A novel nanostructured poly(thionine)-deep eutectic solvent/CuO nanoparticle film-modified disposable pencil graphite electrode for determination of acetaminophen in the presence of ascorbic acid.

A new electrochemical sensor based on thionine (TH), an electroactive polymer, and CuO nanoparticle (CuONP)-modified pencil graphite electrode (PGE) has been developed. Poly(thionine) (PTH) was formed on the CuO/PGE surface by electropolymerisation in ethaline deep eutectic solvent (DES) containing acetic acid dopant to form PTHEthaline/CuO/PGE. Cyclic voltammetry, electrochemical impedance spectroscopy, and differential pulse voltammetry were utilized to evaluate the fabrication process, electrochemical properties, and performance parameters of the modified electrodes. The analytical performance of the PTHEthaline/CuO/PGE was evaluated with respect to linear range, limit of detection, repeatability, and reproducibility for the detection of acetaminophen (APAP) by electrooxidation in the presence of ascorbic acid (AA). Analytical parameters such as pH were optimized. The combined use of PTH and CuONP led to enhanced performance towards APAP due to the large electroactive surface area and synergistic catalytic effect, with a wide linear working range and low detection limit. The reliability of the proposed sensor for the detection of APAP was successfully tested in pharmaceutical samples containing APAP and AA, with very good recoveries. Graphical abstract.

Polyphenazine and polytriphenylmethane redox polymer/nanomaterial-based electrochemical sensors and biosensors: a review.

In recent years, an increasing number of studies has demonstrated that redox polymers can be used in simple and effective electrochemical sensing platforms due to their fast electron transfer and electrocatalytic ability. To develop more sensitive and selective electrochemical (bio)sensors, the electrocatalytic properties of redox polymers and the electrical, mechanical, and catalytic properties of various nanomaterials are combined. This review aims to summarize and contribute to the development of (bio)sensors based on polyphenazine or polytriphenylmethane redox polymers combined with nanomaterials, including carbon-based nanomaterials, metal/metal oxide, and semiconductor nanoparticles. The synthesis, preparation, and modification of these nanocomposites is presented and the contribution of each material to the performance of (bio)sensor has been be examined. It is explained how the combined use of these redox polymers and nanomaterials as a sensing platform leads to improved analytical performance of the (bio)sensors. Finally, the analytical performance characteristics and practical applications of polyphenazine and polytriphenylmethane redox polymer/nanomaterial-based electrochemical (bio)sensors are compared and discussed.

Amperometric biogenic amine biosensors based on Prussian blue, indium tin oxide nanoparticles and diamine oxidase- or monoamine oxidase-modified electrodes.

Biogenic amine biosensors, based on screen-printed carbon electrodes (SPCE) modified with Prussian blue (PB) and indium tin oxide nanoparticles (ITONP), are reported. PB/ITONP-modified SPCE was further modified with diamine oxidase (DAO) or monoamine oxidase (MAO) enzymes to construct the biosensors. The morphology of the modified electrodes was studied by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX) and atomic force microscopy (AFM). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were used to enlighten the electrochemical properties of the modified electrodes at each step of biosensor fabrication. Electrode surface composition and experimental conditions were optimized and analytical performance characteristics of the biosensors were studied. Several biogenic amines were tested and both biosensors responded to histamine, putrescine and cadaverine. DAO/ITONP/PB/SPCE biosensor exhibited the highest response to histamine 6.0 × 10-6-6.9 × 10-4 M with a sensitivity of 1.84 µA mM-1. On the other hand, the highest sensitivity was obtained for cadaverine with the MAO/ITONP/PB/SPCE biosensor. The analytical utility of the presented biosensors were illustrated by the determination of cadaverine and histamine in cheese sample.

Electrochemical synthesis and characterization of poly(thionine)-deep eutectic solvent/carbon nanotube-modified electrodes and application to electrochemical sensing.

