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6CCVD Research

Voltammetric Sensor Based on Molecularly Imprinted Chitosan-Carbon Nanotubes Decorated with Gold Nanoparticles Nanocomposite Deposited on Boron-Doped Diamond Electrodes for Catechol Detection

At a Glance

Section titled “At a Glance”
MetadataDetails
Publication Date2020-02-04
JournalMaterials
AuthorsCoral Salvo‐Comino, Ilhem Rassas, Sylvain Minot, François Bessueille, Madjid Arab
InstitutionsCentre National de la Recherche Scientifique, Université Claude Bernard Lyon 1
Citations38
AnalysisFull AI Review Included

Executive Summary

Section titled “Executive Summary”

This research details the development and characterization of a highly sensitive, biocompatible voltammetric sensor for catechol detection, leveraging advanced nanomaterials and molecular imprinting technology on a robust electrode platform.

  • Core Innovation: A Molecularly Imprinted Polymer (MIP) sensor film composed of Chitosan (CS) encapsulating Gold Nanoparticle (AuNP)-decorated Multi-Walled Carbon Nanotubes (MWCNT) was deposited onto a Boron-Doped Diamond (BDD) electrode.
  • Performance Metrics: The sensor achieved a low Limit of Detection (LOD) of 3.68 x 10-5 M and demonstrated a wide linear dynamic range for catechol detection (75 ”M to 1 mM).
  • Material Synergy: The MWCNT/AuNP nanocomposite significantly improved electron transfer kinetics and electrocatalytic behavior, enhancing the overall sensitivity (339.05 ”A mM-1 cm-2).
  • Selectivity and Stability: Excellent selectivity was confirmed by an MIP/NIP sensitivity ratio of 2.2. The sensor showed high reproducibility (RSD 4.5%) and robustness for multiple uses (repeatability RSD 10.8%).
  • Electrode Platform: The BDD electrode provided exceptional chemical stability and a large potential window, making it ideal for the non-enzymatic electrochemical detection of phenols.
  • Real-World Application: The sensor successfully quantified catechol in a complex matrix, determining a concentration of 170 ”M in a diluted red wine sample.

Technical Specifications

Section titled “Technical Specifications”
ParameterValueUnitContext
Limit of Detection (LOD)3.68 x 10-5MMIP CS-MWCNT/AuNP/BDD Sensor
Sensitivity (MIP)339.05”A mM-1 cm-2Voltammetry, Catechol detection
Dynamic Range (Catechol)75 to 1000”MLinear range of detection
MIP/NIP Sensitivity Ratio2.2N/AMeasure of imprinting efficiency
Reproducibility (RSD)4.5%Three independently prepared MIP sensors
Repeatability (RSD)10.8%Single MIP sensor, reused three times
Scan Rate (CV)100mV/sElectrochemical measurement condition
Potential Range (CV)-800 to 1500mVCatechol oxidation/quinone reduction
BDD Film Thickness300nmPolycrystalline film on Si substrate
BDD Boron Concentration>7000 to 8000ppmHighly doped
AuNP Diameter~40nmDecorated on MWCNT (TEM analysis)
CS Concentration (MIP Prep)1.5mg/mLChitosan solution concentration
BDD Cleaning SolutionH2SO4:H2O2 = 3:1v/v proportionPiranha solution pretreatment

Key Methodologies

Section titled “Key Methodologies”

The sensor fabrication involved the synthesis of the nanocomposite, BDD pretreatment, and molecularly imprinted film deposition via drop-casting.

  1. MWCNT/AuNP Composite Synthesis:

    • Spherical AuNPs were prepared using the Turkevitch/Frens method.
    • MWCNTs (prepared by Catalytic Chemical Vapor Deposition, CCVD) were decorated by dispersing 50 mg MWCNT in 15 mL ethanol, adding 0.5 mL of the CNT suspension to 5.0 mL aqueous gold colloid, and ultrasonication (10 min).

  2. CS-MWCNT/AuNP Solution Preparation:

    • 5 mg of the CNT/AuNP composite was dispersed in 10 mL of Chitosan (CS) solution (5 mg in 10 mL of 1% vol. acetic acid).
    • The pH was adjusted to 9 using ammonia solution.

  3. Cross-Linking and Purification:

    • 7.2 ”L of 25% vol. glutaraldehyde was added for cross-linking.
    • The suspension was heated for 1 hour, centrifuged at 8000 rpm for 20 min, and washed with 1% vol. acetic acid.

  4. BDD Electrode Pretreatment:

    • BDD electrodes were ultrasonicated in acetone (10 min) and washed with Milli Q water.
    • Electrodes were cleaned in Piranha solution (H2SO4:H2O2 = 3:1 v/v) for 5 min, followed by washing and drying under nitrogen flow.

