Near infrared (NIR) assignment of Isopsoralen was performed using deuterated chloroform solvent and two-dimensional correlation spectroscopy (2D-COS) technology. Yunkang Oral Liquid was applied to study Isopsoralen, the characteristic bands by spectral assignment as well as the bands by interval partial least squares (iPLS) and synergy interval partial least squares (siPLS) were used to establish partial least squares (PLS) model. The coefficient of determination in calibration (R2cal) were 0.9987, 0.9970 and 0.9982. The coefficient of determination in cross validation (R2val) were 0.9985, 0.9921 and 0.9982. The coefficient of determination in prediction(R2pre) were 0.9987, 0.9955 and 0.9988. The root mean square error of calibration (RMSEC) were 0.27, 0.40 and 0.31 ppm. The root mean square error of cross validation (RMSECV) were 0.30, 0.67 and 0.32 ppm. The root mean square error of prediction (RMSEP) were 0.23, 0.43 and 0.22 ppm. The residual predictive deviation (RPD) were 31.00, 16.58 and 32.41. It turned out that the characteristic bands by spectral assignment had the same results with the chemometrics methods in PLS model. It provided guidance for NIR spectral assignment of chemical compositions in Chinese Materia Medica (CMM).

In this work, multivariate detection limits (MDL) estimator was obtained based on the microelectro- mechanical systems–near infrared (MEMS–NIR) technology coupled with two sampling accessories to assess the detection capability of four quality parameters (glycyrrhizic acid, liquiritin, liquiritigenin and isoliquiritin) in licorice from different geographical regions. 112 licorice samples were divided into two parts (calibration set and prediction set) using Kennard– Stone (KS) method. Four quality parameters were measured using high-performance liquid chromatography (HPLC) method according to Chinese pharmacopoeia and previous studies. The MEMS–NIR spectra were acquired from fiber optic probe (FOP) and integrating sphere, then the partial least squares (PLS) model was obtained using the optimum processing method. Chemometrics indicators have been utilized to assess the PLS model performance. Model assessment using chemometrics indicators is based on relative mean prediction error of all concentration levels, which indicated relatively low sensitivity for low-content analytes (below 1000 parts per million (ppm)). Therefore, MDL estimator was introduced with alpha error and beta error based on good prediction characteristic of low concentration levels. The result suggested that MEMS– NIR technology coupled with fiber optic probe (FOP) and integrating sphere was able to detect minor analytes. The result further demonstrated that integrating sphere mode (i.e., MDL_0.05;0.05, 0.22%) was more robust than FOP mode (i.e., MDL_0.05;0.05, 0.48%). In conclusion, this research proposed that MDL method was helpful to determine the detection capabilities of low-content analytes using MEMS–NIR technology and successful to compare two sampling accessories.