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.

• Publication type
• Journal Article MeSH

Plasmonic nanomaterials have become an integral part of numerous technologies, where they provide important functionalities spanning from extraction and harvesting of light in thin film optical devices to probing of molecular species and their interactions on biochip surfaces. More recently, we witness increasing research efforts devoted to a new class of plasmonic nanomaterials that allow for on-demand tuning of their properties by combining metallic nanostructures and responsive hydrogels. This review addresses this recently emerged vibrant field, which holds potential to expand the spectrum of possible applications and deliver functions that cannot be achieved by separate research in each of the respective fields. It aims at providing an overview of key principles, design rules, and current implementations of both responsive hydrogels and metallic nanostructures. We discuss important aspects that capitalize on the combination of responsive polymer networks with plasmonic nanostructures to perform rapid mechanical actuation and actively controlled nanoscale confinement of light associated with resonant amplification of its intensity. The latest advances towards the implementation of such responsive plasmonic nanomaterials are presented, particularly covering the field of plasmonic biosensing that utilizes refractometric measurements as well as plasmon-enhanced optical spectroscopy readout, optically driven miniature soft actuators, and light-fueled micromachines operating in an environment resembling biological systems.

• MeSH
• Hydrogels * MeSH
• Nanostructures * chemistry   MeSH
• Polymers MeSH
• Spectrum Analysis MeSH
• Publication type
• Journal Article MeSH
• Review MeSH
• Names of Substances
• Hydrogels * MeSH
• Polymers MeSH

The swelling and collapsing of thermo-responsive poly(N-isopropylacrylamide)-based polymer (pNIPAAm) networks are investigated in order to reveal the dependency on their kinetics and maximum possible actuation speed. The pNIPAAm-based network was attached as thin hydrogel film to lithographically prepared gold nanoparticle arrays to exploit their localized surface plasmon resonance (LSPR) for rapid local heating. The same substrate also served for LSPR-based monitoring of the reversible collapsing and swelling of the pNIPAAm network through its pronounced refractive index changes. The obtained data reveal signatures of multiple phases during the volume transition, which are driven by the diffusion of water molecules into and out of the network structure and by polymer chain re-arrangement. For the micrometer-thick hydrogel film in the swollen state, the layer can respond as fast as several milliseconds depending on the strength of the heating optical pulse and on the tuning of the ambient temperature with respect to the lower critical solution temperature of the polymer. Distinct differences in the time constants of swelling and collapse are observed and attributed to the dependence of the cooperative diffusion coefficient of polymer chains on polymer volume fraction. The reported results may provide guidelines for novel miniature actuator designs and micromachines that take advantages of the non-reciprocal temperature-induced volume transitions in thermo-responsive hydrogel materials.

• MeSH
• Hydrogels chemistry   MeSH
• Kinetics MeSH
• Metal Nanoparticles * MeSH
• Polymers * chemistry   MeSH
• Temperature MeSH
• Gold MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Names of Substances
• Hydrogels MeSH
• Polymers * MeSH
• Gold MeSH