An Optical Device Based on a Chemical Chip and Surface Plasmon Platform for 2-Furaldehyde Detection in Insulating Oil.

2-Furaldehyde (2-FAL) is one of the main by-products of the degradation of hemicellulose, which is the solid material of the oil-paper insulating system of oil-filled transformers. For this reason, it has been suggested as a marker of the degradation of the insulating system; sensing devices for 2-FAL analysis in a wide concentration range are of high interest in these systems. An optical sensor system is proposed; this consists of a chemical chip, able to capture 2-FAL from the insulating oil, coupled with a surface plasmon resonance (SPR) probe, both realized on multimode plastic optical fibers (POFs). The SPR platform exploits gold nanofilm or, alternatively, a double layer of gold and silicon oxide to modulate the sensor sensitivity. The capturing chip is always based on the same molecularly imprinted polymer (MIP) as a receptor specific for 2-FAL. The system with the SPR probe based on a gold nanolayer had a higher sensitivity and a lower detection limit of fractions of µg L-1. Instead, the SPR probe, based on a double layer (gold and silicon oxide), has a lower sensitivity with a worse detection limit, and it is suitable for the detection of 2-FAL at concentrations of 0.01-1 mg L-1.

Splitter-Based Sensors Realized via POFs Coupled by a Micro-Trench Filled with a Molecularly Imprinted Polymer.

An optical-chemical sensor based on two modified plastic optical fibers (POFs) and a molecularly imprinted polymer (MIP) is realized and tested for the detection of 2-furaldehyde (2-FAL). The 2-FAL measurement is a scientific topic of great interest in different application fields, such as human health and life status monitoring in power transformers. The proposed sensor is realized by using two POFs as segmented waveguides (SW) coupled through a micro-trench milled between the fibers and then filled with a specific MIP for the 2-FAL detection. The experimental results show that the developed intensity-based sensor system is highly selective and sensitive to 2-FAL detection in aqueous solutions, with a limit of detection of about 0.04 mg L-1. The proposed sensing approach is simple and low-cost, and it shows performance comparable to that of plasmonic MIP-based sensors present in the literature for 2-FAL detection.

Colorimetric Paper-Based Analytical Devices (PADs) Backed by Chemometrics for Pd(II) Detection.

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).

Chemometric-Assisted Litmus Test: One Single Sensing Platform Adapted from 1-13 to Narrow pH Ranges.

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.

Detection of 2-Furaldehyde in Milk by MIP-Based POF Chips Combined with an SPR-POF Sensor.

An innovative optical-chemical sensor has been used to detect the 2-furaldehyde (2-FAL) in milk. The proposed sensing approach exploits the refractive index changing in a microstructured chip based on a plastic optical fiber (POF) with orthogonal micro-holes containing a specific molecularly imprinted polymer (MIP). This POF-MIP chemical chip modifies the surface plasmon resonance (SPR) phenomena excited in another sensor chip realized in POFs (SPR-POF) and connected in series. The proposed sensor configuration exploits MIP receptors avoiding any modification of the gold film of the SPR platform. This work reports the performance, particularly the high sensitivity and low detection limit, in complex matrices such as buffalo milk fortified with 2-FAL and in different commercial kinds of cow milk thermally treated for pasteurization. The measurements were carried out in about ten minutes by dropping the solution under-test on the planar D-shaped POF surface of the chemical chip. In contrast, on the gold surface of the SPR-POF platform, a water drop is always placed to excite the SPR phenomenon, which is modulated by the chemical chip via MIP-2-FAL binding. Furthermore, the experimental results demonstrated the pros and cons of the proposed sensor system. Thanks to the high sensitivity of the sensor system, the detection of 2-FAL in the diluted milk sample (1:50) was achieved. The dilution is required to reduce the interferent effect of the complex matrix.

Smart sensory materials for divalent cations: a dithizone immobilized membrane for optical analysis.

