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Electrochemical Sensor of Levofloxacin on Boron-Doped Diamond Electrode Decorated by Nickel Nanoparticles

MetadataDetails
Publication Date2022-08-10
JournalIndonesian Journal of Chemistry
AuthorsPrastika Krisma Jiwanti, Irfansyah Rais Sitorus, Grandprix T.M. Kadja, Siti Wafiroh, Yasuaki Einaga
InstitutionsKeio University, Airlangga University
Citations12
AnalysisFull AI Review Included
  • Advanced Sensor Platform: A highly stable and sensitive electrochemical sensor was developed using Nickel Nanoparticles (Ni NPs) decorated on a Boron-Doped Diamond (BDD) electrode (NiBDD) for the detection of Levofloxacin (LEV).
  • Enhanced Catalytic Activity: The Ni NPs successfully deposited (1% Ni content) acted as a catalyst, significantly enhancing the oxidation signal of LEV compared to the unmodified BDD electrode.
  • Optimal Detection Method: Square Wave Voltammetry (SWV) was optimized and selected, achieving a 56% reduction in the Limit of Detection (LOD) compared to Linear Sweep Voltammetry (LSV).
  • High Sensitivity and Range: The sensor demonstrated a linear response in the range of 30-100 ”M LEV, achieving a low LOD of 11.13 ”M and a high sensitivity of 0.9111 ”A/”M (R2 = 0.9958).
  • Robust Performance: The NiBDD electrode showed excellent long-term stability with a low relative standard deviation (RSD) of 1.45% over 10 days of measurement.
  • Real-World Applicability: The method proved selective against common interferences (urea, glucose, ascorbic acid) and yielded a high recovery rate (93.91 ± 0.02%) when tested in human urine samples.
  • Mechanism: The electrochemical oxidation of LEV on the NiBDD surface was determined to be a diffusion-controlled process.
ParameterValueUnitContext
BDD Doping Level1% (B/C)Boron concentration during CVD synthesis
Working Electrode Area0.04cm2Geometric area of the NiBDD electrode
Ni Nanoparticle Content1%Surface concentration (determined by EDS)
Optimal Detection MethodSWVN/ASquare Wave Voltammetry
Optimal pH5.5N/ASupporting electrolyte (0.1 M Na2SO4)
Linear Detection Range30-100”MLevofloxacin concentration
Limit of Detection (LOD)11.13”MCalculated using the SWV method
Sensitivity (SWV)0.9111”A/”MSlope of the linear calibration curve
Reproducibility (RSD)1.45%Measured over 10 consecutive days (n=10)
Real Sample Recovery93.91 ± 0.02%Accuracy in human urine sample analysis
LEV Oxidation Peak Potential+1.0 and +1.1Vvs. Ag/AgCl reference electrode
Optimal Pulse Amplitude50mVSWV optimization parameter
Optimal Frequency50HzSWV optimization parameter
Optimal Step Potential12mVSWV optimization parameter
  1. BDD Film Synthesis: 1% (B/C) BDD electrode was deposited onto a Si (111) substrate using a Microwave Plasma-Assisted Chemical Vapor Deposition (MPCVD) system.
  2. Oxygen Termination (OBDD Preparation): The BDD surface was anodically oxidized in 0.1 M H2SO4 to convert hydrogen functional groups to oxygen functional groups (OBDD). This involved 40 cycles of Cyclic Voltammetry (CV) between -2.5 V and 2.5 V (1 V/s scan rate), followed by Chronoamperometry at 2.5 V for 300 s.
  3. Nickel Nanoparticle Decoration (NiBDD): Ni NPs were electrochemically deposited onto the OBDD surface using Chronoamperometry. The deposition was performed in 1 M NiSO4 solution at a potential of -1.2 V for 250 s.
  4. Material Characterization: The surface topography and elemental composition of the NiBDD electrode were confirmed using Scanning Electron Microscopy-Energy Dispersive Spectroscopy (SEM-EDS).
  5. Electrochemical Measurement: All measurements were conducted in a three-electrode cell using 0.1 M Na2SO4 as the supporting electrolyte. The working electrode was NiBDD, the counter electrode was Pt spiral, and the reference electrode was Ag/AgCl (saturated KCl).
  6. SWV Optimization: The analytical method was optimized for maximum current response and sensitivity, setting the pulse amplitude to 50 mV, frequency to 50 Hz, and step potential to 12 mV.
  7. pH Optimization: The optimal pH for LEV oxidation was determined to be pH 5.5, maximizing the anodic current response.
  • Pharmaceutical Quality Control: Rapid and accurate quantification of Levofloxacin in pharmaceutical formulations, ensuring product quality and compliance with regulatory standards.
  • Clinical Diagnostics and Therapeutic Drug Monitoring (TDM): Development of fast, portable electrochemical devices for monitoring LEV levels in biological fluids (urine, blood) to prevent toxicity, manage dosage, and mitigate the risk of bacterial resistance.
  • Environmental Monitoring and Water Quality: Deployment of NiBDD sensors for the detection and quantification of antibiotic residues (fluoroquinolones) in industrial wastewater and environmental samples, addressing pharmaceutical pollution.
  • Advanced Sensor Manufacturing: Production of highly stable, chemically inert, and sensitive BDD-based electrodes modified with transition metals (Ni, Cu, Pd) for a wide range of electroanalytical applications beyond LEV, including COD and glucose sensing.
  • Field-Deployable Analytical Systems: Integration of the optimized SWV method and NiBDD electrode into low-cost, portable potentiostats for on-site, real-time analysis of pollutants and drugs, reducing reliance on expensive, centralized laboratory instrumentation (e.g., HPLC).
View Original Abstract

Levofloxacin (LEV) was known as one of the fluoroquinolone antibiotics that widely used as an antibacterial agent. Monitoring of LEV is important due to its negative side effect on humans. The determination of LEV was studied for the first time on nickel modified on a boron-doped diamond (NiBDD) electrode using the square wave voltammetry (SWV) method to improve the catalytic and sensitivity of the sensor. The response was linear in the range of 30-100 mM LEV. LEV sensor on NiBDD was found to be selective in the presence of urea, glucose, and ascorbic acid interferences. Good reproducibility with % a relative standard deviation of 1.45% (n = 10) was achieved. Therefore, the NiBDD electrode could be potentially applied for the real detection method of LEV.