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Nanoparticle Loading in Swollen Polymer Gels: An Unexpected Thermodynamic Twist
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    Nanoparticle Loading in Swollen Polymer Gels: An Unexpected Thermodynamic Twist
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    • Seth D. Waugaman
      Seth D. Waugaman
      Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    • Mykyta Dementyev
      Mykyta Dementyev
      Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    • Elmira Abbasi GharehTapeh
      Elmira Abbasi GharehTapeh
      Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    • Carlos G. Lopez
      Carlos G. Lopez
      Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    • Robert T. Mathers
      Robert T. Mathers
      Chemistry, The Pennsylvania State University, New Kensington, Pennsylvania 15068, United States
    • Robert J. Hickey*
      Robert J. Hickey
      Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
      Materials Research Institute, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
      *email: [email protected]
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    Nano Letters

    Cite this: Nano Lett. 2025, 25, 8, 3323–3329
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    https://doi.org/10.1021/acs.nanolett.4c06501
    Published February 17, 2025
    Copyright © 2025 American Chemical Society

    Abstract

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    Tailoring polymer gel functionality by loading small molecules and nanoparticles is critical for drug delivery and tissue regeneration. Typically, solute loading in gels correlates with the degree of solvent swelling, which is controlled by the cross-link density and polymer/solvent interactions. However, the general assumption that the degree of swelling is the primary factor for nanoparticle loading is incorrect. Here, we demonstrate that the pairwise interactions between the polymer, solvent, and solute dictate the solute loading in gels. We performed gel loading studies of ligand-stabilized gold nanoparticles using different solvents, polymer network hydrophobicity, and cross-link densities, and found that nanoparticle distribution between polymer and solvent correlate with calculated thermodynamic partition coefficients. Despite previous assumptions that the maximum nanoparticle loading occurs at the highest degree of gel swelling, we reveal that nanoparticles preferentially load into gels with lower solvent swelling if ligand/polymer interactions are more favorable than ligand/solvent interactions.

    Copyright © 2025 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.nanolett.4c06501.

    • Experimental details and polymer characterization results such as AuNP characterization, UV–vis of the colloidal solutions as well as of the loaded gels, scattering analyses of the colloids and loaded gels, as well as rheological studies of swollen gels (PDF)

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    Nano Letters

    Cite this: Nano Lett. 2025, 25, 8, 3323–3329
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.nanolett.4c06501
    Published February 17, 2025
    Copyright © 2025 American Chemical Society

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