Sheet-like assemblies of spherical particles with point-symmetrical patches

Abstract

We report a computational study on the spontaneous self-assembly of spherical particles into twodimensional crystals. The experimental observation of such structures stabilized by spherical objects appeared paradoxical so far. We implement patchy interactions with the patches point-symmetrically (icosahedral and cubic) arranged on the surface of the particle. In these conditions, preference for self-assembly into sheet-like structures is observed. We explain our findings in terms of the inherent symmetry of the patches and the competition between binding energy and vibrational entropy. The simulation results explain why hollow spherical shells observed in some Keplerate-type polyoxometalates (POM) appear. Our results also provide an explanation for the experimentally observed layer-by-layer growth of apoferritin -a quasi-spherical protein.

Hydrogen Bonding Directed Colloidal Self‐Assembly of Nanoparticles into 2D Crystals, Capsids, and Supracolloidal Assemblies

“…However, continuing the dialysis led to the formation of stacked sheets into bundled structures (see Figure b showing 3 sheets stacked) . This is in analogy with the 2D crystal formation in keplerates (see later) and apoferritin particles, driven by the anisotropic distribution of the interacting patches …”

“…There the self‐assembly of macroanionic clusters was attributed to the H‐bondings, directed by water molecules. Recent theoretical studies using Monte Carlo simulations have shown that the patchy distribution of interacting sites on the clusters is responsible for spherical formation . On the other hand, reverse emulsion mediated assembly of spherical particles into colloidosomes has been shown to display plasmonic broadband absorption properties …”

“…In materials science, exactly defined structures and interactions are rarely accomplished using larger building blocks, such as high molecular weight polymers and, in particular, using colloids. Related to colloidal self‐assembly, for example, spontaneous template‐free defect‐free packing to 2D colloidal crystals would be straighforward if the constituent units have exactly similar sizes and if their interacting sites to the neighbouring particles involve suitable broken symmetry . Bending of the 2D sheets from planarity or total suppression of sheet formation can follow even for a minor polydispersity or when defects and geometric frustrations are involved .…”

Synthesis of Single and Multipatch Particles by Dip-Coating Method and Self-Assembly Thereof

“…11−14 The particles can also be used as model system to study complex interaction of globular proteins, inorganic macromolecules such as polyoxometalates, and virus capside formation by mimicking anisotropic patchy interactions. 15 Patchy colloids can be synthesized by modifying a part of the particle surface through chemical or physical modifications. Different methods such as sputtering of metal films, 16 stamp coating of polymer, 17 particle lithography, 18,19 and glancing angle deposition 20,21 have been employed to prepare patchy particles.…”

Anions coordinating anions: analysis of the interaction between anionic Keplerate nanocapsules and their anionic ligands

“…47,48 Other authors studied the assembly of Keplerates in sheet-like structures using Monte Carlo methods. 49 Since anionic ligands coordinating to an already anionic Keplerate appears paradoxical, and given the key role that Keplerate-ligand interactions play in tuning the chemical properties of the inner surface of these capsules, in this manuscript we are reporting a detailed study of the interaction between the Mo 132 capsule and different types of ligands. The analysis relies on the bonding energy decomposition analysis (EDA).…”