Rapid and interference-free quantification of nine coumarins in Cnidii fructus using HPLC-DAD assisted with second-order calibration model

Abstract

High performance liquid chromatography-diode array detection (HPLC-DAD) assisted with second-order calibration model based on alternating trilinear decomposition-assisted multivariate curve resolution (ATLD-MCR) model was proposed to quantify nine coumarins in traditional Chinese medicine (TCM) samples of Cnidii Fructus. This advanced analytical strategy shows good linearity (r > 0.9991), rapidity (t < 10.50 min) and accuracy, in low chromatographic resolution data even in the presence of potential interfering species. Satisfactory qualitative and quantitative results were achieved in the presence of complex matrix interferences from the TCM samples and the second-order advantage was fully exploited. The average spiked recoveries for most target analytes are in the range of 84.1%–108.0% with the standard deviations less than 6.9%. Furthermore, the quantitative results were further compared with a classical univariate calibration applied to a series of peak area data acquired from HPLC-UV detection. Statistical parameters and analytical figures of merit were calculated according to modern analytical protocols to validate the accuracy of the proposed analytical method. The results show that the proposed analytical method had the advantages of high-efficiency, low-cost and met the requirements of green analytical chemistry. Therefore, it promises to be a potential and universal way for qualitative and quantitative analysis of coumarins in pharmaceutical and food fields.