In this work an innovative, miniaturized and low cost optical chemical sensor (POF-MIP platform), based on a molecular imprinted polymer (MIP) and surface plasmon resonance in a plastic optical fiber (POF), is presented and preliminarily tested for monitoring of furfural (furan-2-carbaldehyde) in transformer oil. To this end, the optical platform was coupled to an MIP layer, highly selective for furfural. The ability of the developed sensor to directly detect furfural in the insulating oil was investigated. The detection limit of the sensor has been found to be 9 ppb, with a linear response up to about 30 ppb. However there is a sensible response up to 0.15 ppm. Because of the small linearity range, the Hill equation is suggested for the quantification. The sensor has been effectively tested in real oil samples collected from aged electrical equipment removed from service. The assessed concentration of furfural is in good agreement with that evaluated by a high pressure liquid chromatography (HLPC) method, confirming the good selectivity of the proposed sensor.
A surface plasmon resonance (SPR) platform, based on a D-shaped plastic optical fiber (POF), combined with a biomimetic receptor, i.e., a molecularly imprinted polymer (MIP), is proposed to detect furfural (2-furaldheide, 2-FAL) in fermented beverages like wine. MIPs have been demonstrated to be a very convenient biomimetic receptor in the proposed sensing device, being easy and rapid to develop, suitable for on-site determinations at low concentrations, and cheap. Moreover, the MIP film thickness can be changed to modulate the sensing parameters. The possibility of performing single drop measurements is a further favorable aspect for practical applications. For example, the use of an SPR-MIP sensor for the analysis of 2-FAL in a real life matrix such as wine is proposed, obtaining a low detection limit of 0.004 mg L−1. The determination of 2-FAL in fermented beverages is becoming a crucial task, mainly for the effects of the furanic compounds on the flavor of food and their toxic and carcinogenic effect on human beings.
The possibility of investigating the binding properties of the same molecularly imprinted polymer (MIP), most probably heterogeneous, at various concentration levels by different methods such as batch equilibration and sensing, is examined, considering two kinds of sensors, based respectively on electrochemical and surface plasmon resonance (SPR) transduction. As a proof of principle, the considered MIP was obtained by non-covalent molecular imprinting of 2-furaldehyde (2-FAL). It has been found that different concentration ranges of 2-FAL in aqueous matrices can be measured by the two sensing methods. The SPR sensor responds in a concentration range from 1 × 10−4 M down to about 1 × 10−7 M, while the electrochemical sensor from about 5 × 10−6 M up to about 9 × 10−3 M. The binding isotherms have been fit to the Langmuir adsorption model, in order to evaluate the association constant. Three kinds of sites with different affinity for 2-FAL have been detected. The sites at low affinity are similar to the interaction sites of the corresponding NIP since they have a similar association constant. This is near to the affinity evaluated by batch equilibration too. The same association constant has been evaluated in the same concentration range. The sensing methods have been demonstrated to be very convenient for the characterization of the binding properties of MIP in comparison to the batch equilibration, in terms of reproducibility and low amount of material required for the investigation.
The present study proposes the application of a recently developed optical–chemical sensor system to glyphosate detection. The device probes the refractive index variation in a chip based on a plastic optical fiber (POF) in which three orthogonal micro-holes were created and filled with an acrylic-based molecularly imprinted polymer (MIP). This sensitive chip, connected in series to a gold-coated SPR-POF platform, can modify the surface plasmon resonance (SPR) phenomena by exploiting the multimode characteristic of the POFs. Therefore, the gold film of the SPR-POF platform is not covered by the MIP layer, improving the sensor’s performance because the interaction between the analyte (glyphosate) and the polymer recognition cavities occurs in the core and not in the cladding of the waveguide. Indeed, the sample solution is dropped on the MIP-based chip while a water drop is constantly maintained above the gold surface of the reference SPR-POF platform to excite the surface plasmons, modulated by the MIP interaction with the target analyte. The device is here for the first time applied for glyphosate sensing in water samples. The high sensitivity and selectivity are proven, and tests on real samples highlight the good performances of the developed sensors.
Optical chemosensors with surface plasmon resonance (SPR) transduction are widely employed, even in complex environments, such as those outside the laboratory. In this context, not only the chemical nature but also the physical form of the receptor layer is particularly relevant. Synthetic receptors as molecularly imprinted polymers (MIPs) are well suited. This is demonstrated here in the case of an SPR sensor platform based on a multimode plastic optical fiber, which is very promising for on site application due to the low dimensions and low cost. A specific MIP was used as the receptor, with high affinity for the substance to be determined, 2-furaldehyde, in water. Here, a medium of high refractive index, i.e., vegetable oil, was considered because of the high interest for its determination in industrial diagnostics. The effects of the MIP layer thickness and the washing extent on the quality of the analytical signal were investigated. Better spectra were generated at the thinner MIP layer, while a lower detection limit is reached with extended washing.