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6CCVD Research

First Screen-Printed Sensor (Electrochemically Activated Screen-Printed Boron-Doped Diamond Electrode) for Quantitative Determination of Rifampicin by Adsorptive Stripping Voltammetry

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2021-07-29
JournalMaterials
AuthorsJędrzej Kozak, Katarzyna Tyszczuk‐Rotko, Magdalena Wójciak, Ireneusz Sowa, Marek Rotko
InstitutionsMedical University of Lublin, Maria Curie-SkƂodowska University
Citations26
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”

This research introduces the first screen-printed boron-doped diamond electrode (SPBDDE) sensor, electrochemically activated (aSPBDDE), for the ultra-trace determination of Rifampicin (RIF) using Differential Pulse Adsorptive Stripping Voltammetry (DPAdSV).

  • Novel Sensor Platform: Successful development and application of the first screen-printed BDDE sensor for RIF quantification, offering a cost-effective and portable analytical solution.
  • Activation Mechanism: Electrochemical activation (CV in 0.1 M NaOH) significantly enhanced sensor performance by increasing surface porosity/roughness (Ra increased from 0.451 ”m to 0.517 ”m) and reducing charge transfer resistance (Rct decreased from 286.5 Ω cm2 to 105.4 Ω cm2).
  • Ultra-Trace Sensitivity: The optimized DPAdSV procedure achieved an exceptionally low Limit of Detection (LOD) of 0.22 pM (0.00000022 ”M), surpassing most existing RIF determination methods.
  • Wide Dynamic Range: Linear RIF quantification was achieved across four distinct concentration ranges, spanning from 0.002 nM up to 20.0 nM.
  • Robust Performance: The sensor demonstrated satisfactory repeatability (RSD 2.5%) and high selectivity against common inorganic and organic interferences (up to 1000-fold excess).
  • Real-World Validation: The method was successfully validated using river water and certified reference bovine urine samples, yielding high recovery rates (91.4% to 98.6%) and strong correlation with reference HPLC/PDA results.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Limit of Detection (LOD)0.22pMRIF determination (DPAdSV)
Limit of Quantification (LOQ)0.73pMRIF determination (DPAdSV)
Charge Transfer Resistance (Rct) - Bare SPBDDE286.5Ω cm2Electrochemical Impedance Spectroscopy (EIS)
Charge Transfer Resistance (Rct) - Activated aSPBDDE105.4Ω cm2Electrochemical Impedance Spectroscopy (EIS)
Active Surface Area (As) - Bare SPBDDE0.0146 ± 0.000510cm2CV measurement (Randles-Sevcik equation)
Surface Roughness (Ra) - Bare SPBDDE0.451”mOptical Profilometry
Surface Roughness (Ra) - Activated aSPBDDE0.517”mOptical Profilometry
RIF Peak Current Repeatability (RSD)2.5%0.1 nM RIF (n=10)
Optimal Accumulation Potential (Eacc)-0.45VDPAdSV optimization
Optimal Accumulation Time (tacc)120sDPAdSV optimization (for analysis speed)
Optimal Amplitude (ΔEA)150mVDPAdSV optimization
Optimal Scan Rate (v)100mV s-1DPAdSV optimization
Optimal Modulation Time (tm)5msDPAdSV optimization
Optimal Supporting Electrolyte0.1M PBS, pH 3.0 ± 0.1RIF determination

Key Methodologies

Section titled “Key Methodologies”
  1. Sensor Platform: Commercial screen-printed boron-doped diamond electrodes (SPBDDE) were used, featuring a BDD working electrode, a carbon auxiliary electrode, and a silver pseudo-reference electrode.
  2. Electrochemical Activation: The SPBDDE was activated using Cyclic Voltammetry (CV) in 0.1 M NaOH solution.
    • Activation Recipe: Five voltammetric cycles were applied between 0 V and 2 V at a scan rate of 100 mV s-1.
  3. Surface Characterization: Scanning Electron Microscopy (SEM) and Optical Profilometry were used to analyze surface morphology, confirming an increase in the number and size of pores post-activation due to the removal of organic binders.
  4. Electrochemical Characterization: CV and Electrochemical Impedance Spectroscopy (EIS) were performed in 0.1 M KCl containing 5.0 mM K3[Fe(CN)6] to measure Rct and active surface area (As).
  5. Analytical Technique: Differential Pulse Adsorptive Stripping Voltammetry (DPAdSV) was selected for RIF quantification due to its high sensitivity.
  6. RIF Oxidation Mechanism: CV studies indicated that RIF oxidation at the aSPBDDE involves quasi-reversible processes, with the overall reaction being controlled by a mixed diffusion/adsorption mechanism (log Ip vs. log v slope of 0.77).
  7. Real Sample Preparation: River water samples were filtered (0.45 ”m). Bovine urine samples and river water were analyzed using the standard addition method, requiring significant dilution (10-fold for river water, 10,000-fold for urine) to minimize matrix interference.

