Hendley, C.T., Fielding, L.A. orcid.org/0000-0002-4958-1155, Jones, E.R. orcid.org/0000-0001-6194-0504 et al. (3 more authors) (2018) Mechanistic insights into diblock copolymer nanoparticle–crystal interactions revealed via in situ atomic force microscopy. Journal of the American Chemical Society, 140 (25). pp. 7936-7945. ISSN 0002-7863
Abstract
Recently, it has become clear that a range of nanoparticles can be occluded within single crystals to form nanocomposites. Calcite is a much-studied model, but even in this case we have yet to fully understand the details of the nanoscale interactions at the organic-inorganic interface that lead to occlusion. Here, a series of diblock copolymer nanoparticles with well-defined surface chemistries were visualized interacting with a growing calcite surface using in situ atomic force microscopy. These nanoparticles comprise a poly(benzyl methacrylate) (PBzMA) core-forming block and a non-ionic poly(glycerol monomethacrylate) (Ph-PGMA), a carboxylic acid-tipped poly(glycerol monomethacrylate) (HOOC-PGMA), or an anionic poly(methacrylic acid) (PMAA) stabilizer block. Our results reveal three modes of interaction between the nanoparticles and the calcite surface: (i) attachment followed by detachment, (ii) sticking to and "hovering" over the surface, allowing steps to pass beneath the immobilized nanoparticle, and (iii) incorporation of the nanoparticle by the growing crystals. By analyzing the relative contributions of these three types of interactions as a function of nanoparticle surface chemistry, we show that ∼85% of PMAA 85 -PBzMA 100 nanoparticles either "hover" or become incorporated, compared to ∼50% of the HOOC-PGMA 71 -PBzMA 100 nanoparticles. To explain this difference, we propose a two-state binding mechanism for the anionic PMAA 85 -PBzMA 100 nanoparticles. The "hovering" nanoparticles possess highly extended polyelectrolytic stabilizer chains and such chains must adopt a more "collapsed" conformation prior to successful nanoparticle occlusion. This study provides a conceptual framework for understanding how sterically stabilized nanoparticles interact with growing crystals, and suggests design principles for improving occlusion efficiencies.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 American Chemical Society. This is an author-produced version of a paper subsequently published in Journal of the American Chemical Society. Uploaded in accordance with the publisher's self-archiving policy. |
Keywords: | Bioengineering; Nanotechnology |
Dates: |
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Institution: | The University of Sheffield |
Academic Units: | The University of Sheffield > Faculty of Science (Sheffield) > Department of Chemistry (Sheffield) |
Funding Information: | Funder Grant number ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/J018589/1 ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/P005241/1 ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/K006290/1 ENGINEERING AND PHYSICAL SCIENCE RESEARCH COUNCIL EP/R003009/1 |
Depositing User: | Symplectic Sheffield |
Date Deposited: | 08 Feb 2023 11:11 |
Last Modified: | 08 Feb 2023 11:14 |
Status: | Published |
Publisher: | American Chemical Society (ACS) |
Refereed: | Yes |
Identification Number: | 10.1021/jacs.8b03828 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:196084 |