A Graphene Oxide‐DNA Electrochemical Sensor Based on Glassy Carbon Electrode for Sensitive Determination of Methotrexate

Methotrexate (MTX) was used as an anti‐cancer drug, but its excessive use can cause serious side effects, it was necessary to monitor MTX in vivo. In this report, DNA was immobilized on a glassy carbon electrode (GCE) modified with graphene oxide (GO) to develop an electrochemical sensor for sensitive determination of MTX for the first time. The adsorptive voltammetric behaviors of MTX on DNA sensor were investigated using differential pulse voltammetry (DPV). The peak current response of guanine in DNA was used as a determination signal of MTX in acetate buffer solution pH 4.6. Voltammetric investigations revealed that the proposed method could determine MTX in the concentration range from 5.5×10⁻⁸ to 2.2×10⁻⁶ mol L⁻¹ with a lower detection limit of 7.6×10⁻9 mol L⁻¹ (S/N=3). The method was applied to detect MTX in human blood serum and diluted urine samples with excellent recoveries of 97.4–102.5 %. Compared with the previous studies, the DNA/GO/GCE electrode constructed by us based on the change rate of guanine current (R%) in DNA, proportionally reflecting the MTX concentration, is simple and sensitive .     

Cost-effective and Facile Production of a Phosphorus-doped Graphite Electrode for the Electrochemical Determination of Pyridoxine

In this study; a sensitive, selective, and simple electrochemical sensor was developed to determine low concentration pyridoxine (Py) using a phosphorus-doped pencil graphite electrode (P-doped/PGE). Electrode modification was implemented using the chronoamperometry method at +2.0 V constant potential and 100 seconds in 0.1 mol L⁻¹ H₃PO₄ supporting electrolyte solution. The characterization processes of the P-doped/PGE were carried out using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), and atomic force microscope (AFM) methods. In the concentration study, using the differential pulse voltammetry (DPV) method, a linear calibration plot was acquired in the concentration range of 0.5 to 300 μmol L⁻¹ Py. The limit of quantification (LOQ) and limit of detection (LOD) of the developed method were calculated as 0.219 μmol L⁻¹ and 0.0656 μmol L⁻¹, respectively. Detection of Py has been successfully performed on the P-doped/PGE in the beverage samples. As a result, the method developed has been shown to have fast, low cost, and simple for the sensitive and selective detection of Py as an effective electrode.     

Carbon‐nanotube Modified Screen‐printed Electrode for the Simultaneous Determination of Nitrite and Uric Acid in Biological Fluids Using Batch‐injection Amperometric Detection

A portable electroanalytical system applied for rapid and simultaneous determination of uric acid (UA) and nitrite (NIT) in human biological fluids (urine, saliva and blood) is reported. The system is based on batch‐injection analysis with multiple‐pulse amperometric (BIA‐MPA) detection using screen‐printed electrodes (SPEs) modified with multi‐walled carbon nanotubes. Sample dilution in optimized electrolyte (0.1 mol L⁻¹ Britton‐Robinson buffer pH 2) followed by injection of 100 μL on the electrode surface using an electronic micropipette is performed. UA is detected at +0.45 V and both UA+NIT at +0.70 V. Linear calibration plots for UA and NIT were obtained over the range of 1–500 μmol L⁻¹ with detection limits of 0.05 and 0.06 μmol L⁻¹, respectively. For comparison, a differential‐pulse voltammetric (DPV) method was optimized, and linear calibration plots for UA and NIT were obtained over range of 1–30 μmol L⁻¹ and 1–40 μmol L⁻¹ with detection limits of 0.1 and 0.3 μmol L⁻¹, respectively. BIA‐MPA is highly precise (RSD<1.3 %), fast (160 h⁻¹) and free from sample‐matrix interferences as recovery values ranged from 77 to 121 % for spiked samples (short contact time of sample aliquot with SPE). Contrarily, recovery tests conducted using DPV did not provide adequate recovery values (>150 %), probably due to the longer contact time of the SPE with the biological samples during analysis leading to a severe interference of sample matrices.     