An optode for Cu(ii), Cd(ii), Zn(ii) and Hg(ii) sensing has been designed by immobilization of dithizone on a triacetylcellulose membrane (mem-DTZ). The sorption of the metal ions on the mem-DTZ has been thoroughly characterized, in particular sorption kinetics, sorption isotherms and profiles as a function of the pH have been studied. Methods to assess the concentrations of the cations, both individually and in a mixture, in unknown samples, have been developed. In particular, UV-vis spectra and digital information of pictures taken by using a common desktop scanner, of the mem-DTZ sensor after equilibration with different solutions, were acquired and they were correlated with the concentration of the metal ions in solutions. For the single analyte determination, the RGB parameters of the pictures were subjected to Principal Component Analysis (PCA); otherwise the UV-vis spectra of a mixture of two cations were elaborated by Partial Least Squares (PLS) Regression. The membrane responds to the divalent cations by changing colour reversibly. The response time of the mem-DTZ is about 1 h for Cd(ii), Hg(ii) and Zn(ii), but longer for Cu(ii): more than 10 h are required. The linear interval is in the range of about 10-7 to 10-5 M for all metal ions. The limit of detection (LOD) is around 10-6 M for Cu(ii), Cd(ii) and Hg(ii); for Zn(ii) a lower LOD of 10-7 M is obtained. The applicability of mem-DTZ to real samples has been proved by analysis of the four metal cations in a certificate material (Sewage Sludge CC136A), white wine, and drinking water samples.

Novel DFO-functionalized mesoporous silica for iron sensing. Part 2. Experimental detection of free iron concentration (pFe) in urine samples.

Successful in vivo chelation treatment of iron(iii) overload pathologies requires that a significant fraction of the administered drug actually chelates the toxic metal. Increased mobilization of the iron(iii) in experiments on animals or humans, most often evaluated from urinary output, is usually used as an assessment tool for chelation therapy. Alternatively, the efficiency of a drug is estimated by calculating the complexing ability of a chelating agent towards Fe(iii). The latter is calculated by the pFe value, defined as the negative logarithm of the concentration of the free metal ion in a solution containing 10 µM total ligand and 1 µM total metal at a physiological pH of 7.4. In theory, pFe has to be calculated taking into account all the complexation equilibria involving the metal and the possible ligands. Nevertheless, complexation reactions in complex systems such as serum and urine may hardly be accurately modelled by computer software. The experimental determination of the bioavailable fraction of iron(iii) in biological fluids would therefore be of the utmost relevance in the clinical practice. The efficiency of the therapy could be more easily estimated as well as the course of overload pathologies. In this context, the aim of the present work was the development of a sensor to assess the free iron directly in biological fluids (urine) of patients under treatment with chelating agents. In the proposed device (DFO-MS), the strong iron chelator deferoxamine (DFO) is immobilized on the MCM-41 mesoporous silica. The characterization of the iron(iii) sorption on DFO-MS was undertaken, firstly in 0.1 M KNO3, then directly in urine samples, in order to identify the sorption mechanism. The stoichiometry of the reaction in the solid phase was found to be: with an exchange constant (average value) of log ßex = 40(1). The application of DFO-MS to assess pFe in SPU (Simulating Pathology Urine) samples was also considered. The results obtained were very promising for a future validation and subsequent application of the sensor in samples of patients undergoing chelation therapy.

Novel DFO-SAM on mesoporous silica for iron sensing. Part I. Synthesis optimization and characterization of the material.

The synthesis and the physico-chemical characterisation of a novel solid phase, designed for iron(iii) sorption, are presented. The solid (indicated in the following as DFO-SAMMS) is made with a hydroxamate siderophore, the deferoxamine (DFO), covalently bound on a self-assembled monolayer on mesoporous silica (SAMMS). The data demonstrate that the DFO molecules are bound to the solid material, grafted on the surface and do not enter the silica pores. A new one-pot synthesis is presented in which DFO is dissolved in DMSO, and left to react with GPTMS with stirring overnight. In the same mixture, SAMMS is added to get the final product. The optimisation of experimental conditions of this novel one-pot synthesis is presented, with results indicating that a temperature of 90 °C, for the reaction between DFO and GPTMS, and the use of MCM-41 silica are the most convenient conditions. The kinetics of sorption reveals that the iron uptake is relatively fast, around 100 min at pH = 2.5, and from the sorption profile of iron(iii), the estimated capacity of the product obtained under optimized conditions was higher than 0.3 mmol g(-1). The results found in the present research are very promising for application in real biological samples.

