Anisotropic Colloidal Particles Research Articles

Monodisperse nanosheet mesophases.

Self-assemblies of anisotropic colloidal particles into colloidal liquid crystals and well-defined superlattices are of great interest for hierarchical nanofabrications that are applicable for various functional materials. Inorganic nanosheets obtained by exfoliation of layered crystals have been highlighted as the intriguing colloidal units; however, the size polydispersity of the nanosheets has been preventing precise design of the assembled structures and their functions. Here, we demonstrate that the anionic titanate nanosheets with monodisperse size reversibly form very unusual superstructured mesophases through finely tunable weak attractive interactions between the nanosheets. Transmission electron microscopy, polarizing optical microscopy, small-angle x-ray scattering, and confocal laser scanning microscopy clarified the reversible formation of the mesophases (columnar nanofibers, columnar nematic liquid crystals, and columnar nanofiber bundles) as controlled by counter cations, nanosheet concentration, solvent, and temperature.

Self-Assembled Ring-Based Complex Colloidal Particles by Lock-And-Key Interaction and Their Self-Assembly into Unusual Colloidal Crystals.

Creating hierarchical crystalline materials using simple colloids or nanoparticles is very challenging, as it is usually impossible to achieve hierarchical structures without nonhierarchical colloidal interactions. Here, we present a hierarchical self-assembly (SA) route that employs colloidal rings and anisotropic colloidal particles to form complex colloids and uses them as building blocks to form unusual colloidal columnar liquid crystals or crystals. This route is realized by designing hierarchical SA driving forces that is controlled by the colloidal shape and shape-dependent depletion attraction. Depletion-induced lock-and-key interaction is the first driving force, which ensures a high efficiency (>90%) to load colloidal particles of other shapes such as spheres, spherocylinders, and oblate ellipsoids into rings, providing high-quality building blocks. Their SA into ordered superstructures has to require a second driving force such as higher volume fraction and/or stronger depletion attraction. As a result, unusual hierarchical colloidal (liquid) crystals, which have previously been difficult to fabricate by simple binary assembly, can be achieved. This work presents a significant advancement in the field of hierarchical SA, demonstrating a promising strategy for constructing many unprecedented crystalline materials by the SA route.

Front Cover: Anisotropic Colloidal Particles by Molecular Self‐Assembly: Synthesis and Application (ChemNanoMat 3/2024)

Front Cover: Anisotropic Colloidal Particles by Molecular Self‐Assembly: Synthesis and Application (ChemNanoMat 3/2024)

Dynamical arrest transition of a bidisperse two-patchy colloidal dispersion: A dynamic Monte Carlo study.

During the last few years, patchy colloidal dispersions have emerged as ideal candidates of glass-formers of systems composed of particles that interact with non-isotropic potentials. However, from the computational point of view, the characterization of their dynamical properties close to the glass transition via any kind of molecular dynamics simulation technique can be very difficult due to the slowing down of both the rotational and translational dynamics. Although a plethora of dynamical techniques have been developed to account for the dynamics of patchy colloids, new and complementary simulation techniques are required to explore, much faster and more efficiently, the dynamical arrest transition of patchy colloidal dispersions when computer simulation consists of a large number of particles and, due to the slow particle dynamics at the glass transition, an extended time window is explicitly required. Then, in this contribution, by means of the so-called dynamic-Monte Carlo method, we report on the dynamical arrest transition, both rotational and translational, of a bidisperse patchy colloidal dispersion, following three different paths along the density-temperature plane, including high densities and low temperatures. Although this method has not been extensively tested at extreme thermodynamic conditions, we show that even at the dynamical arrest transition, it allows us to extract good dynamical data from a complex system. Therefore, it turns out to be a promising technique to explore the onset of vitrification of anisotropic colloidal particles.

