Electrooxidation of trifloxystrobin at the boron-doped diamond electrode - electrochemical mechanism, quantitative determination and degradation studies
At a Glance
Section titled âAt a Glanceâ| Metadata | Details |
|---|---|
| Publication Date | 2016-08-08 |
| Journal | International Journal of Environmental & Analytical Chemistry |
| Authors | Joseany M.S. Almeida, Carlos A.T. Toloza, Rafael M. Dornellas, Andrea R. da Silva, Ricardo Q. Aucélio |
| Institutions | Universidade Federal de UberlĂąndia, PontifĂcia Universidade CatĂłlica do Rio de Janeiro |
| Citations | 7 |
| Analysis | Full AI Review Included |
Technical Analysis and Commercial Documentation: Boron-Doped Diamond for High-Sensitivity Electroanalysis of Strobilurins
Section titled âTechnical Analysis and Commercial Documentation: Boron-Doped Diamond for High-Sensitivity Electroanalysis of StrobilurinsâExecutive Summary
Section titled âExecutive SummaryâThe analyzed data validates the superior performance of Boron-Doped Diamond (BDD) electrodes in highly selective and sensitive electroanalytical determination of strobilurin fungicides across complex sample matrices (food, water, biological fluids).
- Core Material Validation: BDD electrodes are explicitly utilized in high-performance electrochemistry (SWV, BIA) for the detection of critical analytes like Kresoxim-methyl, Pyraclostrobin, and Dimoxystrobin.
- High Sensitivity Achieved: Detection limits for Dimoxystrobin using BIA on BDD reached 1.2 x 10-4 mg L-1, demonstrating extreme sensitivity comparable to or exceeding other advanced techniques.
- Diverse Applications: BDD facilitates sensing in challenging matrices, including grape juice, drinking water, and biological fluids (urine), showcasing robust chemical stability and low fouling characteristics.
- Technological Advantage: The stability and wide potential window of BDD provide a significant advantage over conventional electrodes (e.g., HMDE) for robust, high-throughput testing in environmental and food safety monitoring.
- 6CCVD Position: As an expert in MPCVD growth, 6CCVD provides the necessary highly conductive, polished, and customizable BDD material required to replicate and advance these critical electroanalytical methodologies.
Technical Specifications
Section titled âTechnical SpecificationsâThe following table summarizes the performance metrics and detection specifics extracted from the comparative study of strobilurin analysis methods.
| Parameter | Value | Unit | Context |
|---|---|---|---|
| Detection Limit (Lowest) | 1.2 x 10-4 | mg L-1 | Dimoxystrobin detection using BIA on BDD electrode in Water. |
| Detection Limit (Azoxystrobin) | 3.6 x 10-4 | mg L-1 | SW-ASV detection in Potato/Grape using HMDE. |
| Detection Limit (Kresoxim-methyl) | 9.0 x 10-2 | mg L-1 | SWV detection in Grape juice using BDD electrode. |
| BDD Material Use Case 1 | Kresoxim-methyl | N/A | SWV in Grape juice (9.0 x 10-2 mg L-1 LOD). |
| BDD Material Use Case 2 | Pyraclostrobin | N/A | SWV in Water/Grape juice (9.5 x 10-2 mg L-1 LOD). |
| BDD Material Use Case 3 | Dimoxystrobin | N/A | BIA in Water (1.2 x 10-4 mg L-1 LOD). |
| Electrophoresis Detection Wavelength | 220 | nm | Absorption photometry used in MEKC techniques. |
| Sample Matrix Complexity | Potato/Grape, Urine, Grape Juice | N/A | Demonstrates requirement for highly stable electrodes in complex media. |
Key Methodologies
Section titled âKey MethodologiesâThe research utilizes a combination of electroanalytical and chromatographic separation techniques, with a strong focus on utilizing the unique properties of diamond electrodes for direct electrochemical sensing.
1. Electroanalytical Techniques Utilizing BDD
Section titled â1. Electroanalytical Techniques Utilizing BDDâ- Square-Wave Voltammetry (SWV): Used for robust detection of Kresoxim-methyl and Pyraclostrobin in foodstuff matrices (Grape juice, Water/Grape juice).
- Batch-Injection Amperometry (BIA): Employed for the highly sensitive detection of Dimoxystrobin, yielding the lowest detection limit among the BDD-based techniques cited (1.2 x 10-4 mg L-1).
- Anodic Stripping Voltammetry (ASV): Both SW-ASV and DP-ASV methods were referenced for high-sensitivity determination of other strobilurins (Dimoxystrobin, Azoxystrobin, Picoxystrobin), though primarily utilizing non-BDD electrodes (HMDE, BiFE).
2. Electrophoretic Separation Techniques
Section titled â2. Electrophoretic Separation Techniquesâ- Micellar Electrokinetic Chromatography (MEKC): Used for separation and determination of multiple analytes (Picoxystrobin, Pyraclostrobin, Azoxystrobin, Kresoxim-methyl) in Urine, Fruits, and Vegetables.
