Determination of naproxen by using differential pulse voltammetry with poly (aniline-2-sulfonic acid) modified boron doped diamond electrode
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2022-06-30 |
| Journal | Macedonian Journal of Chemistry and Chemical Engineering |
| Authors | Ăznur GĂŒngör |
| Institutions | Inonu University |
| Citations | 2 |
| Analysis | Full AI Review Included |
Executive Summary
Section titled âExecutive SummaryâThis research details the successful development and characterization of a highly selective electrochemical sensor for Naproxen (NAP) detection, utilizing a Boron Doped Diamond Electrode (BDDE) modified with poly(aniline-2-sulfonic acid) (p(A2SA)).
- Core Achievement: A novel p(A2SA)/BDDE sensor was fabricated via electropolymerization, demonstrating high sensitivity for NAP determination using Differential Pulse Voltammetry (DPV).
- Performance Metrics: The sensor achieved a wide linear detection range (0.05-1.00 mM NAP) with excellent linearity (R2 = 0.9944).
- Sensitivity: The calculated Detection Limit (DL) was 0.0328 mM, confirming suitability for low-concentration analysis.
- Stability and Precision: High stability was demonstrated with a low Relative Standard Deviation (%RSD) of 2.71% across multiple electrodes (n=10).
- Clinical Relevance: The method was successfully validated in synthetic urine samples, yielding high recovery rates (99.15% to 100.18%), proving its applicability in biomedical and clinical settings.
- Mechanism: The p(A2SA) film, optimized to a thickness corresponding to four polymerization cycles, increases the electrode surface area (AFM roughness ~30 nm) and enhances electrocatalytic activity for NAP oxidation (peak observed at ~1.1 V).
Technical Specifications
Section titled âTechnical Specificationsâ| Parameter | Value | Unit | Context |
|---|---|---|---|
| Working Electrode | p(A2SA)/BDDE | N/A | Modified Boron Doped Diamond |
| Optimum Monomer Conc. | 8 | mM | Aniline-2-sulfonic acid (A2SA) |
| Optimum Film Thickness | 4 | Cycles | Electropolymerization cycles (CV) |
| Polymerization Scan Rate | 100 | mV/s | CV during film deposition |
| Analytical Technique | DPV | N/A | Naproxen detection |
| Optimum Analytical Scan Rate | 125 | mV/s | DPV measurement |
| Oxidation Peak Potential (NAP) | ~1.1 | V | Measured in 0.1 M PB (pH 8.00) |
| Linear Range (NAP) | 0.05-1.00 | mM | Concentration range |
| Correlation Coefficient (R2) | 0.9944 | N/A | Calibration curve linearity |
| Detection Limit (DL) | 0.0328 | mM | Calculated (3 s/m) |
| Quantification Limit (QL) | 0.1093 | mM | Calculated (10 s/m) |
| Reproducibility (%RSD) | 2.71 | % | For 0.50 mM NAP (n=10 electrodes) |
| Surface Roughness (AFM) | ~30 | nm | Roughness of p(A2SA) film |
Key Methodologies
Section titled âKey MethodologiesâThe electrochemical sensor was constructed and characterized using the following optimized procedures:
- Electrode Preparation: A bare Boron Doped Diamond Electrode (BDDE) was used as the substrate.
- Monomer Solution: The monomer, Aniline-2-sulfonic acid (A2SA), was prepared at an optimal concentration of 8 mM in a water/acetonitrile (1:1) mixture containing 0.1 M sodium perchlorate (NaClO4).
- Electropolymerization (Film Formation): The p(A2SA) film was deposited onto the BDDE surface using Cyclic Voltammetry (CV) over four cycles. The polymerization scan rate was optimized at 100 mV/s.
- Electrocatalytic Characterization: The modified electrode was characterized using CV in 6 mM K3[Fe(CN)6] solution to confirm satisfactory electrocatalytic activity, despite a slight increase in anodic-cathodic peak separation compared to the bare BDDE.
- Analytical Optimization (Electrolyte): Phosphate Buffer (PB) was selected as the optimal electrolyte (0.1 M). The pH was optimized to 8.00, yielding maximum DPV peak current response for NAP.
- NAP Detection (DPV): Differential Pulse Voltammetry (DPV) was performed using optimized parameters: potential step 10 mV, pulse amplitude 10 mV, and an analytical scan rate of 125 mV/s.
- Validation: The sensorâs applicability was confirmed by spiking synthetic urine samples with known NAP concentrations and measuring recovery via DPV.
Commercial Applications
Section titled âCommercial ApplicationsâThe use of Boron Doped Diamond Electrodes (BDDE) modified with conductive polymers is highly relevant across several high-value engineering and clinical sectors:
- Pharmaceutical Quality Control (QC): Rapid, accurate, and cost-effective determination of Naproxen concentration in drug formulations, replacing slower, solvent-intensive methods like HPLC.
- Clinical Diagnostics and Therapeutic Drug Monitoring (TDM): Real-time monitoring of NAP levels in biological fluids (e.g., urine, plasma) for overdose prevention and personalized medicine, leveraging the sensorâs high stability and low detection limits.
- Environmental Monitoring: Detection of pharmaceutical residues (like NAP) in wastewater treatment effluents and natural water sources, utilizing the robustness and chemical inertness of the BDDE platform.
- Advanced Electrochemical Sensor Development: BDDE substrates provide superior stability, low background current, and wide potential windows, making them ideal for developing next-generation sensors for complex organic molecules.
- Electrocatalysis: The p(A2SA) modification demonstrates enhanced surface area and tailored electrocatalytic properties, applicable in areas requiring selective oxidation or reduction processes.
View Original Abstract
In this study, an electrochemical sensor based on a boron doped diamond electrode (BDDE) was developed for the determination of naproxen (NAP) using a poly(aniline-2-sulfonic acid)/boron doped diamond electrode, p(A2SA/BDDE). Polymerization of A2SA was conducted in a water/acetonitrile (1:1) mixture containing 0.1 M sodium perchlorate (NaClO4) on bare BDDE and the electrochemical properties studied by cyclic voltammetry in ferricyanide/KNO3 solution. The prepared p(A2SA/BDDE) was used for detection of NAP. Effects of parameters such as monomer type and concentration, the number of cycles, and scan rate were investigated using differential pulse voltammetry (DPV) in phosphate buffer containing 0.75 mM NAP. The effect of electrolyte type and pH on DPV responses to NAP were also studied. The oxidative current peak stem from NAP concentration observed at 1.1 V potential. A linear calibration curve was obtained in the range of 0.05-1.00 mM NAP concentration. Correlation coefficient (R2), detection limit, and quantification limit were calculated as 0.9944, 0.0328 mM, and 0.1093 mM, respectively. In conclusion, it may be claimed that the modified electrode constructed in this work can be used successfully as a naproxen-selective membrane due to its ease of preparation, high R2 value, and good reproducibility.