Electrocatalytic Oxidation of Diethylaminoethanethiol and Hydrazine at Single‐walled Carbon Nanotubes Modified with Prussian Blue Nanoparticles

In this work, edged plane pyrolytic graphite electrode EPPGE was modified with functionalised single‐walled carbon nanotubes and Prussian blue nanoparticles (PB). The modified electrode was characterised by techniques such as TEM, FTIR, XPS, EDX and cyclic voltammetry. The EPPGE‐SWCNT‐PB platform exhibited enhanced electron transport and catalytic efficiency towards the oxidation of Diethylaminoethanethiol (DEAET) and hydrazine compared with the other electrodes studied. The EPPGE‐SWCNT‐PB showed good electrochemical stability in the analytical solution, showing limit of detection in the micromolar range and catalytic rate constant of 3.71×10⁶ and 7.56×10⁶ cm³ mol^?1 s^?1 for DEAET and hydrazine respectively. The adsorption properties of these analytes that impact on their detection at the SWCNT‐PB film modified electrode were evaluated and discussed.     

Development of Voltammetric Sensor for Determination of Tryptophan Using MWCNTs‐modified Sol‐gel Electrode

In the present work, an electrochemical sensor was developed for simple and sensitive determination of tryptophan (Trp) using multi‐walled carbon nanotubes modified sol‐gel electrode (MWCNTs/SGE). The electrocatalytic oxidation of tryptophan was investigated by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). It was found that the oxidation peak current of Trp at the MWCNTs/SGE was greatly improved compared with that of the bare SGE. Furthermore, at the MWCNTs/SGE, the anodic peak potential of Trp is shifted about 220 mV to more negative value indicated that modified electrode has better electrocatalytic activity for electro‐oxidation of Trp. The anodic peak currents increased linearly with the concentration of tryptophan in the range of 0.2 × 10^?6 to 15 × 10^?6 M with a detection limit of 0.139 × 10^?6 M (at an S/N = 3).     

Determination of 1‐Naphthol with Denatured DNA–Modified Pretreated Glassy Carbon Electrode

Abstract

A highly sensitive electrochemical biosensor for the detection of trace amount of 1‐naphthol was designed. Acid‐denatured DNA were immobilized onto the pretreated glassy carbon electrode (GCE(ox)) surface. Two well‐defined oxidation peaks were observed on the denatured DNA‐modified GCE(ox) at about +0.80 V and +1.10 V (vs. Ag/AgCl) in 0.10‐M acetate buffer (pH 5.0). The peak current of the guanine residue decreased with increasing concentration of 1‐naphthol. The optimum experimental conditions for the detection of 1‐naphthol were explored, and the calibration was linear for 1‐naphthol in the range of 1.0×10^?8?1.1×10^?6 M, with a correlation coefficient of 0.998. The limit of detection (LOD) was 5.0×10^?9 M (S/N=3).     

Selective Detection of Dopamine in Presence of Ascorbic Acid by Use of Glassy‐Carbon Electrode Modified with Amino‐β‐Cyclodextrin and Carbon Nanotubes

A glassy carbon electrode modified with per‐6‐amino‐β‐cyclodextrin (β‐CDNH₂) and functionalized single‐walled carbon nanotubes (SWCNT‐COOH) was elaborated. This structure was investigated for the detection of dopamine acid (DA) in presence of ascorbic acid (AA). The sensor behavior was studied by cyclic voltammetry, square wave voltammetry and electrochemical impedance spectroscopy. The analysis results show that the electrode modification with CD derivative improves the sensitivity and selectivity of the DA recognition; the electrochemical response was further improved by introduction of SWCNT‐COOH. The sensor shows good and reversible linear response toward DA within the concentration range of 7×10^?7–10^?4 M with a detection limit of 5×10^?7 M.     

Preparation,Characterization and Electrochemical Application of ZnO‐CuO Nanoplates for Voltammetric Determination of Captopril and Tryptophan Using Modified Carbon Paste Electrode

2‐chlorobenzoyl ferrocene, was synthesized and used to construct a modified ZnO‐CuO nanoplates modified carbon paste electrode. The electrooxidation of captopril at the surface of the modified electrode was studied. Under the optimized conditions, the square wave voltammetric (SWV) peak current of captopril increased linearly with captopril concentration in the range of 5.0×10^?7 to 9.0×10^?4 M and detection limit of 90.0 nM was obtained for captopril. The diffusion coefficient and kinetic parameters (such as electron transfer coefficient and the heterogeneous rate constant) for captopril oxidation were also determined. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of captopril and tryptophan which makes it suitable for the detection of captopril in the presence of tryptophan in real samples.     