Macromolecular crowding in chiral assembly of ellipsoidal nanoparticles

Anisotropic colloidal particles have the ability to self-assemble into cholesteric structures. We used molecular dynamics to simulate the self-assembly of ellipsoidal particles with the objective to establish a general framework to reveal the primary factors driving chiral interactions. To characterize these interactions, we introduce a characteristic parameter following the crowding factor (CF) theory. Our simulations and statistical analysis showed good agreement with the CF theory; at the early stages of the assembly process, the ellipsoidal particles go through a critical aggregation point followed by further clustering toward nematic order. Furthermore, we demonstrate that under high CF conditions, small initial clusters may induce a chiral twist, which subsequently forms a cholesteric structure with no directional preference in higher organization states.

Anisotropic Colloidal Particles by Molecular Self‐Assembly: Synthesis and Application

AbstractAnisotropic colloidal particles have attracted great attention over the past few decades because of their significant properties that differ from isotropic particles. Molecular self‐assembly provides the possibility to design and construct anisotropic colloidal particles from the single‐molecule level, and molecular assemblies can both inherit the properties of molecules in single states and integrate the functions of molecules in collective states, which has attracted great interest to researchers. Even in recent years, the self‐assembly strategy of anisotropic colloidal particles has been greatly developed. This review article briefly summarizes the research progress of molecules from small molecules, block copolymers and homopolymers to anisotropic particles, including their self‐assembly strategies and applications. Finally, we discuss the remaining challenges of this topic and we expect that by manipulating the design of diverse molecules/polymers, anisotropic colloidal particles can evolve into a new era.

Anisotropic Multitentacle Janus Particles Synthesized by Selective Asymmetric Growth.

Anisotropic colloidal particles with asymmetric morphology possess functionally rich heterogeneous structures, thus offering potential for intricate superstructures or nanodevices. However, it is a challenge to achieve controlled asymmetric surface partitioned growth. In this work, an innovative strategy is developed based on the selective adsorption and growth of emulsion droplets onto different regions of object which is controlled by wettability. It is found that the emulsion droplets can selectively adsorb on the hydrophilic surface but not the hydrophobic one, and further form asymmetric tentacle by the interfacial sol-gel process along its trajectory. Janus particles with an anisotropic shape and multitentacle structure are achieved via integration of emulsion droplet (soft) and seed (hard) templates. The size and number of tentacles exhibit tunability mediated by soft and hard templates, respectively. This general strategy can be expanded to a variety of planar substrates or curved particles, further confirming the correlation between tentacle growth and Brownian motion. Most interestingly, it can be employed to selectively modify one region of surface partitioned particles to achieve an ABC three-component Janus structure.

Effect of curvature on the diffusion of colloidal bananas.

Anisotropic colloidal particles exhibit complex dynamics which play a crucial role in their functionality, transport, and phase behavior. In this Letter, we investigate the two-dimensional diffusion of smoothly curved colloidal rods-also known as colloidal bananas-as a function of their opening angle α. We measure the translational and rotational diffusion coefficients of the particles with opening angles ranging from 0^{∘} (straight rods) to nearly 360^{∘}(closed rings). In particular, we find that the anisotropic diffusion of the particles varies nonmonotonically with their opening angle and that the axis of fastest diffusion switches from the long to the short axis of the particles when α>180^{∘}. We also find that the rotational diffusion coefficient of nearly closed rings is approximately an order of magnitude higher than that of straight rods of the same length. Finally, we show that the experimental results are consistent with slender body theory, indicating that the dynamical behavior of the particles arises primarily from their local drag anisotropy. These results highlight the impact of curvature on the Brownian motion of elongated colloidal particles, which must be taken into account when seeking to understand the behavior of curved colloidal particles.

Computational design of anisotropic nanocomposite actuators.

This paper presents a theoretical investigation of the design of a new actuator type made of anisotropic colloidal particles grafted with stimuli-responsive polymer chains. These artificial muscles combine the osmotic actuation principle of stimuli-responsive hydrogels with the structural alignment of colloidal liquid crystals to achieve directional motion. The solubility of the stimuli-responsive polymer in the neutral state, its degree of polymerization, the salt concentration, and the grafting density of the polymer chains on the surface of the colloidal particles are investigated and identified as important for actuator performance and tunability. The computational results suggest that the proposed mechanically active material matches or exceeds the performances of natural muscles and provide the guidelines for the realization of artificial muscles with predetermined actuation properties.

