In this work, a novel optical fiber sensor system for ultra-low perfluorooctanoic acid (PFOA) detection in aqueous solutions is proposed. It is based on the connection, in series, of two different plastic optical fiber (POF) platforms: the first is a chemical chip realized by using a D-shaped POF with microholes filled with a specific molecularly imprinted polymer (MIP); the second is a typical surface plasmon resonance (SPR) sensor based on a D-shaped POF. In particular, the MIP-based chemical chip was used to launch the light inside the SPR–POF chip to change the SPR phenomenon by exploiting the PFOA–MIP interaction in the microholes. At first, experimental results were performed in water to demonstrate the applicability of the proposed sensing approach for measuring PFOA (or C8) in a concentration range of 1 ppt to 750 ppt, obtaining an ultra-low limit of detection (LOD) equal to about 0.81 ppt. Then, experimental results were carried out in simulated seawater to implement a complex matrix. The obtained results denoted a slight matrix effect, paving the way for the applicability of the proposed chemical sensing mechanism in several aqueous solutions.

In this work, Fe2O3 was investigated as a doping agent for poly(methyl methacrylate) (PMMA) in order to enhance the plasmonic effect in sensors based on D-shaped plastic optical fibers (POFs). The doping procedure consists of immerging a premanufactured POF sensor chip in an iron (III) solution, avoiding repolymerization and its related disadvantages. After treatment, a sputtering process was used to deposit a gold nanofilm on the doped PMMA in order to obtain the surface plasmon resonance (SPR). More specifically, the doping procedure increases the refractive index of the POF’s PMMA in contact with the gold nanofilm, improving the SPR phenomena. The doping of the PMMA was characterized by different analyses in order to determine the effectiveness of the doping procedure. Moreover, experimental results obtained by exploiting different water–glycerin solutions have been used to test the different SPR responses. The achieved bulk sensitivities confirmed the improvement of the plasmonic phenomenon with respect to a similar sensor configuration based on a not-doped PMMA SPR-POF chip. Finally, doped and non-doped SPR-POF platforms were functionalized with a molecularly imprinted polymer (MIP), specific for the bovine serum albumin (BSA) detection, to obtain dose-response curves. These experimental results confirmed an increase in binding sensitivity for the doped PMMA sensor. Therefore, a lower limit of detection (LOD), equal to 0.04 μM, has been obtained in the case of the doped PMMA sensor when compared to the one calculated for the not-doped sensor configuration equal to about 0.09 μM.