Controlling Adsorption of Diblock Copolymer Nanoparticles onto an Aldehyde-Functionalized Hydrophilic Polymer Brush via pH Modulation

Sterically stabilized diblock copolymer nanoparticles with a well-defined spherical morphology and tunable diameter were prepared by RAFT aqueous emulsion polymerization of benzyl methacrylate at 70 °C. The steric stabilizer precursor used for these syntheses contained pendent cis-diol groups, which...

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Bibliographic Details
Published in:Langmuir 2024-02, Vol.40 (7), p.3667-3676
Main Authors: Astier, Samuel, Johnson, Edwin C., Norvilaite, Oleta, Varlas, Spyridon, Brotherton, Emma E., Sanderson, George, Leggett, Graham J., Armes, Steven P.
Format: Article
Language:English
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Summary:Sterically stabilized diblock copolymer nanoparticles with a well-defined spherical morphology and tunable diameter were prepared by RAFT aqueous emulsion polymerization of benzyl methacrylate at 70 °C. The steric stabilizer precursor used for these syntheses contained pendent cis-diol groups, which means that such nanoparticles can react with a suitable aldehyde-functional surface via acetal bond formation. This principle is examined herein by growing an aldehyde-functionalized polymer brush from a planar silicon wafer and studying the extent of nanoparticle adsorption onto this model substrate from aqueous solution at 25 °C using a quartz crystal microbalance (QCM). The adsorbed amount, Γ, depends on both the nanoparticle diameter and the solution pH, with minimal adsorption observed at pH 7 or 10 and substantial adsorption achieved at pH 4. Variable-temperature QCM studies provide strong evidence for chemical adsorption, while scanning electron microscopy images recorded for the nanoparticle-coated brush surface after drying indicate mean surface coverages of up to 62%. This fundamental study extends our understanding of the chemical adsorption of nanoparticles on soft substrates.
ISSN:0743-7463
1520-5827
DOI:10.1021/acs.langmuir.3c03392