Gold Nanorod-pNIPAM Hybrids with Reversible Plasmon Coupling: Synthesis, Modeling, and SERS Properties.

The thermoresponsive optical properties of Au nanorod-doped poly(N-isopropylacrylamide) (Au NR-pNIPAM) microgels with different Au NR payloads and aspect ratios are presented. Since the volume phase transition of pure pNIPAM microgels is reversible, the optical response reversibility of Au NR-pNIPAM hybrids is systematically analyzed. Besides, extinction cross-section and near-field enhancement simulations for Au NR-microgel hybrids are performed using a new numerical method based on the surface integral equation method of moments formulation (M3 solver). Additionally, the Au NR-microgel hybrid systems are expected to serve as excellent broadband surface-enhanced Raman scattering (SERS) substrates due to the temperature-controlled formation of hot spots and the tunable optical properties. The optical enhancing properties related to SERS are tested with three laser lines, evidencing excitation wavelength-dependent efficiency that can be easily controlled by either the aspect ratio (length/width) of the assembled Au NR or by the Au NR payload per microgel. Finally, the SERS efficiency of the prepared Au NR-pNIPAM hybrids is found to be stable for months.