Plasmon-Enhanced Multiphoton Polymer Crosslinking for Selective Modification of Plasmonic Hotspots

The Journal of Physical Chemistry C, vol. 128, pp. 18641–18650

Abstract

High Resolution Image Download MS PowerPoint Slide A novel approach to selectively modify narrow subareas of metallic nanostructures adjacent to plasmonic hotspots, where strong electromagnetic field amplification occurs upon localized surface plasmon (LSP) excitation, is reported. In contrast to surface plasmon-triggered polymerization, it relies on plasmonically enhanced multiphoton crosslinking (MPC) of polymer chains carrying photoactive moieties. When they are contacted with metallic nanostructures and irradiated with a femtosecond near-infrared beam resonantly coupled with LSPs, the enhanced field intensity locally exceeds the threshold and initiates MPC only at plasmonic hotspots. This concept is demonstrated by using gold nanoparticle arrays coated with two specifically designed polymers. Local MPC of a poly( N, N -dimethylacrylamide)-based copolymer with an anthraquinone crosslinker is shown via atomic force microscopy. Additionally, MPC is tested with a thermoresponsive poly( N -isopropylacrylamide)-based terpolymer. The reversible thermally induced collapse and swelling of the MPC-formed hydrogel at specific nanoparticle locations are confirmed by polarization-resolved localized surface plasmon resonance (LSPR) spectroscopy. These hybrid metallic/hydrogel materials can be further postmodified, offering attractive characteristics for future spectroscopic/bioanalytical applications.

Authors 10

1. Yevhenii M. Morozov corresponding

   AIT Austrian Institute of Technology GmbH

   Affiliation as printed

   Center for Health & Bioresources, AIT-Austrian Institute of Technology, Giefinggasse 4, 1210 Vienna, Austria

2. Nestor Gisbert Quilis

   AIT Austrian Institute of Technology GmbH

   Affiliation as printed

   Biosensor Technologies, AIT-Austrian Institute of Technology, Konrad-Lorenz-Strasse 24, 3430 Tulln an der Donau, Austria

3. Stefan Fossati

   Czech Academy of Sciences · FZU - Institute of Physics of the Czech Academy of Sciences

   Affiliation as printed

   FZU-Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21 Prague, Czech Republic

4. Laura De Laporte Aachen DWI - Leibniz Institute for Interactive Materials Institute for Technical and Macromolecular Chemistry Institute of Applied Medical Engineering Department of Advanced Materials for Biomedicine

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI-Leibniz Institute for Interactive Materials, Forckenbeckstrasse 50, D-52074 Aachen, Germany

   Institute for Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1-2, D-52074 Aachen, Germany

   Institute of Applied Medical Engineering, Department of Advanced Materials for Biomedicine, RWTH Aachen University, Forckenbeckstraße 55, D-52074 Aachen, Germany

5. Claudia Gusenbauer

   BOKU University

   Affiliation as printed

   Institute of Wood Technology and Renewable Materials, University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Strasse 24, 3430 Tulln an der Donau, Austria

6. Andreas Weber

   BOKU University

   Affiliation as printed

   Institute of Biophysics, University of Natural Resources and Life Sciences, Vienna, Muthgasse 11/II, 1190 Vienna, Austria

7. José Luis Toca-Herrera

   BOKU University

   Affiliation as printed

   Institute of Biophysics, University of Natural Resources and Life Sciences, Vienna, Muthgasse 11/II, 1190 Vienna, Austria

8. Fiona Wiesner

   University of Siegen

   Affiliation as printed

   Macromolecular Chemistry, Department of Chemistry and Biology, University of Siegen, Adolf Reichwein-Straße 2, 57074 Siegen, Germany

9. Ulrich Jonas

   University of Siegen

   Affiliation as printed

   Macromolecular Chemistry, Department of Chemistry and Biology, University of Siegen, Adolf Reichwein-Straße 2, 57074 Siegen, Germany

10. Jakub Dostálek corresponding

    Danube Private University · Czech Academy of Sciences · FZU - Institute of Physics of the Czech Academy of Sciences

    Affiliation as printed

    FZU-Institute of Physics, Czech Academy of Sciences, Na Slovance 2, 182 21 Prague, Czech Republic

    LiST-Life Sciences Technology, Danube Private University, Viktor-Kaplan-Strasse 2, 2700 Wiener Neustadt, Austria