Dictating Nanoparticle Assembly via Systems-Level Control of Molecular Multivalency
Name
Santos et al JACS 2019.pdf
Description
Accepted version
Size
1.18 MB
Format
Adobe PDF
Checksum (MD5)
daa8ec67cf80c4822ace6371e44bafab
Author(s)
Santos, Peter J
Cao, Zhen
Zhang, Jianyuan
Alexander-Katz, Alfredo
Macfarlane, Robert J
Date Issued
August 2019
Journal
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Citation
Santo, Peter J. et al. “Dictating Nanoparticle Assembly via Systems-Level Control of Molecular Multivalency.” Journal of the American Chemical Society, 141, 37 (August 2019): 14624–14632 © 2019 The Author(s)
Version
Author's final manuscript
Abstract
Nanoparticle assembly can be controlled by multivalent binding interactions between surface ligands, indicating that more precise control over these interactions is important to design complex nanoscale architectures. It has been well-established in natural materials that the arrangement of different molecular species in three dimensions can affect the ability of individual supramolecular units to coordinate their binding, thereby regulating the strength and specificity of their collective molecular interactions. However, in artificial systems, limited examples exist that quantitatively demonstrate how changes in nanoscale geometry can be used to rationally modulate the thermodynamics of individual molecular binding interactions. As a result, the use of nanoscale design features to regulate molecular bonding remains an underutilized design handle to control nanomaterials synthesis. Here we demonstrate a polymer-coated nanoparticle material where supramolecular bonding and nanoscale structure are used in conjunction to dictate the thermodynamics of their multivalent interactions, resulting in emergent bundling of supramolecular binding groups that would not be expected on the basis of the molecular structures alone. Additionally, we show that these emergent phenomena can controllably alter the superlattice symmetry by using the mesoscale particle arrangement to alter the thermodynamics of the supramolecular bonding behavior. The ability to rationally program molecular multivalency via a systems-level approach therefore provides a major step forward in the assembly of complex artificial structures, with implications for future designs of both nanoparticle- and supramolecular-based materials.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Terms of Use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1021/JACS.9B04999
