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Authors
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Vazirieh Lenjani, S.; Li, C.-W.; Seçkin, S.; König, T. A. F.; Merlitz, H.; Sommer, J.-U.; Rossner, C.
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Title
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Kinetically controlled site-specific self-assembly of hairy colloids
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Date
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06.02.2024
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Number
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0
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Abstract
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The solvophobicity-driven directional self-assembly of polymer-coated gold nanorods is a well-established phenomenon. Yet, the kinetics of this process, the origin of site-selectivity in the self-assembly, and the interplay of (attractive) solvophobic brush interactions and (repulsive) electrostatic forces are not fully understood. Herein, we use a combination of time-resolved (vis/NIR) extinction spectroscopy and finite-difference time-domain (FDTD) simulations to determine conversion profiles for the assembly of gold nanorods with polystyrene shells of distinct thicknesses into their (tip-to-tip) self-assembled structures. In particular, we demonstrate that the assembly process is highly protracted compared with diffusion-controlled rates, and we find that the assembly rate varies for different thickness values of the polymer shell. Our findings were rationalized using coarse-grained molecular dynamics simulations, which also corroborated the tip-to-tip preference in the self-assembly process, albeit with a uniform polymer coating. Utilizing the knowledge of quantified conversion rates for distinct colloidal species, we designed coassembling systems with different brush thicknesses, featuring “narcissistic” self-sorting behavior. This provides new perspectives for high-level supracolloidal self-assembly.
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Publisher
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American Chemical Society
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Wikidata
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Citation
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Langmuir 40 (2024) 2487-2499
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DOI
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https://doi.org/10.1021/acs.langmuir.3c02207
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Tags
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