A simple small size and low cost sensor based on surface plasmon resonance for selective detection of Fe(III).

A simple, small size, and low cost sensor based on a Deferoxamine Self Assembled Monolayer (DFO-SAM) and Surface Plasmon Resonance (SPR) transduction, in connection with a Plastic Optical Fiber (POF), has been developed for the selective detection of Fe(III). DFO-SAM sensors based on appropriate electrochemical techniques can be frequently found in the scientific literature. In this work, we present the first example of a DFO-SAM sensor based on SPR in an optical fiber. The SPR sensing platform was realized by removing the cladding of a plastic optical fiber along half the circumference, spin coating a buffer of Microposit S1813 photoresist on the exposed core, and finally sputtering a thin gold film. The hydroxamate siderophore deferoxamine (DFO), having high binding affinity for Fe(III), is then used in its immobilized form, as self-assembled monolayer on the gold layer surface of the POF sensor. The results showed that the DFO-SAM-POF-sensor was able to sense the formation of the Fe(III)/DFO complex in the range of concentrations between 1 µm and 50 µm with a linearity range from 0 to 30 µm of Fe(III). The selectivity of the sensor was also proved by interference tests.

Molecularly Imprinted Polypyrrole-Modified Screen-Printed Electrode for Dopamine Determination.

This paper introduces a quantitative method for dopamine determination. The method is based on a molecularly imprinted polypyrrole (e-MIP)-modified screen-printed electrode, with differential pulse voltammetry (DPV) as the chosen measurement technique. The dopamine molecules are efficiently entrapped in the polymeric film, creating recognition cavities. A comparison with bare and non-imprinted polypyrrole-modified electrodes clearly demonstrates the superior sensitivity, selectivity, and reproducibility of the e-MIP-based one; indeed, a sensitivity of 0.078 µA µM-1, a detection limit (LOD) of 0.8 µM, a linear range between 0.8 and 45 µM and a dynamic range of up to 350 µM are achieved. The method was successfully tested on fortified synthetic and human urine samples to underline its applicability as a screening method for biomedical tests.

Molecularly Imprinted Polymer-based voltammetric sensor for amino acids/indazole derivatives synthetic cannabinoids detection.

BACKGROUND: Synthetic cannabinoids (SCs) are a broad class of illicit drugs that are classified according to the chemical structure of the aromatic core that they present (i.e., indole, imidazole, pyrrole) and their detection is still a challenge, despite their widespread diffusion. The identification of a specific class of SC in complex matrices, such as real samples with a rapid, economic analytical device useable directly in the field, is highly desirable, as it can provide immediate and reliable information that eventually addresses more targeted analyses. RESULTS: The present paper proposes a Molecularly Imprinted Polymer (MIP)-based voltammetric sensor for the rapid and selective detection of indazole-type SCs. In this context, a polyacrylate-based MIP was used to functionalize a Pt electrode. The MIP composition was optimized through a Design of Experiments approach, and for the sake of safety, a non-psychotropic compound structurally related to the selected SCs was employed as the template in the MIP formulation. A complete characterization of the electrochemical behavior of the selected SCs was performed, and differential pulse voltammetry (DPV) in acetonitrile/lithium perchlorate 0.1 M was the technique applied for their quantification. LOD around 0.01 mM and linearity up to 0.8 mM were found. Comparison with the non-imprinted (NIP) modified and bare electrodes showed better selectivity and reproducibility of the MIP-based sensor. Recovery tests (in the 70-115 % range) were performed on simulated pills and smoking mixtures to test the reliability of the proposed method. SIGNIFICANCE: The method proposed allows the identification and quantification of indazole-based SCs as a class in complex matrices. Due to the selectivity of the obtained device, no clean-up of the sample before analyses is needed. For the same reason, the interference of cutting substances and natural cannabinoids was negligible.

A Screen-Printed Voltammetric Sensor Modified with Electropolymerized Molecularly Imprinted Polymer (eMIP) to Determine Gallic Acid in Non-Alcoholic and Alcoholic Beverages.

