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Electrochemical determination of resveratrol in dietary supplements at a boron-doped diamond electrode in the presence of hexadecyltrimethylammonium bromide using square-wave adsorptive stripping voltammetry

MetadataDetails
Publication Date2016-10-05
JournalJournal of the Serbian Chemical Society
AuthorsYavuz Yardım
InstitutionsVan YĂŒzĂŒncĂŒ Yıl Üniversitesi
Citations14
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Technical Analysis & Documentation: MPCVD Boron-Doped Diamond for Ultra-Sensitive Resveratrol Determination

Section titled “Technical Analysis & Documentation: MPCVD Boron-Doped Diamond for Ultra-Sensitive Resveratrol Determination”

This research validates the use of a bare Boron-Doped Diamond (BDD) electrode combined with Square-Wave Adsorptive Stripping Voltammetry (SW-AdSV) for the highly sensitive and rapid determination of Resveratrol (RES) in commercial supplements. This technique demonstrates the exceptional utility of MPCVD BDD for demanding electroanalytical applications.

  • High Sensitivity: Achieved an ultra-low Limit of Detection (LOD) of 0.0063 ”g mL-1 (2.76 x 10-8 mol L-1), surpassing the sensitivity of many traditional carbon and metallic electrodes.
  • Material Validation: Confirms BDD’s superior chemical stability and wide potential window in aggressive media (0.1 M HNO3), preventing electrode fouling common in organic analysis.
  • Adsorption Control: The electrochemical oxidation of RES is adsorption-controlled, requiring routine cathodic pre-treatment (-1.5 V for 60-180 s) to maintain the BDD surface activity and maximize signal output.
  • Surfactant Enhancement: The cationic surfactant HTAB (100 ”mol L-1) acts as a co-adsorbing agent, increasing the RES oxidation peak current by approximately 2.46 times.
  • Applicability & Accuracy: The method is verified for analyzing RES in complex matrices (dietary supplements), demonstrating high accuracy (recovery range 93.1% to 97.4%) and repeatability (RSD of 2.39%).
  • 6CCVD Value: The robust performance is directly attributable to the high-quality, MPCVD-grown BDD material, a core specialty of 6CCVD.

Extraction of key performance parameters and physical data derived from the SW-AdSV analysis.

ParameterValueUnitContext
Electrode MaterialBoron-Doped Diamond (BDD)N/ABare, Polycrystalline
Electrode Diameter3.0mmWorking electrode size used
Limit of Detection (LOD)0.0063”g mL-1Equivalently: 2.76 x 10-8 mol L-1
Limit of Quantification (LOQ)0.021”g mL-1Equivalently: 9.19 x 10-8 mol L-1
Working Linear Range0.025 to 60.0”g mL-1Total linear calibration curve range
Optimal Electrolyte0.1 M Nitric Acid (HNO3)MChosen for high peak current and shape
Surfactant Doping100”mol L-1Hexadecyl Trimethyl Ammonium Bromide (HTAB)
Optimal Peak Potential (Ep)0.74Vvs. Ag/AgCl reference electrode
Accumulation Time (tacc)60sOptimized period at open-circuit condition
SWV Frequency (f)50HzChosen to minimize noise while maximizing signal
SWV Pulse Amplitude (a)40mVOptimized for peak sharpness
Repeatability (RSD)2.39%Relative Standard Deviation (8 replicates)
pH Dependency Slope (Ep vs. pH)-58.0mV/pHDemonstrates equal electron/proton transfer

The following recipe parameters and procedures were critical for achieving the reported high performance using the BDD electrode:

  1. Electrode Preparation: A bare BDD electrode (3.0 mm diameter) was used, requiring daily pre-treatment to restore initial activity due to the adsorption-controlled nature of the RES oxidation.
  2. BDD Cathodic Pre-treatment (Primary): Polarization in 0.5 M H2SO4 at -1.5 V (cathodic) for an extended duration of 180 s before the start of daily experiments.
  3. BDD Cathodic Pre-treatment (Routine): Application of a shorter 60 s polarization at -1.5 V before each voltammetric experiment to prevent surface fouling.
  4. Electrolyte Composition: The optimal supporting medium was determined to be 0.1 M HNO3 containing 100 ”mol L-1 of the cationic surfactant HTAB.
  5. Adsorptive Stripping Procedure: The accumulation step involved stirring the solution (500 rpm) while applying the pre-concentration potential (optimized as open-circuit condition) for 60 s.
  6. SWV Parameters: The anodic scan (0.0 V to 1.0 V) was performed using optimized parameters: frequency (50 Hz), scan increment (12 mV), and pulse amplitude (40 mV).

