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.

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

Center for Health and Bioresources AIT Austrian Institute of Technology Giefinggasse 4 1210 Vienna Austria

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

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

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

Institute of Biophysics University of Natural Resources and Life Sciences Vienna Muthgasse 11 2 1190 Vienna Austria

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

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

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

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