Self-assembly of "Mickey Mouse" shaped colloids into tube-like structures: experiments and simulations

The self-assembly of anisotropic patchy particles with triangular shape was studied by experiments and computer simulations. The colloidal particles were synthesized in a two-step seeded emulsion polymerization process, and consist of a central smooth lobe connected to two rough lobes at an angle of $\sim$90$^{\circ}$, resembling the shape of a "Mickey Mouse" head. Due to the difference in overlap volume, adding an appropriate depletant induces an attractive interaction between the smooth lobes of the colloids only, while the two rough lobes act as steric constraints. The essentially planar geometry of the "Mickey Mouse" particles is a first geometric deviation of dumbbell shaped patchy particles. This new geometry is expected to form one-dimensional tube-like structures rather than spherical, essentially zero-dimensional micelles. At sufficiently strong attractions, we indeed find tube-like structures with the sticky lobes at the core and the non-sticky lobes pointing out as steric constraints that limit the growth to one direction, providing the tubes with a well-defined diameter but variable length both in experiments and simulations. In the simulations, we found that the internal structure of the tubular fragments could either be straight or twisted into so-called Bernal spirals

In situ single particle characterization of the themoresponsive and co-nonsolvent behavior of PNIPAM microgels and silica@PNIPAM core-shell colloids

Poly(N-isopropylacrylamide) (PNIPAM) microgels and PNIPAM colloidal shells attract continuous strong interest due to their thermoresponsive behavior, as their size and properties can be tuned by temperature. The direct single particle observation and characterization of pure, unlabeled PNIPAM microgels in their native aqueous environment relies on imaging techniques that operate either at interfaces or in cryogenic conditions, thus limiting the observation of their dynamic nature. Liquid Cell (Scanning) Transmission Electron Microscopy (LC-(S) TEM) imaging allows the characterization of materials and dynamic processes such as nanoparticle growth, etching, and diffusion, at nanometric resolution in liquids. Here we show that via a facile post-synthetic in situ polymer labelling step with high-contrast marker core–shell Au@SiO2 nanoparticles (NPs) it is possible to determine the full volume of PNIPAM microgels in water. The labelling allowed for the successful characterization of the thermoresponsive behavior of PNIPAM microgels and core shell silica@PNIPAM hybrid microgels, as well as the co-nonsolvency of PNIPAM in aqueous alcoholic solutions. The interplay between electron beam irradiation and PNIPAM systems in water resulted in irreversible shrinkage due to beam induced water radiolysis products, which in turn also affected the thermoresponsive behavior of PNIPAM. The addition of 2-propanol as radical scavenger improved PNIPAM stability in water under electron beam irradiation

Synthesis of Cone-Shaped Colloids from Rod-Like Silica Colloids with a Gradient in the Etching Rate

We present the synthesis of monodisperse cone-shaped silica colloids and their fluorescent labeling. Rod-like silica colloids prepared by ammonia-catalyzed hydrolysis and condensation of tetraethyl orthosilicate in water droplets containing polyvinylpyrrolidone cross-linked by citrate ions in pentanol were found to transform into cone-shaped particles upon mild etching by NaOH in water. The diameter and length of the resulting particles were determined by those of the initial rod-like silica colloids. The mechanism responsible for the cone-shape involves silica etching taking place with a varying rate along the length of the particle. Our experiments thus also lead to new insights into the variation of the local particle structure and composition. These are found to vary gradually along the length of the rod, as a result of the way the rod grows out of a water droplet that keeps itself attached to the flat end of the bullet-shaped particles. Subtle differences in composition and structure could also be resolved by high-resolution stimulated emission depletion confocal microscopy on fluorescently labeled particles. The incorporation of a fluorescent dye chemically attached to an amine-based silane coupling agent resulted in a distribution of fluorophores mainly on the outside of the rod-shaped particles. In contrast, incorporation of the silane coupling agent alone resulted in a homogeneous distribution. Additionally, we show that etching rods, where a silane coupling agent alone was incorporated and subsequently coupled to a fluorescent dye, resulted in fluorescent silica cones, the orientation of which can be discerned using super-resolution confocal microscopy

Synthesis of Cone-Shaped Colloids from Rod-Like Silica Colloids with a Gradient in the Etching Rate

We present the synthesis of monodisperse cone-shaped silica colloids and their fluorescent labeling. Rod-like silica colloids prepared by ammonia-catalyzed hydrolysis and condensation of tetraethyl orthosilicate in water droplets containing polyvinylpyrrolidone cross-linked by citrate ions in pentanol were found to transform into cone-shaped particles upon mild etching by NaOH in water. The diameter and length of the resulting particles were determined by those of the initial rod-like silica colloids. The mechanism responsible for the cone-shape involves silica etching taking place with a varying rate along the length of the particle. Our experiments thus also lead to new insights into the variation of the local particle structure and composition. These are found to vary gradually along the length of the rod, as a result of the way the rod grows out of a water droplet that keeps itself attached to the flat end of the bullet-shaped particles. Subtle differences in composition and structure could also be resolved by high-resolution stimulated emission depletion confocal microscopy on fluorescently labeled particles. The incorporation of a fluorescent dye chemically attached to an amine-based silane coupling agent resulted in a distribution of fluorophores mainly on the outside of the rod-shaped particles. In contrast, incorporation of the silane coupling agent alone resulted in a homogeneous distribution. Additionally, we show that etching rods, where a silane coupling agent alone was incorporated and subsequently coupled to a fluorescent dye, resulted in fluorescent silica cones, the orientation of which can be discerned using super-resolution confocal microscopy