Time‐dependent viscosity of structured clay suspensions

AbstractTime‐dependent viscosity of structured clay suspensions under a fixed shear was revealed in the prepared slurry samples of clay lenses from the Athabasca oil sands deposit, differing from thixotropic or rheopectic suspensions. At a lower salt (Na or Ca) concentration, the viscosity oscillated with time, which was slowly damped with increasing salt concentrations. The viscosity increased without reaching a maximum plateau, even after a run of a few hours. At 1000 ppm Na concentration, a maximum viscosity was reached, followed by viscosity fluctuation within a narrow range to approach an equilibrium value with time. Both sample ageing and shear history affected the slurry viscosity. It was speculated that the Brownian motion of colloidal clay particles and the applied shear induced rearrangement and continued formation of clay microstructures with time, due to the rotation of anisotropic colloidal clay particles under simple shear flow. Its implications to oil sands research and operation were briefly discussed.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential. We address this fundamental issue by exploiting a recently developed system of fluorohectorite smectite clay mineral that delaminates in water, leading to colloidal dispersions of single-layer, very large (≈20 μm) clay sheets at high dilution. We show that when the clay crystallites are dispersed in water, they swell to form periodic one-dimensional stacks of fluorohectorite sheets with very low volume fraction (<1%) and therefore huge (≈100 nm) periods. Using optical microscopy and synchrotron X-ray scattering, we establish that these colloidal stacks bear strong similarities, yet subtle differences, with a smectic liquid-crystalline phase. Despite the high dilution, the colloidal stacks of sheets, called colloidal accordions, are extremely robust mechanically and can persist for years. Moreover, when subjected to AC electric fields, they rotate as solid bodies, which demonstrates their outstanding internal cohesion. Furthermore, our theoretical model captures the dependence of the stacking period on the dispersion concentration and ionic strength and explains, invoking the Donnan effect, why the colloidal accordions are kinetically stable over years and impervious to shear and Brownian motion. Because our model is not system specific, we expect that similar colloidal accordions frequently appear as an intermediate state during the delamination process of two-dimensional crystals in polar solvents.

Structural Diversity in Dimension-Controlled Assemblies of Tetrahedral Gold Nanocrystals.

Polyhedron packings have fascinated humans for centuries and continue to inspire scientists of modern disciplines. Despite extensive computer simulations and a handful of experimental investigations, understanding of the phase behaviors of synthetic tetrahedra has remained fragmentary largely due to the lack of tetrahedral building blocks with tunable size and versatile surface chemistry. Here, we report the remarkable richness of and complexity in dimension-controlled assemblies of gold nanotetrahedra. By tailoring nanocrystal interactions from long-range repulsive to hard-particle-like or to systems with short-ranged directional attractions through control of surface ligands and assembly conditions, nearly a dozen of two-dimensional and three-dimensional superstructures including the cubic diamond and hexagonal diamond polymorphs are selectively assembled. We further demonstrate multiply twinned icosahedral supracrystals by drying aqueous gold nanotetrahedra on a hydrophobic substrate. This study expands the toolbox of the superstructure by design using tetrahedral building blocks and could spur future computational and experimental work on self-assembly and phase behavior of anisotropic colloidal particles with tunable interactions.