  5. MIP Film Deposition:

    • The CS-MWCNT/AuNP solution (containing 0.1 M catechol template) was drop-cast onto the pretreated BDD electrode surface.
    • The film was dried at room temperature for 3 days.

  6. Template Elution:

    • The catechol template molecule was removed by stirring the modified electrode in 0.1 M KCl solution for 20 min to create specific recognition cavities.

Commercial Applications

Section titled “Commercial Applications”

This technology is highly relevant to industries requiring sensitive, stable, and rapid electrochemical detection, particularly utilizing advanced carbon and diamond materials.

  • Food and Beverage Safety/Quality:
    • Rapid, portable sensing devices for quality control and authentication in the wine industry (quantifying phenolic compounds like catechol).
    • Monitoring antioxidant levels in functional foods and beverages.
  • Environmental Analysis:
    • Development of robust, reusable sensors for detecting trace levels of phenolic pollutants (e.g., bisphenol A, nitrophenols) in industrial wastewater and drinking water sources.
  • Biomedical Diagnostics:
    • Creation of biocompatible electrochemical platforms for detecting biomarkers or antioxidants in complex biological fluids, leveraging the non-toxic nature of chitosan and BDD.
  • Advanced Electrode Manufacturing:
    • Utilization of highly stable, chemically inert Boron-Doped Diamond (BDD) electrodes (grown via MPECVD, as mentioned in the text) for applications requiring extreme potential windows or resistance to fouling.
  • Nanomaterial Synthesis and Integration:
    • Commercialization of functionalized carbon nanotubes (MWCNT/AuNP) as high-performance conductive fillers and electrocatalysts for next-generation sensor and energy storage devices.
View Original Abstract

Phenolic compounds such as catechol are present in a wide variety of foods and beverages; they are of great importance due to their antioxidant properties. This research presents the development of a sensitive and biocompatible molecular imprinted sensor for the electrochemical detection of catechol, based on natural biopolymer-electroactive nanocomposites. Gold nanoparticle (AuNP)-decorated multiwalled carbon nanotubes (MWCNT) have been encapsulated in a polymeric chitosan (CS) matrix. This chitosan nanocomposite has been used to develop a molecular imprinted polymers (MIP) in the presence of catechol on a boron-doped diamond (BDD) electrode. The structure of the decorated MWCNT has been studied by TEM, whereas the characterization of the sensor surface has been imaged by AFM, demonstrating the satisfactory adsorption of the film and the adequate coverage of the decorated carbon nanotubes on the electrode surface. The electrochemical response of the sensor has been analyzed by cyclic voltammetry (CV) where excellent reproducibility and repeatability to catechol detection in the range of 0 to 1 mM has been found, with a detection limit of 3.7 × 10−5 M. Finally, the developed sensor was used to detect catechol in a real wine sample.

Tech Support

Section titled “Tech Support”

Original Source

Section titled “Original Source”

References

Section titled “References”
  1. 2017 - Electrochemical Sensor for Detection of Polyphenols in Tea and Wine with Differential Pulse Voltammetry and Electrochemical Impedance Spectroscopy Utilizing Tyrosinase and Gold Nanoparticles Decorated Biomembrane [Crossref]
  2. 2010 - The use of cyclic voltammetry for wine analysis: Determination of polyphenols and free sulfur dioxide [Crossref]
  3. 2003 - Determination of major phenolic compounds in water by reversed-phase liquid chromatography after pre-column derivatization with benzoyl chloride [Crossref]
  4. 2006 - Determination of totalcontent of phenolic compounds and their antioxidantactivity in vegetables-evaluation of spectrophotometricmethods [Crossref]
  5. 2017 - Selective, sensitive and reliable colorimetric sensor for catechol detection based on anti-aggregation of unmodified gold nanoparticles utilizing boronic acid-diol reaction: optimization by experimental design methodology [Crossref]
  6. 2018 - Ionic liquid-based headspace in-tube liquid-phase microextraction coupled with CE for sensitive detection of phenols [Crossref]
  7. 2010 - Amperometric biosensor based on a high resolution photopolymer deposited onto a screen-printed electrode for phenolic compounds monitoring in tea infusions [Crossref]
  8. 2012 - Multisensor system based on bisphthalocyanine nanowires for the detection of antioxidants [Crossref]
  9. 2001 - A Cyclic Voltammetry Method Suitable for Characterizing Antioxidant Properties of Wine and Wine Phenolics [Crossref]
  10. 2012 - Study on the polyfurfural film modified glassy carbon electrode and its application in polyphenols determination [Crossref]

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