Comparative Study on Electroanalysis of Fenthion Using Silver Amalgam Film Electrode and Glassy Carbon Electrode Modified with Reduced Graphene Oxide

Oxidation and reduction processes of the insecticide fenthion was comparatively investigated at a reduced graphene oxide modified glassy carbon electrode (RGO‐GCE) and a cyclic renewable silver amalgam film electrode (Hg(Ag)FE) using square wave stripping voltammetry (SWSV). The influence of pH and SW parameters was investigated. The linear concentration ranges were found to be 1 × 10⁻⁶ – 2 × 10⁻⁵ and 1 × 10⁻⁷ – 2 × 10⁻⁵ mol L⁻¹ for Hg(Ag)FE and RGO‐GCE, respectively. The detection and quantification limits were calculated as 1.3 × 10⁻⁷ and 4.5 × 10⁻⁷ mol L⁻¹ for Hg(Ag)FE and 7.6 × 10⁻⁹ and 2.5 × 10⁻⁸ mol L⁻¹ for RGO‐GCE. Both of the developed electroanalytical methods offer rapid and simple detection of fenthion and were used on spiked tap and river water and apple juice samples. Scanning electron microscopy was used for RGO‐GCE surface characterization.     

Gold Nanoparticles Stabilized in β‐Cyclodextrin and Decorated with Laccase Applied in the Construction of a Biosensor for Rutin

This paper describes the synthesis and characterization of gold nanoparticles stabilized in β‐cyclodextrin (AuNP‐CD), which were applied as a platform in the immobilization of laccase (LAC). The AuNP‐CD‐LAC were used in the construction of a new biosensor for rutin determination by square‐wave voltammetry (SWV). Under optimized conditions, the calibration curve showed a linear range for rutin of 0.30 to 2.97 μmol L⁻¹, with a limit of detection of 0.17 μmol L⁻¹. The biosensor demonstrated satisfactory repeatability and electrode‐to‐electrode repeatability (with relative standard deviations of 5.6 and 6.0 %, respectively) and good stability. The biosensor was successfully applied in the determination of rutin in different pharmaceutical samples.     

Determination of Anti-Parkinson Drug Pramipexole Using a Label-free Biosensor and Evaluation of its Interaction with ds-DNA

In this study, we fabricated an effective and sensitive DNA biosensor based on flower-like Pt/NiCo₂O₄ modified carbon paste electrode (FL-Pt/NiCo₂O₄/CPE) for detection of pramipexole (PPX). Spectrophotometry, differential pulse voltammetry (DPV) and docking methods were employed to evaluate the interaction of DNA-PPX. Moreover, the DPV technique was chosen to monitor the electrochemical response of guanine on the DNA biosensor. The relationship between the concentration of PPX and the oxidation signal of guanine was linear in the range of 0.4 to 310.0 μM and a limit of detection (LOD) of 0.09 μM was calculated.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotubes and Cobalt Phthalocyanine Composite for Pyridoxine Determination

In this work, an electrochemical sensor based on pyrolytic graphite electrode (PGE), cobalt phthalocyanine (CoPc) and multiwalled carbon nanotube (MWCNT) composite designed as PGE‐MWCNT/CoPc was developed and validated for pyridoxine (vitamin B6) determination employing Differential Pulse Voltammetry (DPV). The electrochemical behaviour of pyridoxine at the PGE‐MWCNT/CoPc has been evaluated and the charge transfer coefficient, α, and the charge transfer rate constant, κ, were calculated as 0.30 and 11.67±0.43 s^?1, respectively, which indicates that, although this system is irreversible, it is viable kinetically to be used as a sensor. The optimized experimental conditions were pH 5.5 in 0.30 mol L^?1 phosphate buffer. The linear range found was 10 to 400 μmol L^?1 of pyridoxine, with r=0.9987. The limits of detection and quantification were 0.50 and 1.67 μmol L^?1, respectively, showing the good sensitivity of the method. The method was successfully applied for the pyridoxine determination in real samples of pharmaceutical formulation with RSD% lower than 5 % indicating that it can be used for routine quality control pharmaceutical formulations containing pyridoxine. Furthermore, it has the advantages of a fast response, a low detection limit and low cost.     

Magnetite Nanoparticles Bonded Carbon Quantum Dots Magnetically Confined onto Screen Printed Carbon Electrodes and their Performance as Electrochemical Sensor for NADH

Hybrid magnetite/carbon quantum dots (MagNP/C‐dots) were prepared and their characterization performed by high resolution transmission electron microscopy (HR‐TEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectroscopy (XPS). Because of their suitable magnetization and electrochemical properties, they were used as versatile electrode modifiers after magnetically confining onto screen printed carbon electrodes (SPE), with the aid of a miniature external magnet. The reported strategy introduces a convenient procedure for assembling modified electrodes, since the nanoparticles can be easily released by removing the magnet. The non‐enzymatic magnetic biosensor showed excellent performance in the determination of NADH at the concentration range 2×10⁻⁷ to 5×10⁻⁶ mol L⁻¹, exhibiting a sensitivity of 0.15 μmol L⁻¹ and detection limit of 20 nmol L⁻¹. The MagNP/C‐dots/SPE sensor was also successfully applied for the determination of NADH in serum samples. The interference of typical biological molecules has also been investigated.     

