Dataset for the article "Electron-Transfer Engineering with Detonation Nanodiamonds Enables Highly Sensitive and Selective Cortisol Immunoassay"
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Electron-Transfer Engineering with Detonation Nanodiamonds Enables Highly Sensitive and Selective Cortisol Immunoassay Chakavak Esmaeili, Jaroslav Kuliček, Markéta Šlapal Bařinková, Bohuslav Rezek Faculty of Electrical Engineering, Czech Technical University in Prague,Technická 2, 16627 Prague, Czechia*email: esmaecha@fel.cvut.cz AbstractDetonation nanodiamonds (DNDs) offer exceptional surface chemistry and biocompatibility that makes them attractive nano building blocks for next‑generation biosensing interfaces. Here, we engineer a DND‑modified screen‑printed carbon electrode (SPE) using EDC/NHS‑mediated covalent crosslinking to create a stable and high‑performance immunosensing platform for cortisol detection. Comprehensive morphological and chemical analyses (AFM, SEM, Raman, FTIR) reveal uniform DND deposition,efficient amide‑bond formation, and sequential immobilization of cortisol antibodies and BSA. Electrochemical characterization demonstrates that DNDs significantly enhance conductivity and redox kinetics, enabling sensitive detection of cortisol via differential pulse voltammetry. We show that DNDs act as an efficient nanoscale mediator for enhanced electron‑transfer, especially in combination with carbon SPE. The sensor achieves a broad linear detection range from 0.1 to 100 nM with a low detectionlimit of 0.01 nM, excellent selectivity against structurally related hormones, and robust stability for at least six weeks. Its applicability is validated through accurate measurements of spiked artificial saliva samples. DND‑based electron‑transfer engineering can thus provide a powerful route toward scalable, low‑cost, and reliable immunosensing. Keywords: Detonation nanodiamond, cross linker, immunosensor, cortisol, artificial saliva sensor Figure 1. The preparation and immobilization step of the cortisol fabrication based on electrochemical immunosensor.Figure 2. 3D AFM images of (1) carbon bare electrode, (2) carbon electrode /DND, (3) carbon electrode/DND/EDC NHS (4)carbon electrode/ DND /EDC NHS/Ab, (5) carbon electrode/ DND /EDC NHS/Ab /BSA, (6) carbon electrode/ DND /EDCNHS/Ab/BSA/Ag.Figure 3. Raman spectra of immunosensor composition.Figure 4. FTIR spectra of DND (gray line), DND/ EDC NHS (blue line), DND/EDC NHS/Ab (green line). All spectra were recorded in the region between 4000–800 cm−1 with a resolution of 4 cm− 1and 128 scans.Figure 5. Functionalization steps: (1) carbon bare electrode, (2) carbon electrode /DND, (3) carbon electrode /DND/EDC NHS,(4) carbon electrode/DND/ EDC NHS/Ab. Sensing step (5) carbon electrode/DND/ EDC NHS/Ab/BSA and (6) carbonelectrode/DND/ EDC NHS/Ab/BSA/Ag (100 nM cortisol) in pH 7.0, containing 250 mM KCl and 5 mM K3[Fe(CN)6] and 5 mM K4[Fe(CN)6], Scan rate 0.1Vs−1.Figure 6. (a) Calibration curve of DPV with varying Ag concentrations. (b) Sensitivity comparison between configurations without Ab receptor (carbon electrode/DND/EDC NHS/Ag) and with Ab receptor (carbon electrode/DND/EDC NHS/Ab/BSA/Ag) in PBS solution, pH 7.0, containing 250 mM KCl and 5 mM K3[Fe (CN)6] and 5 mM K4[Fe (CN)6].Figure 7. Interference study involving progesterone (2430 pg/ml), β-oestradiol (32 pg/ml), cortisone (28.6 nM), and corticosterone (3.94 nM) with respect to cortisol (100nM).Figure 8. Stability of the immunosensor with repeated measurements of cortisol. Figure S1. Optical images obtained for (1) bare carbon electrode, (2) DND, (3) DND/EDC NHS, (4) DND/EDC NHS/Ab, (5) DND/EDC NHS/Ab/BSA, (6) DND/EDC NHS/Ab/BSA/Ag.Figure S2. SEM images of (1) bare carbon SPE, (2) carbon electrode/ DND, (3) carbon electrode/ DND /EDC NHS, (4) carbon electrode/ DND /EDC NHS/Ab, (5) carbon electrode/DND/EDC NHS/Ab/BSA, (6) carbon electrode/ DND /EDC NHS/Ab/BSA/Ag.Figure S3. (a) CV and (b) DPV of carbon bare electrode, carbon electrode /EDC NHS, carbon electrode/EDC NHS/Ab, carbon electrode/EDC NHS/Ab/BSA, carbon electrode/EDC NHS/Ab/BSA/Ag, in the presence of 100 nM cortisol, pH 7.0, containing 250 mM KCl and 5 mM K3[Fe(CN)6] and 5 mM K4[Fe(CN)6], Scan rate 0.1Vs−1. Table 1. Determination of cortisol in artificial saliva sample (n = 3).Table S1. Surface roughness of immunosensors.
