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Micro-band Boron-doped Diamond Electrode in Capillary Electrophoresis for Simultaneous Detection of AMP, ADP, and ATP

MetadataDetails
Publication Date2021-04-13
JournalInternational Journal of Technology
AuthorsPutu Udiyani Prayikaputri, Prastika Krisma Jiwanti, Mochammad Arfin Fardiansyah Nasution, Jarnuzi Gunlazuardi, Endang Saepudin
InstitutionsUniversity of Indonesia, Airlangga University
Citations5
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Technical Documentation & Analysis: Micro-band Boron-doped Diamond Electrodes

Section titled “Technical Documentation & Analysis: Micro-band Boron-doped Diamond Electrodes”

This research successfully demonstrates the fabrication and application of a highly sensitive micro-band Boron-Doped Diamond (BDD) electrode coupled with Capillary Zone Electrophoresis (CZE) for bioanalytical sensing.

  • Material Focus: Polycrystalline Boron-Doped Diamond (BDD) films were synthesized via Microwave Plasma-Assisted Chemical Vapor Deposition (MPCVD), confirming high sp3 crystallinity.
  • Novel Geometry: A micro-band electrode geometry was achieved through a lamination (sandwich) technique, resulting in an effective surface area of 1.11 x 10-7 m2.
  • High Sensitivity: The micro-band geometry leveraged radial diffusion, providing significantly higher sensitivity and better Limits of Detection (LODs) compared to traditional macro-BDD electrodes.
  • Simultaneous Detection: The system successfully achieved simultaneous, well-separated detection of Adenosine Monophosphate (AMP), Adenosine Diphosphate (ADP), and Adenosine Triphosphate (ATP).
  • Performance Metrics: LODs were achieved in the low micromolar range (0.004 ”M to 0.011 ”M) for the three adenosine phosphates.
  • Real-World Application: The method was validated for complex matrices, successfully analyzing and quantifying spiked adenine, guanine, AMP, ADP, and ATP in human urine samples.

The following hard data points were extracted from the research detailing the material properties and optimal operational parameters.

ParameterValueUnitContext
BDD Synthesis MethodMPCVD-Polycrystalline film deposition
BDD Film Thickness (As-deposited)5”mAverage thickness
BDD Film Thickness (Micro-band)~10”mObserved in longitudinal SEM section
Boron Doping Level (B/C)1%Used in methanol solution precursor
Effective Electrode Area1.11 x 10-7m2Calculated via Cottrell equation
Optimal Detection Potential+1.0Vvs Ag/AgCl, for AP oxidation
Optimal Buffer pH2.0-Britton-Robinson buffer for highest oxidation current
Optimal Separation Voltage10kVCapillary Electrophoresis separation
LOD (ATP, Micro-band BDD)0.011”MLimit of Detection
LOD (AMP, Micro-band BDD)0.004”MLimit of Detection
LOD (ADP, Micro-band BDD)0.006”MLimit of Detection
Linear Correlation (R2)0.997 - 0.999-Across 0.1 mM to 2.0 mM range

The fabrication of the micro-band BDD electrode involved precise material synthesis and post-processing steps critical for achieving the desired electrochemical performance.

  1. BDD Synthesis (MPCVD): Polycrystalline BDD film was grown on a Si (100) substrate using a Microwave Plasma-Assisted Chemical Vapor Deposition (MPCVD) system. The precursor solution included methanol doped with boron at a 1% B/C ratio.
  2. Substrate Removal: The BDD film was separated from the Si substrate by immersion in a 1:1 mixture of HF (48%) and HNO3 (60%) for 12 hours, yielding a free-standing BDD film.
  3. Electrode Preparation: The free-standing BDD film and silicone rubber were cut into 1 cm x 1 cm squares.
  4. Micro-band Lamination: The BDD film was sandwiched between insulating plates (Teflon and silicone rubber) in the order: Teflon-silicone-BDD-silicone-Teflon. This lamination technique defined the micro-band geometry (4 mm wide exposed area).
  5. Electrical Contact: A copper wire was inserted into the sandwich structure to provide electrical contact to the BDD film.
  6. Electrochemical Testing: Cyclic Voltammetry (CV) was performed over a potential range of -1.6 V to +2.0 V. Amperometry was coupled with the CZE system for detection at the optimal potential of +1.0 V.