Nano‐Gold Modified Genosensor for Direct Detection of DNA Hybridization

In this paper, nano‐gold modified carbon paste electrode (NGMCPE) was employed to develop an electrochemical DNA hybridization biosensor. The proposed sensor was made up by immobilization of 15‐mer single stranded oligonucleotide probe for detection of target DNA. Hybridization detection relies on the alternation in guanine oxidation signal following hybridization of the probe with complementary genomic DNA. The guanine oxidation was monitored using differential pulse voltammetry (DPV). Different factors such as activation potential, activation time and probe immobilization conditions were optimized. The selectivity of the sensor was investigated by non‐complementary oligonucleotides. Diagnostic performance of the biosensor was described and the detection limit was found 1.9 × 10^?13 M at the NGMCPE surface. All of the investigations were performed in both CPE and NGMCPE and finally their results were compared.     

Graphene Nanosheets Modified Glassy Carbon Electrode as a Highly Sensitive and Selective Voltammetric Sensor for Rutin

Graphene nanosheets modified glassy carbon electrode (GNs/GCE) was fabricated as voltammetric sensor for rutin with good sensitivity, selectivity and reproducibility. The sensor exhibits an adsorption‐controlled, reversible two‐proton and two electron transfer reaction for the oxidation of rutin with a peak‐to‐peak separation (ΔE_p) of 26 mV as revealed by cyclic voltammetry. Moreover, the redox peak current increased about 14 times than that on bare glassy carbon electrode (GCE). The linear response of the sensor is from 1×10^?7 to 1×10^?5 M with a detection limit of 2.1 × 10^?8 M (S/N = 3). The method was successfully applied to determine rutin in tablets with satisfied recovery.     

Electrochemical Characterization of Gold 6‐Amino‐2‐mercaptobenzothiazole Self‐Assembled Monolayer for Dopamine Detection in Pharmaceutical Samples

A new sensor, gold‐6‐amino‐2‐mercaptobenzothiazole (6A2MBT), was fabricated via a self‐assembly procedure. Electrochemical properties of the monolayer were investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The modified electrode showed excellent antifouling property against the oxidation products of DA, allowed us to construct a dynamic calibration curve with two linear parts, 1.00×10^?6 to 3.72×10^?4 and 3.72×10^?4 to 6.42×10^?4 M DA, with correlation coefficients of 0.997 and 0.992 and a detection limit of 1.57×10^?7 M DA by using differential pulse voltammetry (DPV), respectively. Finally, the performance of the Au‐6A2MBT modified electrode was successfully tested for electrochemical detection of DA in a pharmaceutical sample.     

Application of a Modified CuO Nanoparticles Carbon Paste Electrode for Simultaneous Determination of Isoperenaline,Acetaminophen and N‐acetyl‐L‐cysteine

A 1‐[2‐hydroxynaphthylazo]‐6‐nitro‐2‐naphthol‐4‐sulfonate/ CuO nanoparticles modified carbon paste electrode (HNNSCCPE) was constructed and the electro‐oxidation of isoprenaline at the surface of the modified electrode was studied using cyclic voltammetry (CV), chronoamperometry (CHA), and square wave voltammetry (SWV). Under the optimized conditions, the square wave voltammetric peak current of isoprenaline increased linearly with isoprenaline concentrations in the range of 1.0×10^?7 to 7.0×10^?4 M and detection limit of 5.0×10^?8 M was obtained for isoprenaline. The prepared modified electrode exhibits a very good resolution between the voltammetric peaks of isoprenaline, acetaminophen and N‐acetyl‐L‐cysteine which makes it suitable for the detection of isoprenaline in the presence of acetaminophen and N‐acetyl‐L‐cysteine in real samples.     

Electrochemical Study of Interaction Between Clozapine and DNA and Its Analytical Application

Abstract

The interaction between clozapine (CLZ) as an orally administrated antipsychotic drug with double stranded calf thymus DNA (dsDNA) was investigated at electrode surface using differential pulse voltammetry (DPV). Activated carbon paste electrode (CPE) was modified with dsDNA and used for monitoring the changes of the characteristics peak of CLZ in 0.05 M acetate buffer (pH 4.3). The adsorptive stripping voltammetry on dsDNA‐modified carbon paste electrode (dsDNA‐CPE) was used for determination of very low concentration of CLZ. Under optimal conditions, the oxidation peak current is proportional to CLZ concentration in the range of 7×10^?9?1.2×10^?6 mol l^?1 with a detection limit of 1.5×10^?9 mol l^?1 for 180 s accumulation time by DPV. The proposed dsDNA‐CPE was successfully used for determination of CLZ in human serum samples with recovery of 97.0±2.5%.     

