Free thiols regulate the interactions and self-assembly of thiol-passivated metal nanoparticles

Pan Sun; Linsey M. Nowack; Wei Bu; Mrinal K. Bera; Sean Griesemer; Morgan Reik; Joshua Portner; Stuart A. Rice; Mark L. Schlossman; Binhua Lin

doi:10.1021/acs.nanolett.0c04147

Free thiols regulate the interactions and self-assembly of thiol-passivated metal nanoparticles

Pan Sun, Linsey M. Nowack, Wei Bu, Mrinal K. Bera, Sean Griesemer, Morgan Reik, Joshua Portner, Stuart A. Rice, Mark L. Schlossman, Binhua Lin

Research output: Contribution to journal › Article › peer-review

10 Scopus citations

Abstract

Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols). Simulations demonstrate that the presence of free thiols produces a nearly symmetrical coating of ligands on the core. X-ray measurements show that above a critical value of core-ligand coverage the nanoparticle core rises above the water surface, the edge-to-edge distance between neighboring nanoparticles increases, and the nanoparticle coverage of the surface decreases. These results demonstrate the important role of free thiols: they regulate the organization of bound thiols on the core and the interactions of nanoparticles with their surroundings.

Original language	English
Pages (from-to)	1613-1619
Number of pages	7
Journal	Nano Letters
Volume	21
Issue number	4
DOIs	https://doi.org/10.1021/acs.nanolett.0c04147
State	Published - Feb 24 2021
Externally published	Yes

Funding

This research is supported by NSF’s ChemMatCARS. NSF’s ChemMatCARS Sector 15 is funded by the Divisions of Chemistry (CHE) and Materials Research (DMR), National Science Foundation, under grant number NSF/CHE-1834750. We also acknowledge support from the University of Chicago MRSEC NSF/DMR-1420709 for BL and SAR and NSF/DMR-2011854 for JP. Use of the Advanced Photon Source, an Office of Science User Facility operated for the U.S. Department of Energy (DOE) Office of Science by Argonne National Laboratory, was supported by the U.S. DOE under Contract No. DE-AC02-06CH11357.

Funders	Funder number
Materials Research
University of Chicago MRSEC	NSF/DMR-1420709
National Science Foundation	NSF/CHE-1834750, 1834750
U.S. Department of Energy	DE-AC02-06CH11357
Division of Chemistry
Office of Science
Argonne National Laboratory

Keywords

Free thiol
Ligand symmetry
Liquid surface
Nanoparticles

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10.1021/acs.nanolett.0c04147

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title = "Free thiols regulate the interactions and self-assembly of thiol-passivated metal nanoparticles",

abstract = "Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols). Simulations demonstrate that the presence of free thiols produces a nearly symmetrical coating of ligands on the core. X-ray measurements show that above a critical value of core-ligand coverage the nanoparticle core rises above the water surface, the edge-to-edge distance between neighboring nanoparticles increases, and the nanoparticle coverage of the surface decreases. These results demonstrate the important role of free thiols: they regulate the organization of bound thiols on the core and the interactions of nanoparticles with their surroundings.",

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AU - Nowack, Linsey M.

AU - Bu, Wei

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AU - Griesemer, Sean

AU - Reik, Morgan

AU - Portner, Joshua

AU - Rice, Stuart A.

AU - Schlossman, Mark L.

AU - Lin, Binhua

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N2 - Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols). Simulations demonstrate that the presence of free thiols produces a nearly symmetrical coating of ligands on the core. X-ray measurements show that above a critical value of core-ligand coverage the nanoparticle core rises above the water surface, the edge-to-edge distance between neighboring nanoparticles increases, and the nanoparticle coverage of the surface decreases. These results demonstrate the important role of free thiols: they regulate the organization of bound thiols on the core and the interactions of nanoparticles with their surroundings.

AB - Thiol ligands bound to the metallic core of nanoparticles determine their interactions with the environment and self-assembly. Recent studies suggest that equilibrium between bound and free thiols alters the ligand coverage of the core. Here, X-ray scattering and MD simulations investigate water-supported monolayers of gold-core nanoparticles as a function of the core-ligand coverage that is varied in experiments by adjusting the concentration of total thiols (sum of free and bound thiols). Simulations demonstrate that the presence of free thiols produces a nearly symmetrical coating of ligands on the core. X-ray measurements show that above a critical value of core-ligand coverage the nanoparticle core rises above the water surface, the edge-to-edge distance between neighboring nanoparticles increases, and the nanoparticle coverage of the surface decreases. These results demonstrate the important role of free thiols: they regulate the organization of bound thiols on the core and the interactions of nanoparticles with their surroundings.

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Free thiols regulate the interactions and self-assembly of thiol-passivated metal nanoparticles

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