Convectively assembled monolayers of colloidal cubes: evidence of optimal packings

We employ a system of cubic colloids with rounded corners to study the close-packed monolayers that form via convective assembly. We show that by controlled solvent evaporation large densely packed monolayers of colloidal cubes are obtained. Using scanning electron microscopy and particle-tracking algorithms, we investigate the local order in detail and show that the obtained monolayers possess their predicted close-packed optimal packings, the Λ 0-lattice and the Λ 1-lattice, as well as the simple square-lattice and disordered packings. We further show that shape details of the cube corners are important for the final packing symmetry, where the frequency of the Λ 1-lattice increases with decreasing roundness of the corners, whereas the frequency of the Λ 0-lattice is unaffected. The formation of both optimal packings is found to be a consequence of the out-of-equilibrium formation process, which leads to small shifts in rows of cubes, thereby transforming the Λ 1-lattice into the Λ 0-lattice

Convectively Assembled Monolayers of Colloidal Cubes : Evidence of Optimal Packings

We employ a system of cubic colloids with rounded corners to study the close-packed monolayers that form via convective assembly. We show that by controlled solvent evaporation large densely packed monolayers of colloidal cubes are obtained. Using scanning electron microscopy and particle-tracking algorithms, we investigate the local order in detail and show that the obtained monolayers possess their predicted close-packed optimal packings, the Î 0 -lattice and the Î 1 -lattice, as well as the simple square-lattice and disordered packings. We further show that shape details of the cube corners are important for the final packing symmetry, where the frequency of the Î 1 -lattice increases with decreasing roundness of the corners, whereas the frequency of the Î 0 -lattice is unaffected. The formation of both optimal packings is found to be a consequence of the out-of-equilibrium formation process, which leads to small shifts in rows of cubes, thereby transforming the Î 1 -lattice into the Î 0 -lattice

Sculpting Silica Colloids by Etching Particles with Nonuniform Compositions

We present the synthesis of new shapes of colloidal silica particles by manipulating their chemical composition and subsequent etching. Segments of silica rods, prepared by the ammonia catalyzed hydrolysis and condensation of tetraethylorthosilicate (TEOS) from polyvinylpyrrolidone loaded water droplets, were grown under different conditions. Upon decreasing temperature, delaying ethanol addition, or increasing monomer concentration, the rate of dissolution of the silica segment subsequently formed decreased. A watery solution of NaOH (∼mM) selectively etched these segments. Further tuning the conditions resulted in rod–cone or cone–cone shapes. Deliberately modulating the composition along the particle’s length by delayed addition of (3-aminopropyl)-triethoxysilane (APTES) also allowed us to change the composition stepwise. The faster etching of this coupling agent in neutral conditions or HF afforded an even larger variety of particle morphologies while in addition changing the chemical functionality. A comparable step in composition was applied to silica spheres. Biamine functional groups used in a similar way as APTES caused a charge inversion during the growth, causing dumbbells and higher order aggregates to form. These particles etched more slowly at the neck, resulting in a biconcave silica ring sandwiched between two silica spheres, which could be separated by specifically etching the functionalized layer using HF

Regiospecific Nucleation and Growth of Silane Coupling Agent Droplets onto Colloidal Particles

Nucleation-and-growth processes are used extensively in the synthesis of spherical colloids, and more recently regiospecific nucleation-and-growth processes have been exploited to prepare more complex colloids such as patchy particles. We demonstrate that surface geometry alone can be made to play the dominant role in determining the final particle geometry in such syntheses, meaning that intricate chemical surface patternings are not required. We present a synthesis method for “lollipop”-shaped colloidal heterodimers (patchy particles), combining a recently published nucleation-and-growth technique with our recent findings that particle geometry influences the locus of droplet adsorption onto anisotropic template particles. Specifically, 3-methacryloxypropyl trimethoxysilane (MPTMS) is nucleated and grown onto bullet-shaped and nail-shaped colloids. The shape of the template particle can be chosen such that the MPTMS adsorbs regiospecifically onto the flat ends. In particular, we find that particles with a wider base increase the range of droplet volumes for which the minimum in the free energy of adsorption is located at the flat end of the particle compared with bullet-shaped particles of the same aspect ratio. We put forward an extensive analysis of the synthesis mechanism and experimentally determine the physical properties of the heterodimers, supported by theoretical simulations. Here we numerically optimize, for the first time, the shape of finite-sized droplets as a function of their position on the rod-like silica particle surface. We expect that our findings will give an impulse to complex particle creation by regiospecific nucleation and growth