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Chemotactic interactions are ubiquitous in nature and can lead to non-reciprocal and complex emergent behaviour in multibody systems. However, developing synthetic, inanimate embodiments of a chemomechanical framework to generate non-reciprocal interactions of tunable strength and directionality has been challenging. Here we show how chemotactic signalling between microscale oil droplets of different chemistries in micellar surfactant solutions can result in predator–prey-like non-reciprocal chasing interactions. The interactions and dynamic self-organization result from the net directional, micelle-mediated transport of oil between emulsion droplets of differing composition and are powered by the free energy of mixing. We systematically elucidated chemical design rules to tune the interactions between droplets by varying the oil and surfactant chemical structure and concentration. Through the integration of experiment and simulation, we also investigated the active behaviour and dynamic reorganization of multidroplet clusters. Our findings demonstrate how chemically minimal systems can be designed with controllable, non-reciprocal chemotactic interactions to generate emergent self-organization and collective behaviours reminiscent of biological systems.

Transient assembled structures play an indispensable role in a wide variety of processes fundamental to living organisms including cellular transport, cell motility, and proliferation. Typically, the formation of these transient structures is driven by the consumption of molecular fuels via dissipative reaction networks. In these networks, building blocks are converted from inactive precursor states to active (assembling) states by (a set of) irreversible chemical reactions. Since the activated state is intrinsically unstable and can be maintained only in the presence of sufficient fuel, fuel depletion results in the spontaneous disintegration of the formed superstructures. Consequently, the properties and behavior of these assembled structures are governed by the kinetics of fuel consumption rather than by their thermodynamic stability. This fuel dependency endows biological systems with unprecedented spatiotemporal adaptability and inherent self-healing capabilities. Fascinated by these unique material characteristics, coupling the assembly behavior to molecular fuel or light-driven reaction networks was recently implemented in synthetic (supra)molecular systems. In this invited feature article, we discuss recent studies demonstrating that dissipative assembly is not limited to the molecular world but can also be translated to building blocks of colloidal dimensions. We highlight crucial guiding principles for the successful design of dissipative colloidal systems and illustrate these with the current state of the art. Finally, we present our vision on the future of the field and how marrying nonequilibrium self-assembly with the functional properties associated with colloidal building blocks presents a promising route for the development of next-generation materials.

There is a large debate on the destabilization mechanism of emulsions. We present a simple technique using mechanical compression to destabilize oil-in-water emulsions. Upon compression of the emulsion, the continuous aqueous phase is squeezed out, while the dispersed oil phase progressively deforms from circular to honeycomb-like shapes. The films that separate the oil droplets are observed to thin and break at a critical oil/water ratio, leading to coalescence events. Electrostatic interactions and local droplet rearrangements do not determine film rupture. Instead, the destabilization occurs like an avalanche propagating through the system, starting at areas where the film thickness is smallest.

Dimple colloids with well-defined cavities were synthesized by a modified dispersion polymerization. The key step in the procedure is the delayed addition of cross-linkers into the reaction mixture. By systematically studying the effect of the delayed addition time and the concentration of the cross-linker on the resulting particle morphology, we identified the dominating driving force that underlies dimple formation. The delayed addition of cross-linkers results in colloids with a core–shell morphology consisting of a core rich in linear polymers and a cross-linked shell. This morphology was confirmed by selectively etching non-cross-linked material using dimethylformamide. With polymerization proceeding, consumption of monomers present in the swollen particles leads to contraction of the particles, which is larger for the core composed of linear polymers compared to the stiffer cross-linked shell. To accommodate this decrease in volume, the outer cross-linked shell has to buckle, resulting in a well-defined dimple. Furthermore, we extended the procedure to incorporate functional monomers, yielding chemically modifiable dimple particles. Subsequently, we showed that by leveraging the core–shell structure, these dimple particles can be used to prepare dumbbell-shaped colloids with one hollow and one solid lobe. These partially hollow anisotropic particles assemble into strings with well-defined orientations in an alternating current electric field.

Particles with directional interactions are promising building blocks for new functional materials and may serve as models for biological structures. Mutually attractive nanoparticles that are deformable owing to flexible surface groups, for example, may spontaneously order themselves into strings, sheets and large vesicles. Furthermore, anisotropic colloids with attractive patches can self-assemble into open lattices and the colloidal equivalents of molecules and micelles. However, model systems that combine mutual attraction, anisotropy and deformability have not yet been realized. Here we synthesize colloidal particles that combine these three characteristics and obtain self-assembled microcapsules. We propose that mutual attraction and deformability induce directional interactions via colloidal bond hybridization. Our particles contain both mutually attractive and repulsive surface groups that are flexible. Analogously to the simplest chemical bond—in which two isotropic orbitals hybridize into the molecular orbital of H2—these flexible groups redistribute on binding. Via colloidal bond hybridization, isotropic spheres self-assemble into planar monolayers, whereas anisotropic snowman-shaped particles self-assemble into hollow monolayer microcapsules. A modest change in the building blocks thus results in much greater complexity of the self-assembled structures. In other words, these relatively simple building blocks self-assemble into markedly more complex structures than do similar particles that are isotropic or non-deformable.

