Electrochemical determination of emodin in acidic media by high-performance liquid chromatography and its application to Polygoni Multiflori Radix samples

Electrochemical reduction of emodin under acidic media occurs at a less negative potential when compared with that under neutral media. When emodin is electrochemically detected at a less negative potential, a decrease in background noise and improvement in specificity benefit the development of high-performance liquid chromatography with electrochemical detection (HPLC-ECD) for its determination. HPLC-ECD was performed using an octadecyl silica column, acetonitrile-water (60:40, v/v) containing 5 mmol L^-1 hydrochloric acid and 10 mmol L^-1 lithium perchlorate, as a mobile phase, and an applied potential at - 0.4 V vs. Ag/AgCl. Under these optimal HPLC-ECD conditions, the detection limit (signal-to-noise ratio, S/N = 3) of emodin was 0.61 μg L^-1. When this HPLC-ECD system was applied to the determination of emodin in Polygoni Multiflori Radix (PMR) samples, other peaks did not appear close to the emodin peak on a chromatogram. The emodin contents in PMR samples were determined with relative standard deviations (RSDs, n = 6) of less than 3.9%, and their recoveries ranged from 92 to 106%. We have shown that our HPLC-ECD system performed an accurate, precise, and specific determination of emodin in PMR samples.