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Direct Observation of Interactions between Nanoparticles and Nanoparticle Self-Assembly in Solution

TitleDirect Observation of Interactions between Nanoparticles and Nanoparticle Self-Assembly in Solution
Publication TypeJournal Article
Year of Publication2017
AuthorsTan, Shu Fen, Chee See Wee, Lin Guanhua, and Mirsaidov Utkur
JournalAccounts Chem. Res.
Date Published06/2017
Keywordscalcium-carbonate, electron-microscopy, gold nanorods, growth, hydration forces, inorganic nanoparticles, interfaces, liquid-phase, nanocrystals, nucleation

CONSPECTUS: Hierarchically organized nanoparticles (NPs) possess unique properties and are relevant to various technological applications. An important "bottom-up" strategy for building such hierarchical nanostructures is to guide the individual NPs into ordered nanoarchitectures using intermolecular interactions and external forces. However, our current understanding of the nanoscale interactions that govern such self-assembly processes usually relies on post-synthesis/assembly or indirect characterization. Theoretical models that can derive these interactions are presently constrained to systems with only a few particles or on short time scales. Hence, except for a number of special cases, a description that captures the detailed mechanisms of NP self-assembly still eludes us. By imaging the assembly of NPs in solution with subnanometer resolution and in real-time, in situ liquid cell transmission electron microscopy (LC-TEM) can identify previously unknown intermediate stages and improve our understanding of such processes. Here, we review recent studies where we explored NP self-assembly at different organization length scales using LC-TEM: (1) we followed the transformation of atoms into crystalline NPs in solution, (2) we highlighted the role of solvation forces on interaction dynamics between NPs, and (3) we described the assembly dynamics of NPs in solution. In the case of nanocrystal nucleation, we identified the existence of three distinct steps that lead to the formation of crystalline nuclei in solution. These steps are spinodal decomposition of the precursor solution into solute-rich and solute-poor liquid phases, nucleation of amorphous clusters within the solute-rich liquid phase, followed by crystallization of these amorphous clusters into crystalline NPs. The next question we ask is how NPs interact in solution once they form. It turns out that the hydration layer surrounding each NP acts as a repulsive barrier that prevents NPs from readily attaching to each other due to attractive vdW forces. Consequently, two interacting NPs form a metastable pair separated by their one water molecule thick hydration shell and they undergo attachment only when this water between them is drained. Next, we explore the self-assembly of many NP systems where the formation of linear chains from spherical NPs or nanorods (NRs) is mediated by linker molecules. At low linker concentration, both spherical NPs and NRs tend to form linear chains because of the need to reduce electrostatic repulsion between NP building blocks. When the concentration of linkers is increased, the attachment of NPs is no longer linear. For example, we find that two NRs undergo side-to-side assembly due to decreased electrostatic repulsion and the anisotropic distribution of linkers on NR surfaces at high linker concentration. Lastly, we look at the formation of NP nanorings directed by ethylenediaminetetraacetic acid (EDTA) nanodroplets in water. Our study shows that nanoring assemblies form via sequential attachment of NPs to binding sites located along the circumference of the EDTA nanodroplet, followed by rearrangement and reorientation of the attached NPs. Our approach based on real-time visualization of nanoscale processes not only reveals all the intermediate steps of NP assembly, but also provides quantitative description on the interactions between nanoscale objects in solution.


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