A surface acoustic wave sensor functionalized with a polypyrrole molecularly imprinted polymer for selective dopamine detection.

A surface acoustic wave sensor operating at 104 MHz and functionalized with a polypyrrole molecularly imprinted polymer has been designed for selective detection of dopamine (DA). Optimization of pyrrole/DA ratio, polymerization and immersion times permitted to obtain a highly selective sensor, which has a sensitivity of 0.55°/mM (≈ 550 Hz/mM) and a detection limit of ≈ 10 nM. Morphology and related roughness parameters of molecularly imprinted polymer surfaces, before and after extraction of DA, as well as that of the non imprinted polymer were characterized by atomic force microscopy. The developed chemosensor selectively recognized dopamine over the structurally similar compound 4-hydroxyphenethylamine (referred as tyramine), or ascorbic acid,which co-exists with DA in body fluids at a much higher concentration. Selectivity tests were also carried out with dihydroxybenzene, for which an unexpected phase variation of order of 75% of the DA one was observed. Quantum chemical calculations, based on the density functional theory, were carried out to determine the nature of interactions between each analyte and the PPy matrix and the DA imprinted PPy polypyrrole sensing layer in order to account for the important phase variation observed during dihydroxybenzene injection.

In situ diazonium-modified flexible ITO-coated PEN substrates for the deposition of adherent silver-polypyrrole nanocomposite films.

In this paper, we report a simple and versatile process of electrografting the aryl multilayers onto indium tin oxide (ITO)-coated flexible poly(ethylene naphthalate) (PEN) substrates using a diazonium salt (4-pyrrolylphenyldiazonium) solution, which was generated in situ from a reaction between the 4-(1H-pyrrol-1-yl)aniline precursor and sodium nitrite in an acidic medium. The first aryl layer bonds with the ITO surface through In-O-C and Sn-O-C bonds which facilitate the formation of a uniform aryl multilayer that is ∼8 nm thick. The presence of the aryl multilayer has been confirmed by impedance spectroscopy as well as by electron-transfer blocking measurements. These in situ diazonium-modified ITO-coated PEN substrates may find applications in flexible organic electronics and sensor industries. Here we demonstrate the application of diazonium-modified flexible substrates for the growth of adherent silver/polpyrrole nanocomposite films using surface-confined UV photopolymerization. These nanocomposite films have platelet morphology owing to the template effect of the pyrrole-terminated aryl multilayers. In addition, the films are highly doped (32%). This work opens new areas in the design of flexible ITO-conductive polymer hybrids.

Electrochemical sensor based on a ZnO-doped graphitized carbon for the electrocatalytic detection of the antibiotic hydroxychloroquine. Application: tap water and human urine.

Abstract: In December 2019, the world experienced a new coronavirus, SARS-CoV-2, causing coronavirus disease 2019 originating from Wuhan.The virus has crossed national borders and now affects more than 200 countries and territories. Hydroxychloroquine has been considered as a drug capable of treating COVID-19. The objective of this work is to establish a simple platform for electrocatalytic detection of hydroxychloroquine in human urine samples and pharmaceutical samples (tablets) using a ZnO@CPE sensor constructed by simple and inexpensive hydrothermal methods using a square wave voltammetry method. The best results are obtained in a PBS electrolyte with irreversible behavior of the hydroxychloroquine complement and controlled by diffusion coupled with absorption phenomena. The ZnO@CPE shifts the oxidation potential of hydroxychloroquine with the formation of a single very intense peak at the position of Epa = 0.5 V/(vs Ag/AgCl) with a shift is ΔEp = 0.1 V(vs Ag/AgCl) compared to the unmodified electrode. The obtained ZnO@CPE hybrid nanocomposite was characterized by different techniques and showed excellent electrocatalytic activity and higher active surface area compared to the bare carbon paste electrode. Under the optimized experimental conditions, the ZnO@CPE sensor showed good analytical performance for the determination of trace amounts of hydroxychloroquine, a wide linearity range from 10-3 M to 0.8 × 10-6 M with a very low detection limit in the range of 1.33 × 10-7 M, satisfactory selectivity, acceptable repeatability and reproducibility. The calculated recovery and coefficient of variation for the two samples analyzed are very satisfactory, ranging from 97.6 to 102% and 1.2 to 2.3% respectively. The proposed applied method and the fabricated sensor offer the possibility to analyze traces of hydroxychloroquine in real human urine and water samples. Graphical abstract: Strategy for the electro-oxidation reaction of hydroxychloroquine on the electro-catalytic surface of the ZnO@Carbon graphite electrode and real-time detection of hydroxychloroquine.

Acetylcholinesterase immobilized on magnetic beads for pesticides detection: application to olive oil analysis.

This work presents the development of bioassays and biosensors for the detection of insecticides widely used in the treatment of olive trees. The systems are based on the covalent immobilisation of acetylcholinesterase on magnetic microbeads using either colorimetry or amperometry as detection technique. The magnetic beads were immobilised on screen-printed electrodes or microtitration plates and tested using standard solutions and real samples. The developed devices showed good analytical performances with limits of detection much lower than the maximum residue limit tolerated by international regulations, as well as a good reproducibility and stability.

A simple platform for the electro-catalytic detection of the dimetridazole using an electrochemical sensor fabricated by electro-deposition of Ag on carbon graphite: application: orange juice, tomato juice and tap water.