Experimental and theoretical investigation effect of flavonols antioxidants on DNA damage

A new electrochemical biosensor was developed to demonstrate the effect of Acridine Orange (AO) on DNA damage. Then, the biosensor was used to check the inhibitors effect of three flavonols antioxidants (myricetin, fisetin and kaempferol) on DNA damage. Acridine Orange (AO) was used as a damaging agent because it shows a high affinity to nucleic acid and stretch of the double helical structure of DNA. Decreasing on the oxidation signals of adenine and guanine (in the DNA) in the presence of AO were used as probes to study the antioxidants power, using DNA-modified screen printed graphene electrode (DNA/SPGE). The results of our study showed that the DNA-biosensor could be suitable biosensor to investigate the inhibitors ability of the flavonols antioxidants on the DNA damage. The linear dependency was detected in the two regions in the ranges of 1.0–15.0 and 15.0–500.0 pmol L⁻¹. The detection limit was found 0.5 pmol L⁻¹ and 0.6 pmol L⁻¹ for guanine and adenine, respectively. To confirm the electrochemical results, Uv–Vis and fluorescence spectroscopic methods were used too. Finally molecular dynamic (MD) simulation was performed on the structure of DNA in a water box to study any interaction between the antioxidant, AO and DNA.     

Development of Electrochemical Biosensor Based on Nanostructured Carbon Materials for Paracetamol Determination

This work describes the development of a biosensor for paracetamol (PAR) determination based on a glassy carbon electrode (GCE) modified with multiwalled carbon nanotubes (MWCNT) and laccase enzyme (LAC), which was immobilized by means of covalent crosslinking using glutaraldehyde. Voltammetric investigations were carried out by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and square wave voltammetry (SWV). The biosensor was characterized by Scanning Electron Microscope (SEM) and Fourier Transform Infrared Spectroscopy (FT‐IR). The results showed that the use of MWCNT/LAC composite increased the sensor sensitivity, compared to bare glassy carbon electrode. Factors affecting the voltammetric signals such as pH, ionic strength, scan rate and interferents were assessed. Linear range, limit of detection (LOD) and limit of quantitation (LOQ) obtained were 10–320 μmol L^?1, 7 μmol L^?1 and 10 μmol L^{? 1}, respectively. The developed biosensor was successfully applied to PAR determination in urine and pharmaceutical formulations samples, with recovery varying from 99.96 to 106.20 % in urine samples and a relative standard deviation less than 1.04 % for PAR determination in pharmaceutical formulations. Therefore, the MWCNT‐LAC/GCE exhibits excellent sensitivity and can be used to PAR determination as a viable alternative in clinical analyzes and quality control of pharmaceutical formulations, through a simple, fast and inexpensive methodology.     

Time Resolved Direct Determination of Arsenate in the Presence of Arsenite on Pencil Graphite Electrode Modified by Graphene Oxide and Zirconium

Trace amount of arsenate in the presence of arsenite was determined directly on pencil graphite electrode modified by graphene oxide and zirconium (Zr−G−PGE). The layer‐by‐layer modification of PGE was characterized by scanning electron microscopy (SEM), X‐ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Key point of the developed method was quick adsorption of arsenate than arsenite on the Zr−G−PGE. In optimal conditions, the Zr−G−PGE was applied for determination of arsenate using differential pulse voltammetry in a linear range 0.10–40.0 μg L⁻¹ with a limit of determination of 0.12±0.01 μg L⁻¹. The sensitivity of the electrode was 1.36±0.07 μA/μg L⁻¹. The modified electrode was used to measure the concentration of arsenate in the river water. A recovery test was performed by introducing 10 μg L⁻¹ arsenate into the rivers water in order and acceptable data of average recovery of 101.2 % was obtained. From the experimental results, the as‐prepared electrode can provide a satisfactory method for direct determination of arsenate in real samples.     