Fabrication of a Sensitive Impedance Biosensor of DNA Hybridization Based on Gold Nanoparticles Modified Gold Electrode

In this work, we report on the preparation of a simple, sensitive DNA impedance sensor. Firstly gold nanoparticles were electrodeposited on the surface of a gold electrode, and then probe DNA was immobilized on the surface of gold nanoparticles through a 5′‐thiol‐linker. Electrochemical impedance spectroscopy (EIS) was used to investigate probe DNA immobilization and hybridization. Compared to the bare gold electrode, the gold nanoparticles modified electrode could improve the density of probe DNA attachment and the sensitivity of DNA sensor greatly. The difference of electron transfer resistance (ΔR_et) was linear with the logarithm of complementary oligonucleotides sequence concentrations in the range of 2.0×10^?12 to 9.0×10^?8 M, and the detection limit was 6.7×10^?13 M. In addition, the DNA sensor showed a fairly good reproducibility and stability during repeated regeneration and hybridization cycles.     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

Amperometric Nitric Oxide Sensor Based on Poly(Thionine)/Nafion‐Modified Electrode and Its Application in Monitoring Nitric Oxide Release from Rat Kidney

Abstract

A novel amperometric nitric oxide (NO) sensor based on a glassy carbon electrode modified with thionine and Nafion films has been developed. The oxidation peak current of NO increased significantly at the poly(thionine)/Nafion‐modified glassy carbon electrode (GCE), which can be used for the detection of NO. The oxidation peak current was linear with the concentration of nitric oxide over the range from 3.6×10^?7 to 6.8×10^?5 mol · L^?1, and the detection limit was 7.2×10^?8 mol · L^?1. This nitric oxide sensor showed high selectivity to nitric oxide determination, and some potential interference could be eliminated effectively. The nitric oxide sensor has been applied to monitor NO release from rat kidney stimulated by L‐arginine. The results indicated the applicability of the NO sensor to biomedical samples.     

A Highly Selective and Sensitive Barium(II)‐Selective PVC Membrane Based on Dimethyl 1‐Acetyl‐8‐oxo‐2,8‐dihydro‐ 1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate

A poly(vinyl chloride)‐based membrane of dimethyl 1‐acetyl‐8‐oxo‐2,8‐dihydro‐1H‐pyra‐zolo[5,1‐a]isoindole‐2,3‐dicarboxylate as a neutral carrier with sodium tetraphenylborate (NaTPB) as an anion excluder and 2‐nitrophenyl octyl ether (NPOE) as plasticizer was prepared and investigated as a Ba(II)‐selective electrode. The electrode exhibits a Nernstian slope of 29.7±0.4 mV per decade over a wide concentration range (1.0×10^?6 to 1.0×10^?1 M) with a detection limit of 7.6×10^?7 M between pH 3.0 and 11.0. The response time of the sensor is about 10 s and it can be used over a period of 2 months without any divergence in potential. The proposed membrane sensor revealed good selectivity for Ba(II) over a wide variety of other metal ions. It was successfully used in direct determination of barium ions in industrial wastewater samples.     

Nanomolar Determination of Methyldopa in the Presence of Large Amounts of Hydrochlorothiazide Using a Carbon Paste Electrode Modified with Graphene Oxide Nanosheets and 3‐(4′‐Amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic Acid

A novel electrochemical sensor for sensitive detection of methyldopa at physiological pH was developed by the bulk modification of carbon paste electrode (CPE) with graphene oxide nanosheets and 3‐(4′‐amino‐3′‐hydroxy‐biphenyl‐4‐yl)‐acrylic acid (3,′AA). Applying square wave voltammetry (SWV), in phosphate buffer solution (PBS) of pH 7.0, the oxidation current increased linearly with two concentration intervals of methyldopa, one is 1.0×10^?8–1.0×10^?6 M and the other is 1.0×10^?6–4.5×10^?5 M. The detection limit (3σ) obtained by SWV was 9.0 nM. The modified electrode was successfully applied for simultaneous determination of methyldopa and hydrochlorothiazide. Finally, the proposed method was applied to the determination of methyldopa and hydrochlorothiazide in some real samples.     

Electrochemical oxidation behavior of methotrexate at DNA/SWCNT/Nafion composite film-modified glassy carbon electrode

Glassy carbon electrode modified with DNA-functionalized single-walled carbon nanotube (DNA/SWCNT) and Nafion composite film was developed for the detection of methotrexate. The characteristics of the modified electrode were examined by transmission electron microscopy and cyclic voltammetry. Compared with a bare glassy carbon electrode and Nafion- and SWCNT/Nafion-modified electrodes, the DNA/SWCNT/Nafion-modified one exhibited the more superior ability of detecting methotrexate, including the higher sensitivity and the lower overpotentials, due to the synergetic DNA-functionalized SWCNT and Nafion. Also, the dependence of the current on pH, nature of buffer, instrumental parameters, accumulation time, and potential was investigated to optimize the experimental conditions in the determination of methotrexate. Under the selected conditions, the modified electrode in pH?=?2.78 Britton–Robinson buffer solutions showed a linear voltammetric response to methotrexate within the concentration range of 2.0?×?10^?8–1.5?×?10^?6?mol?L^?1, with the detection limit of 8.0?×?10^?9?mol?L^?1. The method was also applied to detect methotrexate in medicinal tablets and spiked human blood serum samples.     

