A surface plasmon resonance (SPR) sodium ion sensor using an ion optode membrane film was experimentally and theoretically described based on an absorption-based SPR principle proposed in our previous article (Kurihara, K.; Suzuki, K. Anal. Chem. 2002, 74, 696-701). The sodium ion concentrations from 10-6 to 10-1 have been successfully determined not only by the resonance angle diagnosis of the SPR curve but also by the minimum reflectance one. The ion optode film was plasticized poly(vinyl chloride) including a neutral sodium ionophore, a pH-sensitive cationic dye, and an anionic additive. Its optical absorption intensity changed with the sodium ion concentrations. The SPR ion sensor physically measured the complex refractive index caused by the absorption in the ion optode film. We have exhaustively investigated the experimental response behavior of the SPR curve relative to the sodium ion concentrations by comparison with numerically simulated SPR curves using a three-layer Fresnel equation including experimental values for the sodium ion optode membrane film. As predicted by the absorption-based SPR principle, the SPR curve behavior of the SPR ion sensors depended on two factors: one was the relation between the excitation frequency of the light source and the absorption maximum frequency in the ion optode film while the other was the gold metallic thickness in the Kretchmann configuration. The concept and practical theory of an absorption-based SPR sensor not only have been proved by the experimental results of the SPR sodium ion sensor but also have successfully allowed flexible ion sensing in an SPR sensor, which would be very difficult without the absorption mechanism in the ion optode film.
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