Differential Pulse Voltammetric Detection of Hepatitis C Virus 1a Oligonucleotide Chain by a Label‐Free Electrochemical DNA Hybridization Biosensor Using Consensus Sequence of Hepatitis C Virus 1a Probe on the Pencil Graphite Electrode

The short sequence related to hepatitis C virus (HCV1) is detected by a label‐free DNA hybridization biosensor. The sensor relies on the immobilization of a 20‐mer oligonucleotide containing 2 guanine and 11 cytosine bases denoted PHCV1 as probe on the pencil graphite electrode (PGE). The hybridization event was monitored by differential pulse voltammetry (DPV) using the guanine signal. The selectivity of the biosensor was studied using some noncomplementary oligonucleotides. Diagnostic performance of the biosensor is described and the detection limit was found to be 6.5 nM.     

Competitive Host-guest Electrochemical Detection of Ivermectin Drug Using a β-Cyclodextrin/Graphene-based Electrode

The present study describes the novel development and application of an ivermectin (IVM) sensing electrochemical platform based on reduced graphene oxide (rGO) and the macrocyclic host β-cyclodextrin (β-CD) molecule. The sensing method was based in the host-guest characteristics of β-CD and competitive interaction between the target analyte and the methylene blue (MB) redox probe. Differential pulse voltammetry (DPV) was employed for the detection of IVM and a linear response between 0.5 and 40.0 μmol L⁻¹ with a limit of detection of 0.25 μmol L⁻¹ was obtained using the glassy carbon (GC)/rGO/β-CD electrode. The sensing platform was successfully applied for the detection of IVM in tap water samples, which may expand the applications of β-CD towards the analysis of other chemical species.     

Electrochemical Nucleic Acid Biosensors for the Detection of Interaction Between Peroxynitrite and DNA

We studied the reactivity of peroxynitrite and different nucleic acid molecules using DNA electrochemical biosensors. SIN‐1 (3‐morpholinosydnonimine) has been used for the simultaneous generation of NO?and superoxide, i.e., as a peroxynitrite (ONOO^?) donor. Double strand DNA (dsDNA), single strand DNA (ssDNA) and 15 guanine bases oligonucleotide (Oligo(dG)₁₅) were immobilized on a carbon paste electrode to generate the biosensor and DPV was selected as the electroanalytical technique. Results showed that electrochemical biosensors were very sensitive for detecting interaction between ONOO^? and DNA. A down/up effect was observed, i.e., at low ONOO^? concentrations the guanine oxidation signal decreased while at high ONOO^? concentrations the guanine oxidation current increased. Oligo(dG)₁₅ exhibited greater interaction at low ONOO^? concentrations than the other DNA molecules. The reactivity between ONOO^? and DNA was also evaluated in solution phase, showing the same down/up effect. Finally, the capacity of DNA to hybridize was prevented after interaction with ONOO^?.     

Fabrication of β‐Cyclodextrin/Glycine/Carbon Nanotubes Electrochemical Neurotransmitters Sensor – Application in Ultra‐sensitive Determination of DOPAC in Human Serum

In this work, an electrochemical sensor was constructed by applying two successive thin layers of glycine‐carbon nanotubes mixture and β‐cyclodextrin (CNTs‐Gly)/CD over glassy carbon electrode surface for some neurotransmitters determination. A host‐guest interaction between CD and neurotransmitters molecules is expected and resulted in enhanced sensitivity, selectivity and stability of sensor response. Other components of the sensor are crucial for the unique electrochemical response. Carbon nanotubes allowed large surface area for glycine distribution that provided hydrogen bonding to CD moieties and contributed to facilitated charge transfer. It was possible to determine 3,4‐dihydroxy phenyl acetic acid (DOPAC) in the linear range of 0.1 μmol L⁻¹ to 80 μmol L⁻¹ with detection limit of 9.40 nmol L⁻¹, quantification limit of 31.5 nmol L⁻¹ and sensitivity of 4.16 μA/μmol L⁻¹. The proposed sensor was applied in synthetic cerebrospinal fluids samples using random standard addition method. Also, the proposed sensor was used to determine DOPAC in presence of common interferences and acceptable recovery results were achieved for its analysis in real blood serum. Figures of merit for (CNTs‐Gly)/CD composite in terms of precision, robustness, repeatability and reproducibility were reported.     

