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.
Irbesartan is a drug used to treat hypertension and high blood pressure. Recent studies associated sartans with several forms of cancer, making removing this class of substances from the environment a high priority. The EU has categorized drugs as emerging pollutants, and they can be more potent than other substances because they were designed to operate at low concentrations. Thus, effective and sensitive methods of determining Irbesartan selectively and accurately in environmental samples are necessary. MIPs have already been used to remove pollutants from complex matrixes, so they were also chosen for this work. In particular, a polyacrylate-based MIP was used to functionalize the graphite working electrode of screen-printed cells (SPCs), aiming to develop a voltammetric method for Irbesartan sensing. The MIP composition and the experimental conditions for the electrochemical determination were optimized through a Design of Experiments (DoE) approach. The whole analysis was replicated with different SPCs obtaining similar results, which highlight the good reproducibility potential. MIP-based electrodes were also applied to determine Irbesartan in fortified tap water samples, obtaining high recovery percentages. Given the good results, the electrochemical method based on MIP-modified screen-printed electrodes is promising for quantifying Irbesartan at a trace level.
2 October 2023 in Colloids and Surfaces B: Biointerfaces
A successful immunosensor is characterized by a proper antibody immobilization and orientation in order to enhance the antigen recognition. In this work, a thorough characterization of the antibody functionalized gold surface is performed to set up the best conditions to implement in an optical platform for the detection of Brucella sp. Two different strategies are evaluated, based on a random immobilization and on an oriented one: a direct antibody immobilization on carboxylic mixed polyethylene (PEG) self-assembled monolayer (SAM) or only carboxylic PEG SAM interface is compared to an oriented immobilization on a layer of protein G on the same PEG SAM interfaces. X-ray Photoelectron Spectroscopy (XPS), Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) and contact angle (CA) are used to chemically characterize the gold functionalized surface and ToF-SIMS is also used to confirm the right antibody orientation. Optical characterization is applied to monitor the functionalization steps and fluorescence measurements are used to set up the proper experimental conditions and also to detect Brucella bacteria on the surface. Best results are obtained with a 10 ng/μl incubation solution of antibody immobilized, in an oriented way, on a mixed PEG SAM interface.
Polymers via high internal phase emulsion (polyHIPEs) were molecularly imprinted with Irbesartan, an antihypertensive drug belonging to the class of angiotensin II receptor antagonists (sartan drugs), chosen for the proof-of-concept extraction of hazardous emerging contaminants from water. Different analyte-functional monomer molar ratios (1:100, 1:30 and 1:15) were investigated, and the MIP polyHIPEs have been characterized, parallel to the not imprinted polymer (NIP), by batch sorption experiments. The material with the highest template-functional monomer ratio was the best for Irbesartan removal, showing a sorption capacity fivefold higher than the NIP. Regarding the adsorption kinetics, the analyte–sorbent equilibrium was reached after about 3 h, and the film diffusion model best fitted the kinetic profile. Selectivity was further demonstrated by testing Losartan, another sartan drug, observing a fourfold lower sorption capacity, but still higher than that of NIP. The polymers were also synthesized in cartridges for solid-phase extraction (SPE), which was helpful for evaluating the breakthrough curves and performing pre-concentrations. These have been done in tap and river water samples (100–250 mL, 15–500 µg L−1 Irbesartan), obtaining quantitative sorption/desorption on the MIP-polyHIPE (RSD < 14%, n = 3). The NIP provided a recovery of just around 30%, evidence of partial uptake of the target from water.
In this work, 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.
In this study, the development of an MIP-based electrode for voltammetric detection of irbesartan is presented. Irbesartan is a drug prescribed to treat hypertension and high blood pressure. Recent studies associated sartans with several forms of cancer, making removing this class of substances from the environment a high priority, and the EU has categorized it as an emerging pollutant. Molecularly imprinted polymers (MIPs) have already been used to remove pollutants from complex matrixes; hence, they were also chosen for this work. In particular, a polymer based on polyacrylate moiety was used to functionalize the graphite working electrode of screen-printed cells (SPCs), aiming to develop a voltammetric method for Irbesartan sensing. The prepolymeric mixture was drop-coated on the working electrode. The electrochemical technique used to quantify irbesartan is the square wave voltammetry (SWV); the experiments were carried out in acetate buffer at pH 5.5. A detection limit of 19 μg/L was obtained, and the linearity ranged from 31 μg/L to 432 μg/L. The procedure was replicated with different SPCs obtaining similar results, highlighting good reproducibility. The electrodes were also applied to determine irbesartan in fortified tap water samples, obtaining high recovery percentages. Considering the good results, the electrochemical methods based on MIP-functionalized screen-printed electrodes are promising for quantifying irbesartan at a trace level.