A Selective Voltammetric Method for Uric Acid Detection at a Glassy Carbon Electrode Modified with Electrodeposited Film Containing DNA and Pt‐Fe(III) Nanocomposites

A novel biosensor by electrochemical codeposited Pt‐Fe(III) nanocomposites and DNA film was constructed and applied to the detection of uric acid (UA) in the presence of high concentration of ascorbic acid (AA). Based on its strong catalytic activity toward the oxidation of UA and AA, the modified electrode resolved the overlapping voltammetric response of UA and AA into two well‐defined peaks with a large anodic peak difference (ΔE_pa) of about 380mV. The catalytic peak current obtained from differential pulse voltammetry (DPV) was linearly dependent on the UA concentration from 3.8×10^?6 to 1.6×10^?4 M (r=0.9967) with coexistence of 5.0×10^?4 M AA. The detection limit was 1.8×10^?6 M (S/N=3) and the presence of 20 times higher concentration of AA did not interfere with the determination. The modified electrode shows good sensitivity, selectivity and stability.     

Electrochemical Determination of 2‐Nitrophenol in Water Samples Using Mg‐Al‐SDS Hydrotalcite‐Like Clay Modified Glassy Carbon Electrode

A glassy carbon electrode (GCE) modified with Mg‐Al‐SDS hydrotalcite‐like clay (SDS‐HTLC) was used for the sensitive voltammetric determination of 2‐nitrophenol (2‐NP) utilizing the oxidation process. The results indicate the prepared modified electrode has an excellent electrocatalytic activity toward 2‐NP oxidation, lowering the oxidation overpotential and increasing the oxidation current. Under optimal conditions, the oxidation current was proportional to 2‐NP concentration in the range from 1.0×10^?6 to 6.0×10^?4 M with the detection limit of 5.0×10^?7 M by DPV (S/N=3). The fabricated electrode was applied for 2‐NP determination in water samples and the recovery for these samples was from 95.6 to 103.5%.     

Electrochemical DNA Biosensor Based on Partially Reduced Graphene Oxide Modified Carbon Ionic Liquid Electrode for the Detection of Transgenic Soybean A2704‐12 Gene Sequence

In this work a partially reduced graphene oxide (p‐RGO) modified carbon ionic liquid electrode (CILE) was prepared as the platform to fabricate an electrochemical DNA sensor, which was used for the sensitive detection of target ssDNA sequence related to transgenic soybean A2704‐12 sequence. The CILE was fabricated by using 1‐butylpyridinium hexafluorophosphate as the binder and then p‐RGO was deposited on the surface of CILE by controlling the electroreduction conditions. NH₂ modified ssDNA probe sequences were immobilized on the electrode surface via covalent bonds between the unreduced oxygen groups on the p‐RGO surface and the amine group at the 5′‐end of ssDNA, which was denoted as ssDNA/p‐RGO/CILE and further used to hybridize with the target ssDNA sequence. Methylene blue (MB) was used as electrochemical indicator to monitor the DNA hybridization. The reduction peak current of MB after hybridization was proportional to the concentration of target A2704‐12 ssDNA sequences in the range from 1.0×10^?12 to 1.0×10^?6 mol/L with a detection limit of 2.9×10^?13 mol/L (3σ). The electrochemical DNA biosensor was further used for the detection of PCR products of transgenic soybean with satisfactory results.     

Voltammetric Determination of 2′‐Deoxyadenosine and Adenine in Urine of Patients with Hepatocellular Carcinoma Using Fullerene‐C60‐modified Glassy Carbon Electrode

A fullerene‐C₆₀‐modified glassy carbon electrode has been examined for the simultaneous determination of 2′‐deoxyadenosine (2′‐dAdo) and adenine in human blood and urine using Osteryoung square‐wave voltammetry (OSWV) at pH 7.2. Compared to bare glassy carbon electrode (GCE), the modified electrode displays a shift of the oxidation potential in the negative direction with significant increase in the peak current for both the analytes. At modified electrode well‐defined anodic peaks at potential of 1248 mV and 994 mV are observed for 2′‐dAdo and adenine respectively. Linear calibration curves were obtained within the concentration range 10 nM to 100 μM for both the compounds in 0.1 M phosphate buffer solution (PBS) with the limit of detection 0.8×10^?8 M and 0.95×10^?8 M for 2′‐dAdo and adenine respectively. The analytical utility of the present method is demonstrated by quantitative detection of 2′‐dAdo and adenine in human urine of normal subjects as well as in patients with hepatocellular carcinoma. Interfering effect of some coexisting metabolites has also been reported.