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. 2024 Nov 3;14(21):1764.
doi: 10.3390/nano14211764.

An MIP-Based PFAS Sensor Exploiting Nanolayers on Plastic Optical Fibers for Ultra-Wide and Ultra-Low Detection Ranges-A Case Study of PFAS Detection in River Water

Rosalba Pitruzzella  1 , Alessandro Chiodi  2 , Riccardo Rovida  1 , Francesco Arcadio  1 , Giovanni Porto  2 , Simone Moretti  3 , Gianfranco Brambilla  4 , Luigi Zeni  1 , Nunzio Cennamo  1
Affiliations

An MIP-Based PFAS Sensor Exploiting Nanolayers on Plastic Optical Fibers for Ultra-Wide and Ultra-Low Detection Ranges-A Case Study of PFAS Detection in River Water

Rosalba Pitruzzella et al. Nanomaterials (Basel). .

Abstract

In this work, a novel optical-chemical sensor for the detection of per- and polyfluorinated substances (PFASs) in a real scenario is presented. The proposed sensing approach exploits the multimode characteristics of plastic optical fibers (POFs) to achieve unconventional sensors via surface plasmon resonance (SPR) phenomena. The sensor is realized by the coupling of an SPR-POF platform with a novel chemical chip based on different polymeric nanolayers over the core of a D-shaped POF, one made up of an optical adhesive and one of a molecularly imprinted polymer (MIP) for PFAS. The chemical chip is used to launch the light into the SPR D-shaped POF platform, so the interaction between the analyte and the MIP's sites can be used to modulate the propagated light in the POFs and the SPR phenomena. Selectivity tests and dose-response curves by standard PFOA water solutions were carried out to characterize the detection range sensor response, obtaining a wide PFAS response range, from 1 ppt to 1000 ppt. Then, tests performed on river water samples collected from the Bormida river paved the way for the applicability of the proposed approach to a real scenario.

Keywords: UV-curable optical adhesive; molecularly imprinted polymers (MIPs); per- and polyfluorinated substances (PFASs); perfluorooctanoic acid (PFOA); persistent organic pollutants (POPs); plastic optical fibers (POFs); surface plasmon resonance (SPR).

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Conflict of interest statement

The authors declare no conflicts of interest.

Figures

Figure 1
Figure 1
(a) A picture of the SPR–POF probe embedded in a 3D-printed holder. (b) A cross-section of the D-shaped POF plasmonic region.
Figure 2
Figure 2
A picture of the MIP-based POF chemical chip embedded into a 3D-printed holder. Insets: The D-shaped POF surface before and after the nanolayer deposition.
Figure 3
Figure 3
A picture of the experimental setup based on a custom 3D-printed holder, a white light source, two POF chips connected in series, and a spectrometer.
Figure 4
Figure 4
Normalized transmitted spectra (SPR spectra) achieved at different PFOA concentrations in MilliQ water ranging from 5 to 2000 ppt.
Figure 5
Figure 5
Resonance wavelength variations (calculated with respect to the blank) versus PFOA concentration in Milli-Q water, with the error bars and experimental fitting achieved by Equation (2), in a semi-log scale.
Figure 6
Figure 6
SPR spectra achieved at different PFOA concentrations in MilliQ water, ranging from 5 to 2000 ppt, via a NIP-based POF sensor configuration.
Figure 7
Figure 7
Selectivity tests: comparison between the resonance wavelength variations produced by 2-FAL, ATZ, and 5-HMF at 10,000 ppt and the analyte (PFOA) at 1000 ppt.
Figure 8
Figure 8
Estimated values of the PFAS concentration in the Bormida river via the sample at two dilution factors (1:1000, 1:500).
Figure 9
Figure 9
PFAS concentration ranges obtained by the same MIP receptor combined with different POF sensor configurations.
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