This paper presents a low-cost disposable sensor for gallic acid (GA) detection in non-alcoholic and alcoholic beverages using a screen-printed cell (SPC) whose working electrode (in graphite) is modified with electrosynthesized molecularly imprinted polypyrrole (eMIP). Our preliminary characterization of the electrochemical process shows that gallic acid (GA) undergoes irreversible oxidation at potentials of about +0.3 V. The peak potential is not affected by the presence of the eMIP film and alcohol percentages (ethanol) up to 20%. The GA determination is based on a differential pulse voltammetry (DPV) analysis leveraging its oxidation peak. The calibration data and the figures of merit of the analytical method (LOD, LOQ, and linear range) are calculated. To validate the feasibility of the sensor's application for the dosing of GA in real matrices, some non-alcoholic and alcoholic beverages are analyzed. The results are then compared with those reported in the literature and with the total polyphenol content determined by the Folin-Ciocalteu method. In all cases, the concentrations of GA align with those previously found in the literature for the beverages examined. Notably, the values are consistently lower than the total polyphenol content, demonstrating the sensor's selectivity in discriminating the target molecule from other polyphenols present.

Exploring albumin-sulfonephthalein dyes interactions by a chemometric-assisted and multi-technique equilibria analysis in solution.

Albumin is undoubtedly the most studied protein thanks to its widespread diffusion and biochemistry; despite its binding ability towards different dyes, provoking dye's colour change, has been exploited for decades for quantification purposes, the joint effect of working pH, ionic strength, and dye's pKa still remains only sporadically discussed. In the present study, the interaction of Bovine Serum Albumin (BSA) with five dyes belonging to the sulfonephthalein group, Bromophenol Blue (BPB, pKa = 3.75), Bromocresol Green (BCG, pKa = 4.42), Chlorophenol Red (CPR, pKa = 5.74), Bromocresol Purple (BCP, pKa = 6.05) and Bromothymol Blue (BTB, pKa = 6.72), is investigated at four working pH values (3.5, 6.0, 7.5 and 9.0) and two ionic strength conditions by UV-Vis spectroscopy. Principal Component Analysis is then applied to rationalize dye behavior upon BSA addition at each pH value and to summarize the protein effect on dyes' spectral features, identifying three general behaviors. The most relevant systems are then submitted to further characterization involving a solution equilibria study aimed at determining conditional binding constants for the selected DSA-dye adducts and fluorescence, CD, and 1H NMR spectroscopy to evaluate the binding effect on the species involved.

The colorful world of sulfonephthaleins: Current applications in analytical chemistry for "old but gold" molecules.

Sulfonephthaleins represent one of the most common and widely employed reactive dyes in analytical chemistry, thanks to their stability, low-cost, well-visible colors, reactivity and possibilities of chemical modification. Despite being first proposed in 1916, nowadays, these molecules play a fundamental role in biological and medical applications, environmental analyses, food quality monitoring and other fields, with a particular focus on low-cost and disposable devices or methods for practical applications. Since up to our knowledge, no reviews or book chapters focused explicitly on sulfonephthaleins have ever been published, in this review, we will briefly describe sulfonephthaleins history, their acid-base properties will be discussed, and the most recent applications in different fields will be presented, focusing on the last ten years literature (2014-2023). Finally, safety and environmental issues will be briefly discussed, despite being quite controversial.

Synthesis, Characterization and Application of a MIP-polyHIPE for Selective Extraction of Angiotensin II Receptor Antagonists Residues in Natural Waters.

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.

RGB-Detector: A Smart, Low-Cost Device for Reading RGB Indexes of Microfluidic Paper-Based Analytical Devices.

A user-friendly, low-cost detector able to read the RGB indexes of microfluidic paper-based analytical devices (µPADs) was developed. The RGB-detector was built with 3D printing using PLA+ and reused Li-ion batteries. It is Arduino-based, which provides an easy interface between the sensor TCS3200, which reads the quadratic wave of the times corresponding to the RGB numbers, the Arduino itself, whose software translates the times into RGB values, and the touchscreen display, NX3224T028, which shows the results. This detector permits multi-sample analysis since it has a sample holder that can keep up to six µPADs simultaneously and rotate after the display's request. This work shows how the readings of the RGB indexes by the proposed RGB-detector implement the measurements' reproducibility. As a proof-of-concept, the RGB-detector application to a green array of µPADs for pH measurement coupled with chemometric analysis allowed us to achieve good results in terms of precision and agreement with the pH values measured by a classical pH-meter.