Electropolymerization of thionine (TH) on multiwalled carbon nanotube (MWCNT)-modified glassy carbon electrodes (GCE) in ethaline deep eutectic solvent (DES) was carried out for the first time, to prepare poly(thionine) (PTH) films with different nanostructured morphologies. PTH films were formed on MWCNT/GCE by potential cycling electropolymerization in ethaline with the addition of different acid dopants CH3COOH, HClO4, HNO3, H2SO4 and HCl, acetic acid being the best. The electropolymerization process was monitored with an electrochemical quartz crystal microbalance. The polymerization scan rate was a key factor affecting the electrochemical and morphological properties of the PTHEthaline-CH3COOH/MWCNT/GCE; electrodeposition at 200 mV s-1 showing the best performance. The PTH/MWCNT/GCE platform was characterized using cyclic and differential pulse voltammetry, electrochemical impedance spectroscopy and scanning electron microscopy. The analytical characteristics of the PTH films were evaluated for sensing of ascorbic acid and biosensing of uric acid. The developed sensor exhibited a low detection limit (1.1 µM), wide linear range (2.8-3010 µM) and high sensitivity (1134 µA cm-2 mM-1) for ascorbic acid. After immobilization of uricase, UOx, on PTH/MWCNT/GCE, the biosensor was successfully applied to the determination of uric acid, with fast response (˂ 7 s), good sensitivity (450 µA cm-2 mM-1, wide linear range (0.48-279 µM) and low detection limit (58.9 nM), better than in the literature and than with PTH prepared in aqueous solution. The determination of uric acid in synthetic urine samples was successfully tested and the mean analytical recovery was 100.8 ± 1.4%. This is a promising approach for the determination of uric acid in real samples. Graphical abstract.

Electrochemical biosensing of galactose based on carbon materials: graphene versus multi-walled carbon nanotubes.

In this study, two enzyme electrodes based on graphene (GR), Co3O4 nanoparticles and chitosan (CS) or multi-walled carbon nanotubes (MWCNTs), Co3O4 nanoparticles, and CS, were fabricated as novel biosensing platforms for galactose determination, and their performances were compared. Galactose oxidase (GaOx) was immobilized onto the electrode surfaces by crosslinking with glutaraldehyde. Optimum working conditions of the biosensors were investigated and the analytical performance of the biosensors was compared with respect to detection limit, linearity, repeatability, and stability. The MWCNTs-based galactose biosensor provided about 1.6-fold higher sensitivity than its graphene counterpart. Moreover, the linear working range and detection limit of the MWCNTs-based galactose biosensor was superior to the graphene-modified biosensor. The successful application of the purposed biosensors for galactose biosensing in human serum samples was also investigated.

Dual functional graphene derivative-based electrochemical platforms for detection of the TP53 gene with single nucleotide polymorphism selectivity in biological samples.

Novel disposable electrochemical DNA sensors were prepared for the detection of a target DNA sequence on the p53 tumor suppressor (TP53) gene. The electrochemical platform consisted of screen-printed carbon electrodes (SPCEs) functionalized with a water-soluble reduced graphene oxide-carboxymethylcellulose (rGO-CMC) hybrid nanomaterial. Two different configurations involving hairpin specific capture probes of different length covalently immobilized through carbodiimide chemistry on the surface of rGO-CMC-modified SPCEs were implemented and compared. Upon hybridization, a streptavidin-peroxidase (Strep-HRP) conjugate was employed as an electrochemical indicator. Hybridization was monitored by recording the amperometric responses measured at -0.10 V (vs an Ag pseudo-reference electrode) upon the addition of 3,3',5,5'-tetramethylbenzidine (TMB) as a redox mediator and H2O2 as an enzyme substrate. The implemented DNA platforms allow single nucleotide polymorphism (SNP) discrimination in cDNAs from human breast cancer cell lines, which makes such platforms excellent as new diagnosis tools in clinical analysis.

