An official website of the United States government
Observations of nanoparticle superlattice formation over minutes during colloidal nanoparticle synthesis elude description by conventional understanding of self-assembly, which theorizes superlattices require extended formation times to allow for diffusively driven annealing of packing defects. It remains unclear how nanoparticle position annealing occurs on such short time scales despite the rapid superlattice growth kinetics. Here we utilize liquid phase transmission electron microscopy to directly image the self-assembly of platinum nanoparticles into close packed supraparticles over tens of seconds during nanoparticle synthesis. Electron-beam induced reduction of an aqueous platinum precursor formed monodisperse 2–3 nm platinum nanoparticles that simultaneously self-assembled over tens of seconds into 3D supraparticles, some of which showed crystalline ordered domains. Experimentally varying the interparticle interactions ( e.g. , electrostatic, steric interactions) by changing precursor chemistry revealed that supraparticle formation was driven by weak attractive van der Waals forces balanced by short ranged repulsive steric interactions. Growth kinetic measurements and an interparticle interaction model demonstrated that nanoparticle surface diffusion rates on the supraparticles were orders of magnitude faster than nanoparticle attachment, enabling nanoparticles to find high coordination binding sites unimpeded by incoming particles. These results reconcile rapid self-assembly of supraparticles with the conventional self-assembly paradigm in which nanocrystal position annealing by surface diffusion occurs on a significantly shorter time scale than nanocrystal attachment.
more »
« less
Inverse design of a pyrochlore lattice of DNA origami through model-driven experiments
Sophisticated statistical mechanics approaches and human intuition have demonstrated the possibility of self-assembling complex lattices or finite-size constructs. However, attempts so far have mostly only been successful in silico and often fail in experiment because of unpredicted traps associated with kinetic slowing down (gelation, glass transition) and competing ordered structures. Theoretical predictions also face the difficulty of encoding the desired interparticle interaction potential with the experimentally available nano- and micrometer-sized particles. To overcome these issues, we combine SAT assembly (a patchy-particle interaction design algorithm based on constrained optimization) with coarse-grained simulations of DNA nanotechnology to experimentally realize trap-free self-assembly pathways. We use this approach to assemble a pyrochlore three-dimensional lattice, coveted for its promise in the construction of optical metamaterials, and characterize it with small-angle x-ray scattering and scanning electron microscopy visualization.
more »
« less
- Award ID(s):
- 2227650
- PAR ID:
- 10549931
- Publisher / Repository:
- AAAS
- Date Published:
- Journal Name:
- Science
- Volume:
- 384
- Issue:
- 6697
- ISSN:
- 0036-8075
- Page Range / eLocation ID:
- 776 to 781
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Colloidal particles with mobile binding molecules constitute a powerful platform for probing the physics of self-assembly. Binding molecules are free to diffuse and rearrange on the surface, giving rise to spontaneous control over the number of droplet–droplet bonds, i.e. , valence, as a function of the concentration of binders. This type of valence control has been realized experimentally by tuning the interaction strength between DNA-coated emulsion droplets. Optimizing for valence two yields droplet polymer chains, termed ‘colloidomers’, which have recently been used to probe the physics of folding. To understand the underlying self-assembly mechanisms, here we present a coarse-grained molecular dynamics (CGMD) model to study the self-assembly of this class of systems using explicit representations of mobile binding sites . We explore how valence of assembled structures can be tuned through kinetic control in the strong binding limit. More specifically, we optimize experimental control parameters to obtain the highest yield of long linear colloidomer chains. Subsequently tuning the dynamics of binding and unbinding via a temperature-dependent model allows us to observe a heptamer chain collapse into all possible rigid structures, in good agreement with recent folding experiments. Our CGMD platform and dynamic bonding model (implemented as an open-source custom plugin to HOOMD-Blue) reveal the molecular features governing the binding patch size and valence control, and opens the study of pathways in colloidomer folding. This model can therefore guide programmable design in experiments.more » « less
-
Colloidal and nanoparticle self-assembly enables the creation of ordered structures with a variety of electronic and photonic functionalities. The outcomes of the self-assembly processes used to synthesize such structures, however, strongly depend on the uniformity of the individual nanoparticles. Here, we explore the simplest form of particle size dispersity—bidispersity—and its impact on the self-assembly process. We investigate the robustness of self-assembling bcc-type crystals via isotropic interaction potentials in binary systems with increasingly disparate particle sizes by determining their terminal size ratio—the most extreme size ratio at which a mixed binary bcc crystal forms. Our findings show that two-well pair potentials produce bcc crystals that are more robust with respect to particle size ratio than one-well pair potentials. This suggests that an improved self-assembly process is accomplished with a second attractive length scale encoded in the particle–particle interaction, which stabilizes the second-nearest neighbor shell. In addition, we document qualitative differences in the process of ordering and disordering: in bidisperse systems of particles interacting via one-well potentials, we observe a breakdown of order prior to demixing, while in systems interacting via two-well potentials, demixing occurs first and bcc continues to form in parts of the droplet down to low size ratios.more » « less
-
Light-induced self-assembly (LISA) is a non-invasive method for tuning material properties. Photoresponsive ligands coated on the surfaces of nanoparticles are often used to achieve LISA. We report simulation studies for a photoresponsive ligand, azobenzene dithiol (ADT), which switches from a trans-to-cis configuration on exposure to ultraviolet light, allowing self-assembly in ADT-coated gold nanoparticles (NPs). This is attributed to a higher dipole moment of cis-ADT over trans-ADT which leads to a dipole–dipole attraction facilitating self-assembly. Singh and Jha [Comput. Theor. Chem., 2021, 1206, 113492] used quantum-chemistry calculations to quantify the interaction energy of a pair of ADT ligands in their cis and trans conformations. The interaction energy between ligands was fit to a potential energy function of the Lennard–Jones (LJ) form having distinct exponents for attractive and repulsive contributions. Using this generalized equation for the ligand–ligand interaction energy, we calculated the total effective interaction energy between a pair of cis as well as trans ADT-coated NPs. Specifically, we calculated the effective interaction energies between cis/trans-NPs using discrete as well as continuous approaches. Given the limitations of experiments in probing individual ligand conformations, we also studied the effect of varying the functional ligand length on the interaction energy between NPs and identified the optimal functional ligand length to capture the steric and conformational effects. Finally, using the effective interaction energy, we obtained a generalized potential energy function, which was applied in Langevin dynamics simulations to capture self-assembly in NPs.more » « less
-
In contrast to most self-assembling synthetic materials, which undergo unbounded growth, many biological self-assembly processes are self-limited. That is, the assembled structures have one or more finite dimensions that are much larger than the size scale of the individual monomers. In many such cases, the finite dimension is selected by a preferred curvature of the monomers, which leads to self-closure of the assembly. In this article, we study an example class of self-closing assemblies: cylindrical tubules that assemble from triangular monomers. By combining kinetic Monte Carlo simulations, free energy calculations, and simple theoretical models, we show that a range of programmable size scales can be targeted by controlling the intricate balance between the preferred curvature of the monomers and their interaction strengths. However, their assembly is kinetically controlled—the tubule morphology is essentially fixed shortly after closure, resulting in a distribution of tubule widths that is significantly broader than the equilibrium distribution. We develop a simple kinetic model based on this observation and the underlying free-energy landscape of assembling tubules that quantitatively describes the distributions. Our results are consistent with recent experimental observations of tubule assembly from triangular DNA origami monomers. The modeling framework elucidates design principles for assembling self-limited structures from synthetic components, such as artificial microtubules that have a desired width and chirality.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1126/science.adl5549