Simultaneous Determination of Rosmarinic Acid and Protocatechuic Acid at Poly(o‐Phenylenediamine)/Pt Nanoparticles Modified Glassy Carbon Electrode

A system of Pt nanoparticles and poly(ortho‐phenylenediamine) film electrochemically deposited onto a glassy carbon electrode (GCE/PoPD/Pt) was fabricated. Scanning electron microscopy, Fourier‐transform infrared spectroscopy, and atomic force microscopy techniques were used to identify the surface characteristics of the composite electrode. The conductive polymers and Pt nanoparticles together resulted in a synergistic effect, and the new formed surface was highly active against polyphenolic structures. Rosmarinic acid (RA) and protocatechuic acid (PCA) are phenolic compounds found in plants, and they are used in many applications, particularly as pharmaceuticals. The GCE/PoPD/Pt was used for the simultaneous determination of RA and PCA in a pH 2.0 H₂SO₄ solution for the first time. The RA and PCA concentrations were determined using differential pulse voltammetry (DPV) and chronoamperometry. By the amperometry measurement, for RA and PCA, a linear relation was observed in the concentration ranges of 1–55 μmol L^?1 and 1–60 μmol L^?1, with detection limits of 0.5 μmol L^?1 and 0.6 μmol L^?1, respectively. In the simultaneous determination with DPV, the detection limits for both RA and PCA were calculated as 0.7 μmol L^?1. The GCE/PoPD/Pt was successfully used for the simultaneous determination of RA and PCA in a real sample, and its accuracy was verified by high‐performance liquid chromatography studies.     

Label-free electrochemical detection of Avian Influenza Virus genotype utilizing multi-walled carbon nanotubes–cobalt phthalocyanine–PAMAM nanocomposite modified glassy carbon electrode

A novel DNA electrochemical biosensor for label-free determination of DNA sequence related to the Avian Influenza Virus (AIV) genotype was demonstrated in this paper. First, the multi-walled carbon nanotubes–cobalt phthalocyanine (MWNTs–CoPc) nanocomposite and poly (amidoamine) (PAMAM) dendrimer (generation 4.0) were modified on the glassy carbon electrode (GCE) sequentially. Then, DNA probes were successfully immobilized on the modified electrode with G4 PAMAM dendrimer acting as the coupling agent. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement based on the oxidation signals of guanine without any external labels. Under the optimal conditions, the difference in guanine oxidation signal of the probe modified GCE in the absence and presence of complementary target (ΔI_p) was linear with the logarithmic value of the complementary target concentration from 0.01 to 500 ng/ml with a correlation coefficient of 0.998 and a detection limit of 1.0 pg/ml.     

A Self‐assembled L‐Cysteine and Electrodeposited Gold Nanoparticles‐reduced Graphene Oxide Modified Electrode for Adsorptive Stripping Determination of Copper

Glassy carbon electrode (GCE) modified with L‐cysteine and gold nanoparticles‐reduced graphene oxide (AuNPs‐RGO) composite was fabricated as a novel electrochemical sensor for the determination of Cu²⁺. The AuNPs‐RGO composite was formed on GCE surface by electrodeposition. The L‐cysteine was decorated on AuNPs by self‐assembly. Physicochemical and electrochemical properties of L‐cysteine/AuNPs‐RGO/GCE were characterized by scanning electron microscopy, atomic force microscopy, energy dispersive spectroscopy, Raman spectroscopy, X‐ray diffraction, cyclic voltammetry and adsorptive stripping voltammetry. The results validated that the prepared electrode had many attractive features, such as large electroactive area, good electrical conductivity and high sensitivity. Experimental conditions, including electrodeposition cycle, self‐assembly time, electrolyte pH and preconcentration time were studied and optimized. Stripping signals obtained from L‐cysteine/AuNPs‐RGO/GCE exhibited good linear relationship with Cu²⁺ concentrations in the range from 2 to 60 μg L⁻¹, with a detection limit of 0.037 μg L⁻¹. Finally, the prepared electrode was applied for the determination of Cu²⁺ in soil samples, and the results were in agreement with those obtained by inductively coupled plasma mass spectrometry.     

Direct Electrochemical Determination of Glyphosate at Copper Phthalocyanine/Multiwalled Carbon Nanotube Film Electrodes

A copper phthalocyanine/multiwalled carbon nanotube film‐modified glassy carbon electrode has been used for the determination of the herbicide glyphosate (Gly) at ?50 mV vs. SCE by electrochemical oxidation using differential pulse voltammetry (DPV). Cyclic voltammetry and electrochemical impedance spectroscopy showed that Gly is adsorbed on the metallic centre of the copper phthalocyanine molecule, with formation of Gly‐copper ion complexes. An analytical method was developed using DPV in pH 7.4 phosphate buffer solution, without any pretreatment steps: Gly was determined in the concentration range of 0.83–9.90 μmol L^?1, with detection limit 12.2 nmol L^?1 (2.02 μg L^?1).