The objective of this paper is to evaluate and optimize the experimental parameters of the electro-deposition of silver atom nuclei on a graphite carbon paste to elaborate an electrochemical sensor. The electro-deposition process was performed using the cyclic voltammetry. The electrochemical studies show that the deposited silver micro-particle array offers an excellent electro-catalytic activity towards the NO2 attractor group of the dimetridazole side chain. SEM morphological analysis of the silver deposits indicates the presence of a large number of Ag micro-particles on the graphite carbon with good nucleation. The size of the Ag micro-particles is of the order of 19,7621 µm and their distribution is normal over the entire range of the pulp. DRX analysis of the deposit also indicates that the microcrystalline structure of the silver microcrystals in the deposit is face-centered cubic. The electrochemical behavior of dimetridazole is totally irreversible, the transfer process is controlled by diffusion phenomena on the surface of the electrode covered by a silver deposit realized µAg@CPE. The analytical performance of the constructed electrode shows a good selectivity. Calibration curves for the detection of dimetridazole have been drawn in the concentration range of 3,5 × 10-4 mol/L to 10-6 mol/L using cyclic voltammetry method, with a detection and quantification limits of 6.565 × 10-7 mol/L and 2.216 × 10-6 mol/L respectively. The applicability of the constructed electrode has been tested in real samples including orange juice, tomato juice, tap water. The results obtained show a recovery rate above 94%, which is very satisfactory.

Electrochemical impedimetric sensor based on molecularly imprinted polymers/sol-gel chemistry for methidathion organophosphorous insecticide recognition.

We report here a novel method to detect methidathion organophosphorous insecticides. The sensing platform was architected by the combination of molecularly imprinted polymers and sol-gel technique on inexpensive, portable and disposable screen printed carbon electrodes. Electrochemical impedimetric detection technique was employed to perform the label free detection of the target analyte on the designed MIP/sol-gel integrated platform. The selection of the target specific monomer by electrochemical impedimetric methods was consistent with the results obtained by the computational modelling method. The prepared electrochemical MIP/sol-gel based sensor exhibited a high recognition capability toward methidathion, as well as a broad linear range and a low detection limit under the optimized conditions. Satisfactory results were also obtained for the methidathion determination in waste water samples.

Molecularly imprinted polymer cartridges coupled to high performance liquid chromatography (HPLC-UV) for simple and rapid analysis of fenthion in olive oil.

A combination of molecular modelling and a screening of the library of non-imprinted polymers (NIPs) was used to identify acrylamide as a functional monomer with high affinity towards fenthion, organophosphate insecticide, which is frequently used in the treatment of olives. A good correlation was found between the screening tests and modelling of monomer-template interactions performed using a computational approach. Acrylamide-based molecularly imprinted polymer (MIP) and non-imprinted polymer (NIP) were thermally synthesised in dimethyl formamide (porogen) using ethylene glycol dimethacrylate as a cross-linker and 1,1-azo-bis (isobutyronitrile) as an initiator. The chemical and physical properties of the prepared polymers were characterised. The binding of fenthion by the polymers was studied using solvents with different polarities. The developed MIP showed a high selectivity towards fenthion, compared to other organophosphates (dimethoate, methidathion malalthion), and allowed extraction of fenthion from olive oil samples with a recovery rate of about 96%. The extraction of fenthion using MIPs was much more effective than traditional C18 reverse-phase solid phase extraction and allowed to achieve a low detection limit (LOD) (5 µg L(-1)).

Computational and experimental investigation of molecular imprinted polymers for selective extraction of dimethoate and its metabolite omethoate from olive oil.

This work presents the development of molecularly imprinted polymers (MIPs) for the selective extraction of dimethoate from olive oil. Computational simulations allowed selecting itaconic acid as the monomer showing the highest affinity towards dimethoate. Experimental validation confirmed modelling predictions and showed that the polymer based on IA as functional monomer and omethoate as template molecule displays the highest selectivity for the structurally similar pesticides dimethoate, omethoate and monocrotophos. Molecularly imprinted solid phase extraction (MISPE) method was developed and applied to the clean-up of olive oil extracts. It was found that the most suitable solvents for loading, washing and elution step were respectively hexane, hexane-dichloromethane (85:15%) and methanol. The developed MIPSE was successfully applied to extraction of dimethoate from olive oil, with recovery rates up to 94%. The limits of detection and quantification of the described method were respectively 0.012 and 0.05 µg g(-1).

Molecular imprinting solid phase extraction for selective detection of methidathion in olive oil.

A specific adsorbent for extraction of methidathion from olive oil was developed. The design of the molecularly imprinted polymer (MIP) was based on the results of the computational screening of the library of polymerisable functional monomers. MIP was prepared by thermal polymerisation using N,N'-methylene bisacrylamide (MBAA) as a functional monomer and ethylene glycol dimethacrylate (EGDMA) as a cross-linker. The polymers based on the itaconic acid (IA), methacrylic acid (MAA) and 2-(trifluoromethyl)acryl acid (TFMAA) functional monomers and one control polymer which was made without functional monomers with cross-linker EGDMA were also synthesised and tested. The performance of each polymer was compared using corresponding imprinting factor. As it was predicted by molecular modelling the best results were obtained for the MIP prepared with MBAA. The obtained MIP was optimised in solid-phase extraction coupled with high performance liquid chromatography (MISPE-HPLC-UV) and tested for the rapid screening of methidathion in olive oil. The proposed method allowed the efficient extraction of methidathion for concentrations ranging from 0.1 to 9 mg L(-1) (r(2)=0.996). The limits of detection (LOD) and quantification (LOQ) in olive oil were 0.02 mg L(-1) and 0.1 mg L(-1), respectively. MIPs extraction was much more effective than traditional C18 reverse-phase solid phase extraction.