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Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels

[Image: see text] The diffusion coefficients of poly(ethylene glycol) methyl ether thiol (PEGSH)-functionalized gold nanoparticles (NPs) with different effective grafting densities were measured in polyacrylamide hydrogels. The NP core size was held constant, and the NPs were functionalized with mix...

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Autores principales: Moncure, Paige J., Millstone, Jill E., Laaser, Jennifer E.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10626584/
https://www.ncbi.nlm.nih.gov/pubmed/37857360
http://dx.doi.org/10.1021/acs.jpcb.3c03249
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author Moncure, Paige J.
Millstone, Jill E.
Laaser, Jennifer E.
author_facet Moncure, Paige J.
Millstone, Jill E.
Laaser, Jennifer E.
author_sort Moncure, Paige J.
collection PubMed
description [Image: see text] The diffusion coefficients of poly(ethylene glycol) methyl ether thiol (PEGSH)-functionalized gold nanoparticles (NPs) with different effective grafting densities were measured in polyacrylamide hydrogels. The NP core size was held constant, and the NPs were functionalized with mixtures of short oligomeric ligands (254 Da PEGSH) and longer (either 1 or 2 kDa PEGSH) ligands. The ratio of short and long ligands was varied such that the grafting density of the high-molecular-weight (MW) ligand ranged from approximately 1 to 100 high-MW ligands/NP. The diffusion coefficients of the NPs were then measured in gels with varying average mesh sizes. The measured diffusion coefficients decreased with higher MW ligand density. Interestingly, the diffusion coefficients for NPs with high effective grafting densities were well-predicted by their hydrodynamic diameters, but the diffusion coefficients for NPs with low effective grafting densities were higher than expected from their hydrodynamic diameters. These results suggest that crowding in the NP ligand shell influences the mechanism of diffusion, with lower grafting densities allowing ligand chain relaxations that facilitate movement through the gel. This work brings new insights into the factors that dictate how NPs move through hydrogels and will inform the development of models for applications such as drug delivery in complex viscoelastic biological materials.
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spelling pubmed-106265842023-11-07 Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels Moncure, Paige J. Millstone, Jill E. Laaser, Jennifer E. J Phys Chem B [Image: see text] The diffusion coefficients of poly(ethylene glycol) methyl ether thiol (PEGSH)-functionalized gold nanoparticles (NPs) with different effective grafting densities were measured in polyacrylamide hydrogels. The NP core size was held constant, and the NPs were functionalized with mixtures of short oligomeric ligands (254 Da PEGSH) and longer (either 1 or 2 kDa PEGSH) ligands. The ratio of short and long ligands was varied such that the grafting density of the high-molecular-weight (MW) ligand ranged from approximately 1 to 100 high-MW ligands/NP. The diffusion coefficients of the NPs were then measured in gels with varying average mesh sizes. The measured diffusion coefficients decreased with higher MW ligand density. Interestingly, the diffusion coefficients for NPs with high effective grafting densities were well-predicted by their hydrodynamic diameters, but the diffusion coefficients for NPs with low effective grafting densities were higher than expected from their hydrodynamic diameters. These results suggest that crowding in the NP ligand shell influences the mechanism of diffusion, with lower grafting densities allowing ligand chain relaxations that facilitate movement through the gel. This work brings new insights into the factors that dictate how NPs move through hydrogels and will inform the development of models for applications such as drug delivery in complex viscoelastic biological materials. American Chemical Society 2023-10-19 /pmc/articles/PMC10626584/ /pubmed/37857360 http://dx.doi.org/10.1021/acs.jpcb.3c03249 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Moncure, Paige J.
Millstone, Jill E.
Laaser, Jennifer E.
Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title_full Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title_fullStr Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title_full_unstemmed Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title_short Role of Ligand Shell Density in the Diffusive Behavior of Nanoparticles in Hydrogels
title_sort role of ligand shell density in the diffusive behavior of nanoparticles in hydrogels
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10626584/
https://www.ncbi.nlm.nih.gov/pubmed/37857360
http://dx.doi.org/10.1021/acs.jpcb.3c03249
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