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Copper-Modified Boron-Doped Diamond (Cu/Bdd) Electrode for the Electrochemical Detection of Paclitaxel and Oxaliplatin in Aqueous Solutions

MetadataDetails
Publication Date2020-01-19
JournalRevista de Chimie
AuthorsSorina-Claudia Negrea, Lidia Ani Diaconu, Valeria Nicorescu, Anamaria Baciu, Aniela Pop
InstitutionsPolytechnic University of Timißoara, National Institute for Research and Development for Industrial Ecology
Citations3
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Technical Documentation & Analysis: Copper-Modified BDD for Cytostatic Detection

Section titled “Technical Documentation & Analysis: Copper-Modified BDD for Cytostatic Detection”

This documentation analyzes the research demonstrating the successful use of a Copper-Modified Boron-Doped Diamond (Cu/BDD) electrode for the sensitive electrochemical detection of two critical cytostatic drugs, Paclitaxel (PCX) and Oxaliplatin (OXA), in aqueous solutions.

  • Core Achievement: Development of a simple, fast, and highly sensitive electrochemical method for monitoring emerging pharmaceutical pollutants (PCX and OXA).
  • Material Modification: Commercial Boron-Doped Diamond (BDD) electrodes were electrochemically modified with copper (Cu) via Chronoamperometry (CA).
  • Optimization: Optimal Cu electrodeposition parameters were determined to be -0.75 V/SCE for 120 seconds, resulting in a uniform distribution of small Cu particles on the BDD surface (confirmed by SEM).
  • Performance Improvement: The Cu modification was critical; bare BDD showed no detectable signal for the cytostatics, while Cu/BDD exhibited clear anodic oxidation peaks.
  • High Sensitivity: Excellent sensitivity was achieved for PCX (5.47 ”A/”M) and OXA (0.65 ”A/”M) using Cyclic Voltammetry (CV).
  • Application Potential: The modified Cu/BDD electrode exhibits strong potential for developing robust electroanalytical methods for environmental monitoring and dosage control of cytostatic drugs.

The following table summarizes the key electrochemical and analytical parameters achieved using the Cu/BDD electrode.

ParameterValueUnitContext
BDD Boron Content (Commercial)~0.1-Used for electroanalytic modification
Optimal Cu Deposition Potential-0.75V/SCEDetermined via Chronoamperometry (CA)
Optimal Cu Deposition Time120secondsDetermined via Chronoamperometry (CA)
Supporting Electrolyte0.1 M NaOH-Used for all detection studies
Oxaliplatin Oxidation Potential (CV)+0.6V/SCELimiting anodic current observed
Paclitaxel Oxidation Potential (CV)+0.75V/SCELimiting anodic current observed
Paclitaxel Sensitivity (CV)5.47”A/”MHighest sensitivity achieved
Oxaliplatin Sensitivity (CV)0.65”A/”MAchieved using CV
Paclitaxel LOD (CV)0.05”MLimit of Detection
Paclitaxel LOD (CA)1.60”MLimit of Detection (Chronoamperometry)
Paclitaxel Correlation Coefficient (CA)0.994RExcellent linearity for Chronoamperometry

The experimental procedure focused on optimizing the electrochemical modification of the BDD surface to maximize the electrocatalytic effect.

  1. Electrochemical Setup: A standard three-electrode cell was employed, using a Saturated Calomel Electrode (SCE) as the reference, Platinum (Pt) as the counter electrode, and the BDD or Cu/BDD as the working electrode.
  2. BDD Pre-treatment: The commercial BDD electrode was stabilized by performing 10 repetitive Cyclic Voltammograms (CV) in 0.1 M NaOH across the potential range of -1 V to +1 V/SCE.
  3. Copper Modification (Electrodeposition): Copper particles were deposited onto the BDD surface using Chronoamperometry (CA) from a 0.05 M copper sulphate solution.
  4. Deposition Potential Optimization: The deposition potential was varied from -0.15 V to -1.2 V/SCE. The optimal potential was determined to be -0.75 V/SCE, yielding the best electroanalytical signal for Oxaliplatin.
  5. Deposition Time Optimization: The deposition time was varied from 30 s to 150 s at the optimal potential (-0.75 V/SCE). The optimal time was determined to be 120 s.
  6. Characterization: Scanning Electron Microscopy (SEM) was used to confirm the morpho-structural characteristics, showing small, well-distributed Cu particles on the BDD surface.
  7. Detection Techniques: Cyclic Voltammetry (CV) and Chronoamperometry (CA) were used to determine the sensitivity and limits of detection (LOD/LOQ) for PCX and OXA in 0.1 M NaOH.

