical, or lamellar aggregates. Transitions between these structures may be driven by varying the homopolymer diblock molecular weight or composition. Using self-consistent field theory (SCFT), we reproduce these effects.

A Monte Carlo study of amphiphilic dendrimers: spontaneous asymmetry and dendron separation.

We study via Monte Carlo simulation the conformation of amphiphilic dendrimers for which terminal monomers (t) and internal monomers (i) interact differently with the solvent (s). Specifically, we have studied g = 3,6 dendrimers as a function of chi(it), chi(is), and chi(ts) (chi is the differential contact energy between the different particles) for parameter values chi(it) = 0, +/-1 and -1 < chi(is), chi(ts) < 1. We have allowed negative chi values in order to model attractive polar interactions (e.