Search

The paper describes the development and application of a screen-printed electrode cell with a graphite-ink working electrode modified by a molecularly imprinted electropolymerized polypyrrole for the voltammetric determination of the herbicide 4‑chloro-2-methylphenoxyacetic acid (MCPA). The method exploits the direct measurement of the analyte by applying the differential pulse voltammetry (DPV) technique, taking advantage of the irreversible oxidation peak at about +1.0 V vs. Ag/AgCl pseudo reference electrode. The presence of the molecularly imprinted polypyrrole enhances the sensor's selectivity and sensitivity. A chemometric approach has been crucial for quantitative analysis because of the peak's broad and not well-defined shape. Firstly, a proper pretreatment of the voltammetric signals is identified, proving the most effective is the first-derivative function transformation of the signal. The Partial Least Square regression (PLS) is the tool applied for MCPA quantification. A preliminary PLS model has been developed and validated in dihydrogen phosphate solution at pH 5.5, aiming to optimize the data treatment approach. Then, the same approach is used to develop a PLS model analyzing tap water samples fortified with MCPA and other pesticides as possible interferents to simulate contaminated natural waters. The model correctly predicted the analyte concentration in the range of 2.5–75 μM, assuring the reliability and robustness of the sensor for the possible quantification of MCPA in wastewater samples.

This paper presents the development of cheap and selective Paper-based Analytical Devices (PADs) for selective Pd(II) determination from very acidic aqueous solutions. The PADs were obtained by impregnating two cm-side squares of filter paper with an azoic ligand, (2-(tetrazolylazo)-1,8 dihydroxy naphthalene-3,6,-disulphonic acid), termed TazoC. The so-obtained orange TazoC-PADs interact quickly with Pd(II) in aqueous solutions by forming a complex purple-blue-colored already at pH lower than 2. The dye complexes no other metal ions at such an acidic media, making TazoC-PADs highly selective to Pd(II) detection. Besides, at higher pH values, other cations, for example, Cu(II) and Ni(II), can interact with TazoC through the formation of stable and pink-magenta-colored complexes; however, it is possible to quantify Pd(II) in the presence of other cations using a multivariate approach. To this end, UV-vis spectra of the TazoC-PADs after equilibration with the metal ions solutions were registered in the 300–800 nm wavelength range. By applying Partial Least Square regression (PLS), the whole UV-vis spectra of the TazoC-PADs were related to the Pd(II) concentrations both when present alone in solution and also in the presence of Cu(II) and Ni(II). Tailored PLS models obtained with matrix-matched standard solutions correctly predicted Pd(II) concentrations in unknown samples and tap water spiked with the metal cation, making the method promising for quick and economical sensing of Pd(II).

This paper presents the development of a cheap and rapid electrochemical sensor for ascorbic acid detection. In particular, the graphite ink working electrode of screen-printed cells was covered by a film of elecrosynthesized molecularly imprinted polypyrrole (e-MIP); differential pulse voltammetry (DPV) was the selected method for the analyte detection. The ascorbic acid molecules were successfully entrapped in the polypyrrole film, creating the recognition sites. The best results were obtained after polypyrrole overoxidation and performing the measurements in phosphate buffer solution 0.05 M/KCl 0.1 M at pH 7.5. A comparison with the bare and the not-imprinted polypyrrole-modified electrodes showed that the e-MIP-based sensor had the highest selectivity and reproducibility. The developed method was applied to assess ascorbic acid in farmaceutical products, obtaining values not significantly different from the declared content.

Abstract In this work, two colourimetric sensors for metal ions detection are presented. The devices are obtained by fixing two classical dyes, Eriochrome Black T (EBT) and 1-(2-pyridylazo)-2-naphthol (PAN), on the commercial paper sheet “Colour Catcher®” (here named under the acronym CC) generally used in the washing machine to prevent colour run problems. The devices are optical sensors, since the indicator dye, fixed on the solid material, changes its spectral properties (colour and hence UV-vis spectrum) upon contact with the metal ion solution. We used the partial least squares (PLS) regression for obtaining the relationship between the metal ion content and the UV-vis spectrum change of each sensor.

A novel 3 × 4 colorimetric sensing platform, named the chemometric-assisted litmus test (CLT), has been developed by covalently anchoring commercial pH indicators to ethylene vinyl alcohol (EVOH). The proposed device can be exploited for pH determinations in a wide range from 1 to 13 and in specific narrow ranges, achieving sufficient accuracy and errors below 0.5 pH units. The experimental procedure is simple, quick and reliable; equilibration is reached in less than 2 h, CLT pictures are acquired by a camera, and data treatment is performed applying chemometric techniques such as principal component analysis (PCA) and partial least square regression (PLS) to RGB indices.

In recent years, plasmonic sensors have been used in various fields ranging from environmental monitoring, pharmaceutical analysis, medical diagnosis, and food quality assessment to forensics. A significant amount of information on plasmonic sensors and their applications already exists and there is a continuing development of reliable, selective, sensitive, and low-cost sensors. Combining molecularly imprinting technology with plasmonic sensors is an increasingly timely and important challenge to obtain portable, easy-to-use, particularly selective devices helpful in detecting analytes at the trace level. This review proposes an overview of the applications of molecularly imprinted plasmonic chemosensors and biosensors, critically discussing the performances, pros, and cons of the more recently developed devices.

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.

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.

