Onion-like Carbons Provide a Favorable Electrocatalytic Platform for the Sensitive Detection of Tramadol Drug

[Image: see text] This work reports the first study on the possible application of nanodiamond-derived onion-like carbons (OLCs), in comparison with conductive carbon black (CB), as an electrode platform for the electrocatalytic detection of tramadol (an important drug of abuse). The physicochemical properties of OLCs and CB were determined using X-ray diffraction (XRD), Raman, scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), and thermogravimetric analysis (TGA). The OLC exhibits, among others, higher surface area, more surface defects, and higher thermal stability than CB. From the electrochemical analysis (interrogated using cyclic voltammetry, differential pulse voltammetry, and electrochemical impedance spectroscopy), it is shown that an OLC-modified glassy carbon electrode (GCE-OLC) allows faster electron transport and electrocatalysis toward tramadol compared to a GCE-CB. To establish the underlying science behind the high performance of the OLC, theoretical calculations (density functional theory (DFT) simulations) were conducted. DFT predicts that OLC allows for weaker surface binding of tramadol (E(ad) = −26.656 eV) and faster kinetic energy (K.E. = −155.815 Ha) than CB (E(ad) = −40.174 eV and −305.322 Ha). The GCE-OLC shows a linear calibration curve for tramadol over the range of ∼55 to 392 μM, with high sensitivity (0.0315 μA/μM) and low limit of detection (LoD) and quantification (LoQ) (3.8 and 12.7 μM, respectively). The OLC-modified screen-printed electrode (SPE-OLC) was successfully applied for the sensitive detection of tramadol in real pharmaceutical formulations and human serum. The OLC-based electrochemical sensor promises to be useful for the sensitive and accurate detection of tramadol in clinics, quality control, and routine quantification of tramadol drugs in pharmaceutical formulations.