Gold nanorods (NRs), which were modified with polyions, were fixed on polycation-modified glass substrates. Adsorption of antibodies and antigens on the glass substrates induced large peak shifts (44 nm) of longitudinal surface plasmon bands in the near-infrared region. The shifts were assignable to changes of refractive indices of polyion layers at the glass surfaces.Gold nanorods (NRs) are rod-shaped nanoparticles that exhibit transverse and longitudinal surface plasmon (SP) bands in the visible and near-infrared (near-IR) regions, respectively. 13 The positions of the SP bands are tunable depending on the shape of the NRs and the refractive indices of their surroundings. 46 In previous papers, label-free optical sensors based on peak shifts of the longitudinal SP bands have been used to determine refractive indices of solvents 7 and to detect avidin biotin conjugation 8 and antibodyantigen binding. 9, 10 We also reported that longitudinal SP bands of NRs on a clean surface of a glass substrate showed peak shifts when they were immersed in some solvents.7 However, the peak shift from water to chloroform (36 nm) was much smaller than the half bandwidth of NRs (205 nm). It was shown that the refractive indices of the surrounding medium did not perturb the local refractive indices of the NRs on a glass substrate.In the present work, NRs were deposited on a glass substrate through electrostatic interaction between polyanions on NRs and polycationic-modified surfaces. Peak shifts of the longitudinal SP bands were monitored as a function of concentration of antigen in aqueous solution.The NRs were synthesized by a photochemical method 11 in a joint research project between Mitsubishi Materials Corp. and Dai-Nihon-Toryo Co., Ltd. The initial ¦ potential of the NRs was +20 mV, which originates from hexadecyltrimethylammonium bromide (CTAB) bilayers on the NR surfaces. A typical procedure for surface modification of NRs was as follows. Asprepared NRs were centrifuged twice at 15000 © g for 10 min and decanted to remove excess CTAB from the solution. The positively charged surfaces of the NRs were wrapped with poly(styrene sulfonate) (PSS, M w = 70000 g mol
¹1, Aldrich) through electrostatic interaction.12,13 The PSS-modified NRs are denoted PSSNR. The ¦ potential of PSSNRs was typically ¹21.5 mV. The absorption spectrum of a PSSNR solution shows double peaks that are typical for colloidal NRs, indicating modification by PSS of the NRs without formation of aggregates.To deposit PSSNRs on a glass substrate, water-soluble polymers were coated on the substrate layer-by-layer. 7 The resulting hydrophilic glass substrate was sequentially immersed in a poly(allylamine hydrochloride) (PAH, M w = 15000 g mol , 20 min) to obtain a multilayered polymer film (polyion substrate). The outermost layer on the substrate was positively charged due to the presence of PAH. The polyionsubstrate was then immersed in a PSSNR solution for 24 h to deposit PSS NR on the substrate surface. After immersion, the substrate was washed with water an...