Amperometric determination of heavy metal using an HRP inhibition biosensor based on ITO nanoparticles-ruthenium (III) hexamine trichloride composite: Central composite design optimization.

A novel horseradish peroxidase (HRP) enzyme inhibition biosensor based on indium tin oxide (ITO) nanoparticles, hexaammineruthenium (III) chloride (RUT), and chitosan (CH) modified glassy carbon electrode (GCE) was developed. The biosensor fabrication process was investigated using scanning electron microscopy, energy-dispersive X-ray spectroscopy, cyclic voltammetry, and electrochemical impedance spectroscopy. The amounts of ITO nanoparticles and RUT were optimized using a 22 central composite design for the optimization of electrode composition. The detection limits were determined as 8 nM, 3 nM, and 1 nM for Pb2+, Ni2+, and Cd2+, respectively. The inhibition calibration curves of the biosensor were found to be within the range of 0.009-0.301 µM with a sensitivity of 11.97 µA µM-1 cm-2 (0.85 µA µM-1) for Pb2+, 0.011-0.368 µM with a sensitivity of 10.84 µA µM-1 cm-2 (0.77 µA µM-1) for Ni2+, and 0.008-0.372 µM with a sensitivity of 10.99 µA µM-1 cm-2 (0.78 µA µM-1) for Cd2+. The type of HRP inhibition by Pb2+, Ni2+ and Cd2+ was investigated by the Dixon and Cornish-Bowden plots. The effects of possible interfering species on the biosensor response were examined. The analysis of Pb2+, Ni2+, and Cd2+ in tap water was demonstrated using the HRP/ITO-RUT-CH/GCE with satisfactory experimental results. The proposed method agreed with the atomic absorption spectrometry results.

Amperometric biosensors based on carboxylated multiwalled carbon nanotubes-metal oxide nanoparticles-7,7,8,8-tetracyanoquinodimethane composite for the determination of xanthine.

A comparison of the analytical performances of two xanthine biosensors, based on the use of different metal oxide nanoparticles (MONPs: Co3O4 or Fe3O4)-modified carboxylated multiwalled carbon nanotubes (c-MWCNTs)-7,7',8,8'-tetracyanoquinodimethane (TCNQ)-chitosan (CHIT) composite, is discussed. Xanthine oxidase (XOD) enzyme was covalently attached to c-MWCNTs/MONPs/TCNQ/CHIT/GCE via N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) chemistry and the electrode surface was further modified with Nafion in order to minimize the effect of possible interfering substances. The results showed that analytical performance of the Fe3O4 based biosensor was better than the Co3O4 based biosensor. The linear working range, limit of detection and sensitivity were found to be 1.9×10-6-2.3×10-4M, 0.20µM (S/N=3), 25.07µAmM-1cm-2 for the Fe3O4 based biosensor and 1.9×10-6-1.2×10-4M, 0.36µM (S/N=3), 13.24µAmM-1cm-2 for the Co3O4 based biosensor, respectively. The purposed biosensors were applied in the determination of xanthine in coffee samples, and satisfactory results were obtained.

Graphene and tricobalt tetraoxide nanoparticles based biosensor for electrochemical glutamate sensing.

An amperometric biosensor based on tricobalt tetraoxide nanoparticles (Co3O4), graphene (GR), and chitosan (CS) nanocomposite modified glassy carbon electrode (GCE) for sensitive determination of glutamate was fabricated. Scanning electron microscopy was implemented to characterize morphology of the nanocomposite. The biosensor showed optimum response within 25 s at pH 7.5 and 37 °C, at +0.70 V. The linear working range of biosensor for glutamate was from 4.0 × 10-6 to 6.0 × 10-4 M with a detection limit of 2.0 × 10-6 M and sensitivity of 0.73 µA/mM or 7.37 µA/mMcm2. The relatively low Michaelis-Menten constant (1.09 mM) suggested enhanced enzyme affinity to glutamate. The glutamate biosensor lost 45% of its initial activity after three weeks.