Commercial Applications

Section titled “Commercial Applications”

The development of the highly sensitive, screen-printed BDDE sensor for RIF determination is relevant to several high-value commercial and industrial sectors:

  • Therapeutic Drug Monitoring (TDM): Enables rapid, decentralized monitoring of RIF levels in biological fluids (urine, plasma) for tuberculosis and leprosy patients, ensuring optimal dosing and preventing drug resistance.
  • Point-of-Care (POC) Diagnostics: The screen-printed format facilitates the creation of portable, low-cost electrochemical sensors suitable for field use or resource-limited clinical settings, replacing complex laboratory chromatography.
  • Environmental Water Quality Control: Provides an ultra-sensitive tool for monitoring trace levels of antibiotic residues (like RIF) in wastewater effluent and natural water bodies, addressing pharmaceutical pollution concerns.
  • BDDE Sensor Manufacturing: Validates the use of electrochemical activation as a simple, effective post-processing step to enhance the performance of mass-produced screen-printed BDDEs for various sensing applications.
  • Harsh Environment Sensing: Leveraging the inherent chemical inertness and stability of BDDEs, the sensor platform is suitable for long-term deployment in challenging matrices where traditional carbon electrodes would foul rapidly.
View Original Abstract

In this paper, a screen-printed boron-doped electrode (aSPBDDE) was subjected to electrochemical activation by cyclic voltammetry (CV) in 0.1 M NaOH and the response to rifampicin (RIF) oxidation was used as a testing probe. Changes in surface morphology and electrochemical behaviour of RIF before and after the electrochemical activation of SPBDDE were studied by scanning electron microscopy (SEM), CV and electrochemical impedance spectroscopy (EIS). The increase in number and size of pores in the modifier layer and reduction of charge transfer residence were likely responsible for electrochemical improvement of the analytical signal from RIF at the SPBDDE. Quantitative analysis of RIF by using differential pulse adsorptive stripping voltammetry in 0.1 mol L−1 solution of PBS of pH 3.0 ± 0.1 at the aSPBDDE was carried out. Using optimized conditions (Eacc of −0.45 V, tacc of 120 s, ΔEA of 150 mV, Îœ of 100 mV s−1 and tm of 5 ms), the RIF peak current increased linearly with the concentration in the four ranges: 0.002-0.02, 0.02-0.2, 0.2-2.0, and 2.0-20.0 nM. The limits of detection and quantification were calculated at 0.22 and 0.73 pM. The aSPBDDE showed satisfactory repeatability, reproducibility, and selectivity towards potential interferences. The applicability of the aSPBDDE for control analysis of RIF was demonstrated using river water samples and certified reference material of bovine urine.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2017 - Simultaneous determination of isoniazid and rifampicin by UV spectrophotometry
  2. 2015 - Development of a sensitive and rapid method for rifampicin impurity analysis using supercritical fluid chromatography [Crossref]
  3. 2019 - A validated stable HPLC method for the simultaneous determination of rifampicin and 25-O-desacetyl rifampicin—evaluation of in vitro metabolism [Crossref]
  4. 2015 - Detection of residual rifampicin in urine via fluorescence quenching of gold nanoclusters on paper [Crossref]
  5. 2012 - Quantification of rifampicin in human plasma and cerebrospinal fluid by a highly sensitive and rapid liquid chromatographic-tandem mass spectrometric method [Crossref]
  6. 2011 - LC-MS/MS method for the simultaneous determination of clarithromycin, rifampicin and their main metabolites in horse plasma, epithelial lining fluid and broncho-alveolar cells [Crossref]
  7. 2019 - Fast and simple LC-MS/MS method for rifampicin quantification in human plasma
  8. 2017 - Determination of protein-unbound, active rifampicin in serum by ultrafiltration and ultra performance liquid chromatography with UV detection. A method suitable for standard and high doses of rifampicin [Crossref]
  9. 2021 - Determination of rifampin concentrations by urine colorimetry and mobile phone readout for personalized dosing in tuberculosis treatment [Crossref]
  10. 2005 - Optimization of a cyclodextrin-based sensor for rifampicin monitoring [Crossref]

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