This research confirms that Boron-Doped Diamond (BDD) is the optimal material for sensitive and reproducible voltammetric analysis of complex organic molecules like Resveratrol. 6CCVD, as an expert MPCVD diamond manufacturer, is uniquely positioned to supply and customize the BDD required to replicate or scale this revolutionary analytical technique.

Requirement from Paper6CCVD Capability & SolutionValue Proposition for Engineers
Material: Electroactive BDD (Polycrystalline)Heavy Boron-Doped PCD Wafers/Plates. We provide electrochemical-grade BDD fabricated via MPCVD, offering uniform boron incorporation and high graphitic purity necessary for low background current and maximum sensitivity.Guaranteed quality and superior performance for demanding electroanalysis, ensuring low noise and ultra-wide potential range stability in aggressive solvents.
Dimensions: Standard 3.0 mm electrode diskCustom Dimensions up to 125mm (PCD). We supply wafers and plates significantly larger than required, or offer custom laser cutting services to produce complex geometries and micro-electrode arrays.Supports pilot production scale-up and high-throughput sensor design, moving research & development towards commercial application.
Surface Quality: Requires repeatable surface preparation (Ra < 5nm for PCD)Precision Polishing Services. Our in-house polishing achieves roughness metrics of Ra < 5nm on inch-size PCD material, minimizing surface defects that can cause fouling or irreproducibility.Reduces the need for aggressive, time-consuming pre-treatment protocols, improving electrode lifespan and measurement repeatability (RSD).
System Integration: Requires electrical contactsIn-House Metalization Expertise. We offer custom deposition of common electrode contacts (e.g., Ti/Pt/Au, W/Au, etc.) directly onto the BDD surface, tailored for specific electrochemical cell requirements.Simplifies device fabrication, ensuring robust electrical integration and reliable long-term sensor operation.

To replicate and extend this research on trace organic analysis using voltammetry, 6CCVD recommends Heavy Boron-Doped Polycrystalline Diamond (BDD PCD). This material grade provides the highest conductivity and stability required for SW-AdSV techniques in strong acidic media (0.1 M HNO3).

The utilization of BDD electrodes in this study highlights the need for precise geometry control. 6CCVD offers:

  • Custom Wafer Sizes: BDD plates up to 125 mm diameter, allowing for the creation of multiple electrodes from a single source.
  • Laser Cutting: Precise cutting and shaping services for creating micro-arrays or custom tip electrodes for specialized sensing devices.

6CCVD’s in-house PhD material science and engineering team can assist clients with material selection and design consultation for similar analytical projects, including trace analysis of pharmaceuticals, food contaminants, or biological redox compounds utilizing advanced diamond electrochemistry.


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

View Original Abstract

A sensitive electroanalytical methodology for the determination of resveratrol is presented for the first time using adsorptive stripping voltammetry at a bare boron-doped diamond (BDD) electrode. In cyclic voltammetry, resveratrol shows one irreversible and an adsorption-controlled oxidation peak at a BDD electrode. The voltammetric results indicated that in the presence of hexadecyl trimethyl ammonium bromide, the BDD electrode remarkably enhanced the oxidation of resveratrol, which leads to an improvement in the peak current with a shift of the peak potential to more positive values. Using the square-wave stripping mode, the compound yielded a well-defined voltammetric response in 0.1 M nitric acid solution containing 100 ?mol L-1 hexadecyl trimethyl ammonium bromide at 0.74 V (vs. Ag/AgCl), after 60 s accumulation at the open-circuit condition. A linear calibration graph was obtained in the concentration range 0.025 to 60.0 ?g mL-1, with a detection limit of 0.0063 ?g mL-1. The applicability of the proposed method was verified by analysis of resveratrol in commercial dietary supplements.