Abstract
HypothesisSelf-assembly using anisotropic colloidal building blocks may lead to superstructures similar to those found in molecular systems yet can have unique optical, electronic, and structural properties. To widen the spectrum of achievable superstructures and related properties, significant effort was devoted to the synthesis of new types of colloidal particles. Despite these efforts, the preparation of anisotropic colloids carrying chemically orthogonal anchor groups on distinct surface patches remains an elusive challenge. ExperimentsWe report a simple yet effective method for synthesizing patchy particles via seed-mediated heterogeneous nucleation. Key to this procedure is the use of 3-(trimethoxysilyl)propyl methacrylate (TPM) or 3-(trimethoxysilyl)propyl acrylate (TMSPA), which can form patches on a variety of functional polymer seeds via a nucleation and growth mechanism. FindingsA family of anisotropic colloids with tunable numbers of patches and patch arrangements were prepared. By continuously feeding TPM or TMSPA the geometry of the colloids could be adjusted accurately. Furthermore, the patches could be reshaped by selectively polymerizing and/or solvating the individual colloidal compartments. Relying on the chemically distinct properties of the TPM/TMSPA and seed-derived domains, both types of patches could be functionalized independently. Combining detailed control over the patch chemistry and geometry opens new avenues for colloidal self-assembly.
Highlights
Analogous to atoms and molecules, colloidal particles under thermal agitation are able to spontaneously assemble into larger superstructures
Inspired by the work of Sacanna et al, we introduce a general route towards bifunctional anisotropic colloids with chemically orthogonal functional patches by combining seeded dispersion polymerizations with patch formation via heterogeneous nucleation
Compared to conventional dispersion [42,43] and emulsion [44,45] polymerization procedures towards patchy particles, the method outlined here allows for controlling the morphology of the colloidal particles over a significantly broader window [7,46]
Summary
Analogous to atoms and molecules, colloidal particles under thermal agitation are able to spontaneously assemble into larger superstructures. The swelling monomer undergoes a (heat-induced) phase separation from the crosslinked polymer network to form an additional lobe on the surface of the seed particles This phase separation is driven by an elastic stress that is generated upon contraction of the cross-linked polymer network. In addition to the limitations in particle anisotropy, seeded polymerizations can only be employed with monomers that are compatible with the cross-linked seed, i.e., that are able to swell the polymer matrix. This severely limits the chemical freedom in generating particles with distinct lobes. The combined geometric and sitespecific chemical control reported here is a significant step forwards to the next-generation of colloidal model systems for (self-)assembly
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