Behavior of colloidal gels made of thermoresponsive anisotropic nanoparticles

Amongst colloidal gels, those designed by the assembly of anisotropic colloidal particles tend to form fibrillar gels and are attracting interest as artificial cell growth environments since they have a structure reminiscent of biological extracellular matrices. Their properties can be tuned by controlling the size, shape, and rigidity of the nanoparticles used during their formation. Herein, the relationship between the physical and mechanical properties of the nanocolloidal building blocks and the properties of the resulting gels is investigated. Thermoresponsive particles with different aspect ratios and controlled rigidity were prepared, and the gelation and the properties of the resulting gels were studied. The results show how the aspect ratio and rigidity of polymer colloids tune the properties of the gels. An increase in the aspect ratio of the nanocolloid used led to a sol–gel transition observed at lower particle concentration, but an increase in the rigidity of the nanocolloids delayed the sol–gel transition to higher concentration. However, at a constant concentration, increases in the anisotropy produced gels with higher modulus and lower yield strain. Similarly, an increase in rigidity of the colloids increased the modulus and reduced the yield strain of the resulting gels.

Anisotropic colloidal particles near boundaries

Anisotropic colloidal particles are regularly found in applications ranging from health to energy. These particles, typically with non-uniform shape or surface chemistry, interact with boundaries in unique ways, offering pathways to complex assemblies and active systems. Work in this field over the past two decades rapidly advanced, with the last five years seeing significant innovation. One common thread joining many studies and applications is that of the presence of boundaries in the form of a nearby wall or neighboring particle. Asymmetry introduced by a neighboring boundary often leads to unique and surprising particle dynamics from the resulting anisotropic surface interactions. Herein, we provide background for the area, some recent distinctive examples, and describe recent work from our group developing a technique to measure surface interactions of anisotropic particles. Note that we focused on anisotropic “colloidal” particles with the size ranging from 0.1 to 10 μm in the presence of externally or internally generated fields. Within this context, we then motivate and describe recent work from our group developing an ultra-microscopy technique called Scattering Morphology Resolved Total Internal Reflection Microscopy. Finally, we finish the perspective article by identifying challenges and providing an outlook for the field.

Depletion torques between anisotropic colloidal particles.

We explore how the entropic notion of depletion forces between spheres, introduced by Asakura and Oosawa, can be extended to depletion torques that affect the orientations of colloidal particles having complex shapes. In prior experimental work, systems of microscale plate-like particles in the presence of a nanoscale depletion agent have been shown to form polymer-like columnar chains; restoring depletion torques act to align lithographically-structured platelets within a chain orientationally about the chain's axis. We consider depletion torques corresponding to parallel, face-to-face, near-contact pair interactions for complex-shaped, plate-like, prismatic lithographic particles in colloidal dispersions containing a spherical nanoscale depletion agent. We calculate depletion torques for a wide variety of such particles, including rotationally symmetric, asymmetric, achiral, chiral, and elongated particles. Moreover, we determine depletion torques between two non-parallel proximate square platelets connected by a lossless hinge along a common edge. Our investigations show that depletion torques can be tailored through lithographic or synthetic designof specific geometrical features in the shapes of particles.

Probing roto-translational diffusion of small anisotropic colloidal particles with a bright-field microscope

Soft and biological materials are often composed of elementary constituents exhibiting an incessant roto-translational motion at the microscopic scale. Tracking this motion with a bright-field microscope becomes increasingly challenging when the particle size becomes smaller than the microscope resolution, a case which is frequently encountered. Here we demonstrate squared-gradient differential dynamic microscopy (SG-DDM) as a tool to successfully use bright-field microscopy to extract the roto-translational dynamics of small anisotropic colloidal particles, whose rotational motion cannot be tracked accurately in direct space. We provide analytical justification and experimental demonstration of the method by successful application to an aqueous suspension of peanut-shaped particles.Graphic abstract

Entropic formation of a thermodynamically stable colloidal quasicrystal with negligible phason strain