This research highlights the critical role of high-quality Boron-Doped Diamond (BDD) substrates in advanced electrochemical sensing. 6CCVD is uniquely positioned to supply and customize the materials required to replicate, scale, and extend this research into commercial applications.

To achieve the high conductivity and stability required for sensitive cytostatic detection, 6CCVD recommends the following materials:

  • Heavy Boron-Doped Polycrystalline Diamond (PCD): Ideal for large-scale electrochemical applications. Our MPCVD process allows for precise control over boron doping levels (up to 1021 atoms/cm3) and crystal quality, ensuring superior electrochemical stability and low background current compared to commercial alternatives.
  • Boron-Doped Single Crystal Diamond (SCD): Recommended for high-precision, low-noise applications where ultra-low defect density is paramount. We offer SCD with controlled boron incorporation for specific conductivity targets.

The success of the Cu/BDD electrode relies on the quality of the substrate and the subsequent modification. 6CCVD offers comprehensive services to optimize the working electrode:

Research Requirement6CCVD Customization ServiceTechnical Capability
Custom DimensionsSupply of BDD plates/wafers cut to exact specifications for integration into flow cells or sensor arrays.Plates/wafers up to 125mm (PCD). Substrate thickness up to 10mm.
Surface PreparationUltra-smooth polishing to minimize surface defects and maximize the uniformity of subsequent metal deposition, reducing potential fouling.Polishing to Ra < 5nm (PCD) or Ra < 1nm (SCD).
Metalization PrecursorsWhile the paper used electrochemical Cu deposition, 6CCVD can apply high-adhesion precursor layers (e.g., Ti/Pt/Au) via sputtering or e-beam evaporation to ensure robust, uniform metal contact points for external wiring or subsequent modification.Internal capability for high-purity Au, Pt, Pd, Ti, W, and Cu metalization layers.
Thickness ControlPrecise control over the BDD layer thickness, ranging from thin films for high-speed sensing to thick substrates for mechanical robustness.SCD/PCD thickness control from 0.1 ”m up to 500 ”m.

6CCVD’s in-house PhD team specializes in optimizing diamond material properties for advanced electrochemical applications. We offer consultation services to assist researchers and engineers in:

  • Doping Optimization: Tailoring the boron concentration and uniformity to achieve specific conductivity targets for enhanced electron transfer kinetics.
  • Surface Termination: Advising on optimal surface termination (e.g., hydrogen or oxygen) prior to metal modification to improve adhesion and electrocatalytic performance.
  • Application Scaling: Assisting with material selection and design for scaling up cytostatic detection projects from lab-bench CV experiments to automated, in-field Chronoamperometry systems.

For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

The aim of this study was to obtain a simple and fast modified electrode for the detection of paclitaxel (PCX) and oxaliplatin (OXA) in aqueous solution. PCX and OXA are some of the most used cytostatic drugs suitable to treat various types of cancer, e.g., ovarian, breast, lung, cervical, pancreatic, Kaposi’s sarcoma. The development of an easy method for its determination is required for both the dosage in cancer therapy and due its potential presence in environment and especially, in water samples. Boron doped diamond (BDD) electrode was electrochemically modified with copper (Cu) by chronoamperometry (CA) operated under optimized conditions of -0.75 V/SCE potential level for 120 minutes. Copper-modified boron-doped diamond (Cu/BDD) exhibited the electrocatalytic effect towards the paclitaxel and oxaliplatin oxidation, allowing their detection in 0.1 M NaOH supporting electrolyte. The limiting anodic current was noticed at the potential value of +0.75 V/SCE that increased linearly with PCX concentration, and at the potential value of + 0.6V/SCE for the oxaliplatin. Some mechanical aspects related to the PCX oxidation at Cu/BDD electrode in 0.1 M NaOH supporting electrolyte were determined using cyclic voltammetry (CV) recorded at various scan rates. CV was based on compounds detection and achieved the sensitivity of 0.65 ÎŒA/”M for oxaliplatin and respective, 5.47 ÎŒA/”M for paclitaxel. Keywords: copper, electrochemical detection, modified boron-doped diamond electrode paclitaxel, oxaliplatin