We put forward a modified Zipper model inspired by the statics and dynamics of the spontaneous reconstitution of rodlike tobacco mosaic virus particles in solutions containing the coat protein and the single-stranded RNA of the virus. An important ingredient of our model is an allosteric switch associated with the binding of the first protein unit to the origin-of-assembly domain of the viral RNA. The subsequent addition and conformational switching of coat proteins to the growing capsid we believe is catalyzed by the presence of the helical arrangement of bound proteins to the RNA. The model explains why the formation of complete viruses is favored over incomplete ones, even though the process is quasi-one-dimensional in character. We numerically solve the relevant kinetic equations and show that time evolution is different for the assembly and disassembly of the virus, the former exhibiting a time lag even if all forward rate constants are equal. We find the late-stage assembly kinetics in the presence of excess protein to be governed by a single-exponential relaxation, which agrees with available experimental data on TMV reconstruction.

We demonstrate a mechanism to intrinsically stabilize a hollow shell composed of individual nanoparticles. Using Monte Carlo simulations, we show that if nanoparticles that interact via short-range attraction and long-range repulsion are assembled on a template, the resulting shell can be stabilized upon the removal of the template. The interplay of attractive and repulsive interactions provides energy barriers that dynamically arrest the particles and stabilize the shell. We present a well-defined stability region in the interaction parameters space. We find a transition from single layered to multilayered stable shell by increasing the range of attraction, and show that the mechanism is not limited to spherical shells but can also be extended to stabilize nonspherical shells such as torus shells. This study can potentially be useful in understanding and engineering the assembly of nanoparticles into hollow objects of various shapes.

We present a statistical mechanical model based on the principle of mass action that explains the main features of the in vitro aggregation behavior of the coat protein of tobacco mosaic virus (TMV). By comparing our model to experimentally obtained stability diagrams, titration experiments, and calorimetric data, we pin down three competing factors that regulate the transitions between the different kinds of aggregated state of the coat protein. These are hydrophobic interactions, electrostatic interactions, and the formation of so-called “Caspar” carboxylate pairs. We suggest that these factors could be universal and relevant to a large class of virus coat proteins.

A fundamental step in the replication of a viral particle is the self-assembly of its rigid shell (capsid) from its constituent proteins. Capsids play a vital role in genome replication and intercellular movement of viruses, and as such, understanding viral assembly has great potential in the development of new antiviral therapies and a systematic treatment of viral infection. In this article, we assume that nucleation is the underlying mechanism for self-assembly and combine the theoretical methods of the physics of equilibrium polymerization with those of the classical nucleation to develop a theory for the kinetics of virus self-assembly. We find expressions for the size of the critical capsid, the lag time, and the steady-state nucleation rate of capsids, and how they depend on both protein concentration and binding energy. The latter is a function of the acidity of the solution, the ionic strength, and the temperature, explaining why capsid nucleation is a sensitive function of the ambient conditions.

We present a thermodynamic evaluation of the self-assembly of charged nanometer-sized particles at the wateroil interface. The chemical potentials of the nanoparticles in the bulk aqueous phase and at the wateroil interface are calculated taking into account interfacial energies, van der Waals interactions, and electrostatic repulsions. An isotherm of the interfacial particle density as a function of the surface charge density on the particles is obtained and compared with experimental results on gold and CdTe nanoparticles self-assembled at the waterheptane interface. Our model provides a semi-quantitative explanation for the spontaneous self-assembly of several types of metallic and semiconducting charged nanoparticles upon reduction of their surface charge.

Recent experiments show that, in the range from ∼15 to 45°C, an increase in the temperature promotes the spontaneous assembly into capsids of the Escherichia coli-expressed coat proteins of hepatitis B virus. Within that temperature interval, an increase in ionic strength up to five times that of standard physiological conditions also acts to promote capsid assembly. To explain both observations we propose an interaction of mean force between the protein subunits that is the sum of an attractive hydrophobic interaction, driving the self-assembly, and a repulsive electrostatic interaction, opposing the self-assembly. We find that the binding strength of the capsid subunits increases with temperature virtually independently of the ionic strength, and that, at fixed temperature, the binding strength increases with the square root of ionic strength. Both predictions are in quantitative agreement with experiment. We point out the similarities of capsid assembly in general and the micellization of surfactants. Finally we make plausible that electrostatic repulsion between the native core subunits of a large class of virus suppresses the formation in vivo of empty virus capsids, that is, without the presence of the charge-neutralizing nucleic acid.

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We show that coupling between a fast and a slow relaxation time causes the spontaneous formation of protrusions in colloids made of cross-linked polymers. The volume of the protrusions can be controlled by adjusting the ratio between the relaxation times. This, in principle, results in particles with levels of anisotropy that can be made “to order”.