Quasicrystals have been discovered in a variety of materials ranging from metals to polymers. Yet, why and how they form is incompletely understood. In situ transmission electron microscopy of alloy quasicrystal formation in metals suggests an error-and-repair mechanism, whereby quasiperiodic crystals grow imperfectly with phason strain present, and only perfect themselves later into a high-quality quasicrystal with negligible phason strain. The growth mechanism has not been investigated for other types of quasicrystals, such as dendrimeric, polymeric, or colloidal quasicrystals. Soft-matter quasicrystals typically result from entropic, rather than energetic, interactions, and are not usually grown (either in laboratories or in silico) into large-volume quasicrystals. Consequently, it is unknown whether soft-matter quasicrystals form with the high degree of structural quality found in metal alloy quasicrystals. Here, we investigate the entropically driven growth of colloidal dodecagonal quasicrystals (DQCs) via computer simulation of systems of hard tetrahedra, which are simple models for anisotropic colloidal particles that form a quasicrystal. Using a pattern recognition algorithm applied to particle trajectories during DQC growth, we analyze phason strain to follow the evolution of quasiperiodic order. As in alloys, we observe high structural quality; DQCs with low phason strain crystallize directly from the melt and only require minimal further reduction of phason strain. We also observe transformation from a denser approximant to the DQC via continuous phason strain relaxation. Our results demonstrate that soft-matter quasicrystals dominated by entropy can be thermodynamically stable and grown with high structural quality--just like their alloy quasicrystal counterparts.

Frame-Guided Synthesis of Polymeric Colloidal Discs.

Anisotropic colloidal particles are important building blocks for the studies of self-assembly, which are visualized models for basic research and can be used to construct structured materials. Discs are one of the most typical anisotropic colloids; however, the synthesis of monodisperse colloidal discs with well-defined shape remains a challenge. Here we report a novel strategy for synthesizing polymeric discs based on frame-guided droplet shrinkage. This was realized by creating frame/liquid core/shell rings and utilizing the shrinking instability of the liquid rings. The resulting disc's shape parameters are tunable. The method is general, is not limited to specific polymers, solvents, and frames, and therefore has the potential to afford a variety of polymer discs. We also demonstrate the possibility of tuning the surface chemistry of the discs through surface-initiated polymerization. The frame-guided droplet shrinkage method opens up a new way to design and fabricate colloidal particles.

Anisotropic colloidal interactions & assembly in AC electric fields.

We match experimental and simulated configurations of anisotropic epoxy colloidal particles in high frequency AC electric fields by identifying analytical potentials for dipole-field and dipole-dipole interactions. We report an inverse Monte Carlo simulation algorithm to determine optimal fits of analytical potentials by matching simulated and experimental distribution functions for non-uniform liquid, liquid crystal, and crystal microstructures in varying amplitude electric fields. Two potentials that include accurate particle volume and dimensions along with a concentration dependent prefactor quantitatively capture experimental observations. At low concentrations, an effective ellipsoidal point dipole potential works well, whereas a novel stretched point dipole potential is found to be suitable at all concentrations, field amplitudes, and degrees of ordering. The simplicity, accuracy, and adjustability of the stretched point dipole potential suggest it can be applied to model field mediated microstructures and assembly of systematically varying anisotropic particle shapes.

Synthesis of anisotropic colloids with concave and convex structures.

Anisotropic colloidal particles with concave and convex structures are useful in both theoretical studies and applications. In this work, we mass-produced polystyrene (PS) colloidal particles with multiple concavities through dispersion polymerization techniques. By increasing the delayed feeding time td of the cross-linker divinylbenzene (DVB), the morphological evolution of particles can be classified into two stages, during which the formation of different concavities is consistent with either the buckling mechanism or phase separation mechanism. By varying the DVB dosage, we found that the size of the big chamber formed on the particle surfaces decreases as the DVB dosage increases. Then, using these concave particles as seeds, 2-5 μm anisotropic colloids with various shapes, including spherical, ellipsoidal, snowman and multi-protrusion, were synthesized by seeded emulsion polymerization. Moreover, our results show that both the chambers and long narrow ditches on the surface of seeds can be the active sites for monomers to gather and polymerize, but monomers in the big chamber have a priority to polymerize first when big and small concavities both exist on seeds. The results of this study could mean great potential in synthesizing a variety of anisotropic particles with well-controlled concave morphologies.