Towards intelligent packaging: BCP-EVOH@ optode for milk freshness measurement.

Intelligent packaging represents an emerging trend in the food industry, especially for highly perishable foods like milk and dairy products. Despite the apparent simplicity, miniaturized BCP-EVOH@ sensor, made of bromocresol purple (BCP) covalently bound to ethylene-vinyl alcohol (EVOH) copolymer, meets the goal of milk freshness monitoring during chilled storage, allowing both naked-eye evaluation and chemometric-assisted spoilage modelling and measurements.

Potentiometric MIP-Modified Screen-Printed Cell for Phenoxy Herbicides Detection.

In this study, a molecularly imprinted polymer (MIP)-based screen-printed cell is developed for detecting phenoxy herbicides using 2-methyl-4-chlorophenoxyacetic acid (MCPA) as the template. MCPA is a phenoxy herbicide widely used since 1945 to control broadleaf weeds via growth regulation, primarily in pasture and cereal crops. The potentiometric cell consists of a silver/silver chloride pseudo-reference electrode and a graphite working electrode coated with a MIP film. The polymeric layer is thermally formed after drop-coating of a pre-polymeric mixture composed of the reagents at the following molar ratio: 1 MCPA: 15 MAA (methacrylic acid): 7 EGDMA (ethylene glycol dimethacrylate). After template removal, the recognition cavities function as the ionophore of a classical ion selective electrode (ISE) membrane. The detected ion is the deprotonated MCPA specie, negatively charged, so the measurements were performed in phosphate buffer at pH 5.5. A linear decrease of the potential with MCPA concentration, ranging from 4 × 10-8 to 1 × 10-6 mol L-1, was obtained. The detection limit and the limit of quantification were, respectively, 10 nmol L-1 and 40 nmol L-1. A Nernstian slope of about -59 mV/dec was achieved. The method has precision and LOD required for MCPA determination in contaminated environmental samples.

Quick and Easy Covalent Grafting of Sulfonated Dyes to CMC: From Synthesis to Colorimetric Sensing Applications.

Carboxymethyl cellulose, the most promising cellulose-derivatives, pulls together low cost, abundancy, biocompatibility, unique properties and, unlike the precursor, chemical reactivity. This latter aspect arouses the curiosity of chemists around the possibility of chemical modification and the production of interesting functional materials. Here, a two-step reaction is proposed for the covalent anchoring of a wide variety of molecules containing sulfonic groups to CMC. The strength points of the proposed pathway have to be found in the quick and easy reactions and workup that allow to obtain ready-to-use functional materials with very high yields. Having in this case exploited a pH-sensitive dye as a sulfonated molecule, the functional material is an interesting candidate for the development of colorimetric miniaturized sensors via the following drop-casting deposition: once optimized sensors preparation by design of experiments, an example of application on real samples is reported.

An Optical Fiber Sensor for Uranium Detection in Water.

An optical sensor for uranyl has been prepared based on a gold-plated D-shaped plastic optical fiber (POF) combined with a receptor consisting of a bifunctional synthetic molecule, 11-mercaptoundecylphosphonic acid (MUPA), with a phosphonic group for complexing the considered ion, and a sulfide moiety through which the molecule is fixed at the gold resonant surface as a molecular layer in an easy and reproducible way. The sensor is characterized by evaluating the response in function of the uranyl concentration in aqueous solutions of different compositions and real-life samples, such as tap water and seawater. The mechanism of the uranyl/MUPA interaction was investigated. Two different kinds of interactions of uranyl with the MUPA layer on gold from water are observed: a strong one and a weak one. In the presence of competing metal ions as Ca2+ and Mg2+, only the strong interaction takes place, with a high affinity constant (around 107 M-1), while a somewhat lower constant (i.e., around 106 M-1) is obtained in the presence of Mg2+ which forms stronger complexes with MUPA than Ca2+. Due to the high affinity and the good selectivity of the recognition element MUPA, a detection limit of a few µg L-1 is reached directly in natural water samples without any time-consuming sample pretreatment, making it possible for rapid, in situ controls of uranyl by the proposed sensor.