Deferoxamine (DFO) is a siderophore widely studied for its ability to bind iron(III) strongly. Thanks to its versatility, it is suitable for several clinical and analytical applications, from the recognized iron(III) chelation therapy to the most recent applications in sensing. The presence of three hydroxamic functional groups enables Deferoxamine to form stable complexes with iron(III) and other divalent and trivalent metal ions. Moreover, the terminal amino group in the DFO molecule, not involved in metal ion complexation, allows modification or functionalization of solid phases, nanoobjects, biopolymers, electrodes and optical devices. This review summarizes and discusses deferoxamine-based applications for the chelation and recognition of Fe(III).

This work presents the development of a MIP-based screen-printed potentiometric cell for sensing the pesticide atrazine. The cell comprises three screen-printed electrodes; the working and the counter are obtained by graphite-ink and the pseudo-reference by silver/silver chloride-ink. All electrodes are printed on the support of polyester. Obviously, only the working and the pseudo-reference electrodes are connected for potentiometric measurements. The prepolymeric mixture was composed of the reagents at the following molar ratio: 1 atrazine (ATZ):5 methacrylic acids (MAA):4 ethylene glycol dimethacrylate (EGDMA). An amount of 7 µL of the prepolymeric solution was drop coated on the graphite working electrode of the cell, and the polymerization was carried out in an oven at 70 °C overnight. The specific sites obtained after polymerization and template elution can be viewed as the ionophore of a usual ISE membrane. The active ion is the atrazine in its protonated form, positively charged, so the determination was carried out in aqueous solutions at pHs1.5. At these conditions, the potential increases linearly with atrazine concentration ranging from 5 × 10−7 to 5 × 10−6 M; the limit of detection obtained is 4 × 10−7 M. The slope of the calibration curve E vs. log c (obtained as an average value of the slope of different standardization performed with several electrodes) is 40(6) mV/dec; the sub-Nernstian behavior can be ascribed to the interference of the anions present in the solution media.

Deferoxamine (DFO), a hydroxamic siderophore with a high affinity for Fe(III), is immobilized as a functionalized self-assembled monolayer of a thiol (SAM) on the gold surface of a screen-printed cell to develop a voltammetric sensor for iron(III). The surface of the working electrode was characterized, before and after functionalization, by determining surface properties such as the area and the double-layer capacitance. The Fe(III) detection was performed by DPV analysis after preconcentration of the cation at the open circuit potential in solution at pH = 1 for two minutes. The method was applied to the iron(III) quantification in water samples giving promising results.

Gold and Silver nanoparticles (AuNPs and AgNPs) are perfect platforms for developing sensing colorimetric devices thanks to their high surface to volume ratio and distinctive optical properties, particularly sensitive to changes in the surrounding environment. These characteristics ensure high sensitivity in colorimetric devices. Au and Ag nanoparticles can be capped with suitable molecules that can act as specific analyte receptors, so highly selective sensors can be obtained. This review aims to highlight the principal strategies developed during the last decade concerning the preparation of Au and Ag nanoparticle-based colorimetric sensors, with particular attention to environmental and health monitoring applications.

This review illustrates various types of polymer and nanocomposite polymeric based sensors used in a wide variety of devices. Moreover, it provides an overview of the trends and challenges in sensor research. As fundamental components of new devices, polymers play an important role in sensing applications. Indeed, polymers offer many advantages for sensor technologies: their manufacturing methods are pretty simple, they are relatively low-cost materials, and they can be functionalized and placed on different substrates. Polymers can participate in sensing mechanisms or act as supports for the sensing units. Another good quality of polymer-based materials is that their chemical structure can be modified to enhance their reactivity, biocompatibility, resistance to degradation, and flexibility.

The paper presents the synthesis and preliminary characterization of two novel solid-phase sorbents for iron(III), resulting from the functionalization of ethylene-vinyl alcohol copolymer (EVOH) with deferoxamine, DFO (DFO@EVOH), and a novel tripodal 3-hydroxy-4-pyridinone, named 3,4-HP (3,4-HP@EVOH). DFO and 3,4-HP have been covalently bonded to EVOH, using carbonyldiimidazole as a coupling agent. Before their use as Fe(III) sorbents, they were warm-pressed to obtain a thin film. Polymers have been characterized by conventional physico-chemical techniques; furthermore, the sorption properties towards Fe(III) were investigated. The physico-chemical characterization of the new solid-state devices demonstrates the effective linkage of the two receptors on the polymeric support. Despite a relatively low sorption capacity for both materials, the stoichiometry and the complexation constants of Fe(III)/DFO@EVOH and Fe(III)/3,4-HP@EVOH are in pretty good agreement with those obtained for the same ligands in aqueous solutions.

Meat spoilage is a very complex combination of processes related to bacterial activities. Numerous efforts are underway to develop automated techniques for monitoring this process. We selected a panel of pH indicators and a colourimetric dye, selective for thiols. Embedding these dyes into an anion exchange cellulose sheets, i.e., the commercial paper sheet known as “Colour Catcher®” commonly used in the washing machine to prevent colour run problems, we obtained an array made of six coloured spots (here named Dye name-CC@). The array, placed over the tray containing a sample of meat or fish (not enriched at any extend with spoilage products), progressively shows a colour change in the six spots. Photos of the array were acquired as a function of time, RGB indices were used to follow the spoilage, Principal Component Analysis to model the data set. We demonstrate that the array allows for the monitoring the overall spoilage process of chicken, beef, pork and fish, obtaining different models that mimic the degradation pathway. The spoilage processes for each kind of food, followed by the array colour evolution, were eventually compared using three-way PCA, which clearly shows same degradation pattern of protein foods, altered only according to the different substrates.