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Time-Resolved Analysis of the Structural Dynamics of Assembling Gold Nanoparticles

  • Stefan Merkens
    Stefan Merkens
    CIC nanoGUNE, Tolosa Hiribidea 76, 20018 Donostia - San Sebastián, Spain
    The Hamburg Centre for Ultrafast Imaging (CUI), University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany
  • Mohammad Vakili
    Mohammad Vakili
    The Hamburg Centre for Ultrafast Imaging (CUI), University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany
  • Ana Sánchez-Iglesias
    Ana Sánchez-Iglesias
    CIC biomaGUNE and CIBER-BBN, Paseo Miramón 182, 20014, Donostia - San Sebastián, Spain
  • Lucio Litti
    Lucio Litti
    Dipartimento di Scienze Chimiche, Univerisità degli Studi di Padova, Via Marzolo 1, 35131 Padova, Italy
    More by Lucio Litti
  • Yunyun Gao
    Yunyun Gao
    Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany
    More by Yunyun Gao
  • Paul V. Gwozdz
    Paul V. Gwozdz
    Center for Hybrid Nanostructures (CHyN), University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany
  • Lewis Sharpnack
    Lewis Sharpnack
    Beamline ID02, The European Synchrotron (ESRF), 71 Avenue des Martyrs, 38043 Grenoble, France
  • Robert H. Blick
    Robert H. Blick
    Center for Hybrid Nanostructures (CHyN), University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany
  • Luis M. Liz-Marzán
    Luis M. Liz-Marzán
    CIC biomaGUNE and CIBER-BBN, Paseo Miramón 182, 20014, Donostia - San Sebastián, Spain
    Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain
  • Marek Grzelczak*
    Marek Grzelczak
    Ikerbasque, Basque Foundation for Science, 48013 Bilbao, Spain
    Donostia International Physics Center (DIPC), Manuel Lardizabal Ibilbidea 4, 20018 Donostia - San Sebastián, Spain
    *E-mail: [email protected] (M.G.).
  • , and 
  • Martin Trebbin*
    Martin Trebbin
    Department of Chemistry, The State University of New York at Buffalo, 760 Natural Sciences Complex, Buffalo, New York 14260-3000, United States
    The Hamburg Centre for Ultrafast Imaging (CUI), University of Hamburg, Luruper Chaussee 149, 22761 Hamburg, Germany
    *E-mail: [email protected] (M.T.).
Cite this: ACS Nano 2019, 13, 6, 6596–6604
Publication Date (Web):May 16, 2019
Copyright © 2019 American Chemical Society

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    Abstract Image

    The hydrophobic collapse is a structural transition of grafted polymer chains in a poor solvent. Although such a transition seems an intrinsic event during clustering of polymer-stabilized nanoparticles in the liquid phase, it has not been resolved in real time. In this work, we implemented a microfluidic 3D-flow-focusing mixing reactor equipped with real-time analytics, small-angle X-ray scattering (SAXS), and UV–vis–NIR spectroscopy to study the early stage of cluster formation for polystyrene-stabilized gold nanoparticles. The polymer shell dynamics obtained by in situ SAXS analysis and numerical simulation of the solvent composition allowed us to map the interaction energy between the particles at early state of solvent mixing, 30 ms behind the crossing point. We found that the rate of hydrophobic collapse depends on water concentration, ranging between 100 and 500 nm/s. Importantly, we confirmed that the polymer shell collapses prior to the commencement of clustering.

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    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.9b00575.

    • Calculation of water amount in mixed solution; effect of gas bubbles and requirement of spectral data processing; additional time-resolved optical experiments showing the effect of Au@PS and water concentration and solvent exchange on cluster size and morphology; (static) SAXS reference experiments and fitting of scattering data; theoretical modeling of the interparticle interaction energy (PDF)

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