Investigation of Electrochemical Fingerprints for Buzhong Yiqi Tang Extract Granules Using Diamond-Graphene Composite Electrode

Abstract

This study presents a novel electrochemical fingerprinting method for Buzhong Yiqi Tang extract granules using a diamond-graphene composite electrode. The electrode was fabricated through chemical vapor deposition of graphene on high-pressure high-temperature synthetic diamond, resulting in a few-layer graphene coating as confirmed by Raman spectroscopy (I₂D/IG ratio ≈ 1.2) and XPS analysis (78% sp² C-C signal). Cyclic voltammetry revealed four anodic and three cathodic peaks, while differential pulse voltammetry provided enhanced resolution with eight distinct oxidation peaks. The method demonstrated high sensitivity (LODs 0.08-0.15mg/mL) and good linearity (R² > 0.995) over a concentration range of 0.5-10mg/mL. Comparison of fingerprints from individual herb extracts (Astragalus membranaceus, Panax ginseng, and Glycyrrhiza uralensis) elucidated the origins of major peaks in the Buzhong Yiqi Tang profile. Principal component analysis of fingerprints successfully differentiated between samples from three manufacturers, accounting for 87.3% of total variance. Strong correlations (r > 0.92) were observed between key DPV peak intensities and HPLC-determined concentrations of traditional chemical markers. The rapid analysis time, minimal sample preparation, and holistic representation of multiple electroactive components make this approach a promising complement to existing chromatographic methods for quality assessment of traditional Chinese medicine formulations.