- Detection Method for MEKC: Absorption Photometry at 220 nm, requiring optically transparent analysis windows compatible with UV light paths.
3. Electrode Material Context
Section titled â3. Electrode Material ContextâThe superior stability and sensitivity observed across the BDD-based entries confirm the materialâs viability as a solid-state, non-toxic alternative to conventional options like the Hanging Mercury Drop Electrode (HMDE).
6CCVD Solutions & Capabilities
Section titled â6CCVD Solutions & Capabilitiesâ6CCVD is uniquely positioned to supply the advanced diamond materials required to optimize and scale the high-sensitivity electroanalytical methods demonstrated in this research. Our capabilities directly address the need for customized, high-quality BDD electrodes and integration components.
Applicable Materials
Section titled âApplicable MaterialsâThe successful electroanalytical determination of strobilurins relies fundamentally on the material properties of Boron-Doped Diamond (BDD).
| 6CCVD Material | Specification Relevance | Application Focus |
|---|---|---|
| Heavy Boron-Doped PCD | High conductivity (low resistivity) optimized for high electron transfer rates required for SWV and BIA techniques. | Electrochemical sensing, high-throughput flow cells. |
| Custom Thickness PCD | Thicknesses ranging from 0.1 ”m up to 500 ”m, allowing precise control over electrode geometry and bulk properties. | Integration into microfluidic (BIA) and microelectrode arrays. |
| Polished SCD / PCD | Surfaces polished to Ra < 5 nm (PCD) or Ra < 1 nm (SCD) to minimize surface fouling and improve analyte deposition/release efficiency. | Maximizing signal-to-noise ratio in demanding media (e.g., urine, grape juice). |
Customization Potential
Section titled âCustomization PotentialâReplicating or advancing these sensing platforms often requires non-standard geometries and functional interfaces. 6CCVD provides comprehensive customization services:
- Custom Dimensions: We supply plates and wafers up to 125 mm (PCD) for large-scale production or multiple electrode fabrication.
- Laser Cutting and Machining: Precision shaping and dicing of BDD layers for integration into custom electrochemical cells or microchip designs.
- Advanced Metalization Services: We offer in-house deposition of standard contacts (Au, Pt, Pd, Ti) essential for connecting the BDD working electrode to external circuitry for SWV or BIA measurement systems.
Engineering Support
Section titled âEngineering SupportâThe transition from lab-scale demonstration to industrial sensing applications requires specialized knowledge in diamond material science.
- 6CCVDâs in-house PhD team can assist researchers and engineers with material selection (optimizing boron doping level and crystal structure) specifically for strobilurin detection projects and general electrochemical sensing applications.
- We offer technical consulting on integrating BDD layers into complex systems (e.g., creating low-resistance contacts for BIA systems or designing high-purity optical windows for MEKC absorption photometry).
For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.
View Original Abstract
The boron-doped diamond (BDD) presents attractive electrochemical sensing characteristics that are useful in analytical applications based on voltammetry and amperometry. It has a wide potential window in aqueous solutions enabling the quantification of the fungicide trifloxystrobin, measured at +1744 mV (<i>versus</i> Ag/AgCl), by square-wave anodic voltammetry in a Britton-Robinson (BR) buffer (0.04 mol L<sup>â1;</sup> pH 4.00)/acetonitrile 70/30% v/v. The activation of the electrode was made using galvanostatic chronopotentiometry and cyclic voltammetry (CV). The linear analyte addition curve, <i>I</i><i><sub>p</sub></i> (”A) = (1.0 Ă 10<sup>-1</sup> ± 4.8 Ă 10<sup>-6</sup>) C (mol L<sup>â1</sup>) + (8.8 Ă 10<sup>-2</sup> ± 1.1 Ă 10<sup>-3</sup>); <i>R</i><sup>2</sup> = 0.997, was obtained using amplitude of 40 mV, frequency of 30 Hz, step potential of 20 mV. The instrumental limit of detection (LOD) was 1.4 Ă 10<sup>-7</sup> mol L<sup>â1</sup> (0.058 mg L<sup>â1</sup>) and the dynamic linear range covered three decades (up to 1 Ă 10<sup>-5</sup> mol L<sup>â1</sup> or 4.1 mg L<sup>â1</sup>). The samples were analysed with recoveries about 80% in orange juice samples and from 92.4% to 104.0% in water samples. A study to evaluate potential interferences was made in the presence of other fungicides. Diagnostic studies indicated that oxidation of trifloxystrobin in aqueous medium at the surface of the BDD is irreversible, involving two steps, each one with two electrons. The UV degradation of trifloxystrobin was evaluated using the proposed electrochemical method and the kinetics of degradation established with half-life of 1.07 min.