6CCVD is uniquely positioned to supply the advanced BDD materials and custom fabrication services required to replicate, optimize, and scale the high-performance electrochemical sensor demonstrated in this research.

The core material requirement is high-quality, heavily Boron-Doped Diamond (BDD) film suitable for electrochemical detection.

Research Requirement6CCVD SolutionTechnical Advantage
Polycrystalline BDD Film (5 ”m thick)Heavy Boron-Doped PCD WafersWe offer PCD films from 0.1 ”m up to 500 ”m thick, allowing precise matching of the 5 ”m requirement.
High sp3 PurityHigh-Quality MPCVD SynthesisOur advanced MPCVD reactors ensure minimal sp2 carbon impurities, critical for achieving the wide potential window and low background current characteristic of high-performance BDD.
Free-Standing FilmCustom Substrate RemovalWe supply BDD films either on standard Si substrates or as free-standing wafers (up to 500 ”m thick), eliminating the need for in-house HF/HNO3 etching by the end-user.

The research noted potential delamination defects in the manually laminated micro-band structure (Figure 3b). 6CCVD’s integrated fabrication capabilities can eliminate these issues and optimize the electrode geometry.

  • Precision Geometry: While the paper used 1 cm x 1 cm squares, 6CCVD offers precision laser cutting services to define micro-band or micro-array geometries directly onto the BDD wafer with micron-level accuracy, ensuring consistent, defect-free electrode edges superior to manual lamination.
  • Integrated Metalization: The use of a simple copper wire contact is prone to defects. 6CCVD offers in-house metalization services (Ti/Pt/Au, W/Cu, etc.) to deposit robust, low-resistance contact pads directly onto the BDD surface. This ensures reliable electrical contact and simplifies integration into CZE/potentiostat systems.
  • Large Format Capability: For scaling up production or creating multi-channel CZE systems, 6CCVD can provide PCD wafers up to 125 mm in diameter, far exceeding the small 1 cm x 1 cm pieces used in the study.
  • Polishing: We offer ultra-smooth polishing (Ra < 5 nm for inch-size PCD) to ensure the BDD surface is optimally prepared for subsequent lamination or patterning steps, minimizing surface roughness that can affect electrochemical performance.

The successful application of BDD in complex bioanalytical systems, such as the simultaneous detection of adenosine phosphates in urine, requires specialized material knowledge.

  • Application Expertise: 6CCVD’s in-house PhD team specializes in the electrochemical properties of diamond. We offer consultation on optimizing BDD material parameters (doping concentration, surface termination, and thickness) for similar Capillary Electrophoresis (CE) and Amperometric Detection projects.
  • Material Selection: We provide expert guidance on selecting the appropriate diamond grade (SCD for ultimate purity/smoothness, or PCD for cost-effective large area coverage) based on the specific sensitivity and stability requirements of the target analyte.

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

View Original Abstract

A micro-band boron-doped diamond (BDD) electrode was prepared by sealing a piece of BDD film with an area of 1.11ÂŽ10-7 m2 between two insulating plates, one Teflon and one silicon rubber, to form sandwich-like layers, so the surface area could be investigated. The micro-band BDD was combined with capillary zone electrophoresis as an electrode for the simultaneous detection of adenosine monophosphate (AMP), adenosine diphosphate (ADP), and adenosine triphosphate (ATP) in a solution. These adenosine phosphates can be separated with a 0.3 m-long fused silica capillary using Britton-Robinson buffers at pH 2.0. Current in the concentration range of 0.1 to 2.0 mM were linear with the limits of detection of 0.004 ?M, 0.006 ?M, and 0.011 ?M for AMP, ADP, and ATP, respectively. A comparison with an unmodified BDD as the detector in the same electrophoresis system showed that the micro-band generated better limits of detection (LODs) than the macroelectrode. This method was successfully applied to human urine samples injected with three adenosine phosphates, as well as adenine and guanine, which can be well-separated with recovery percentages of adenine, guanine, AMP, ADP, and ATP of 99.2%, 102.5%, 107.4%, 107.7%, and 105.4%, respectively.