The Determination Of The Ferulic Acid,Dectamnine And Salidroside In Medicine By Three-dimensional Fluorescence Coupled With Second-order Calibration Methods

Chemometrics,also known as chemometrics,is a branch of chemistry,combined by mathematics,statistics,computer science,and chemistry.The research object is the basic theory and methodology of chemical measurement.The second-order correction method in chemometrics replaces the "physical and chemical separation" with mathematical separation by virtue of its own "second-order advantage",it can directly and accuratly realize qualitative and quantitative interests even in the presence of unknown interferences in the analysis system.There are many complex and diverse chemical compositions in Traditional Chinese Medicines(TCM).Most of the active components in TCMs can produce fluorescence.In this paper,the content of ferulic acid,dectamnine and salidroside in TCM were determined respectively by excitation–emission fluorescence matrices(EEMs)coupled with different second-order data analysis algorithms.In chapter 2,the use of Mg(II)as a sensitizer greatly improves the fluorescence intensity of ferulic acid,achieving fluorescence spectrum analysis.This paper presents the feasibility of determination of ferulic acid in three herbal medicines and three herbal formulaes through excitation–emission fluorescence matrices(EEMs)coupled with different second-order data analysis algorithms:parallel factor analysis(PARAFAC),alternating trilinear decomposition(ATLD)and unfolded partial least squares coupled to residual bilinearization(U-PLS/RBL).The results show that although the matrix of TCM system is complex,PARAFAC and ATLD can quickly and accurately extract the fluorescence spectrum of ferulic acid,indicating that the qualitative properties of the above two methods are good.To further verify the reliability of the proposed methods,the samples were analyzed by high performance liquid chromatography method.The relative errors were obtained by comparing the content of ferulic acid calculated in six herbal medicines by three second-order calibration methods with the result determined by HPLC method.Relative errors between the quantitative results of trilinear algorithms(PARAFAC,ATLD)methods and those of HPLC-UV are large and unacceptable.However,U-PLS/RBL yielded better predictions with lower relative errors,suggesting that U-PLS/RBL method has good quantitative ability.T-test demonstrated that there are no significant differences between the prediction results of the two methods.And then the recovery rate of ferulic acid in the six traditional Chinese medicines is analyzed using U-PLS/RBL.The recovery rate is close to 100%.Thus,PARAFAC and ATLD are used to screen samples rapidly for qualitative analysis,while U-PLS/RBL is used for accurate quantitative analysis.Two kinds of chemometric algorithms were applied simultaneously to ensure the accuracy of the analysis results.In chapter 3,three different second-order correction algorithms were used to analyze the content of dectamnine in Cortex dictamni from different producing areas.There are similar components to dectamnine in Cortex dictamni,in this case,the obtained results by PARAFAC showed that the resolved spectra and real spectra of dectamnine matched quite well with each other.In addition,the quantitative results of PARAFAC,U-PLS/RBL and N-PLS/RBL were compared with the results of high performance liquid chromatography,showing that the analytical results of U-PLS/RBL method and N-PLS/RBL method were closer to the chromatographic results.At the same time,U-PLS/RBL and N-PLS/RBL methods were used to analyze the recovery rate of dectamnine in Cortex dictamni from different producing areas.The results showed that the recovery was good.In chapter 4,Three-dimensional fluorescence combined with second-order calibration methods(PARAFAC,ATLD,U-PLS/RBL and N-PLS/RBL)were used to determine the content of salidroside in the Rhodiola which were from different areas.The analytical results were verified by HPLC.The analytical spectrum resolved by PARAFAC and ATLD are basically the same as the real spectrum,but the quantitative results in some places are too large,while U-PLS/RBL and N-PLS/RBL better quantitative results.At the same time,the recovery rates of salidroside in Rhodiola from different habitats are analyzed by these two methods and the results is acceptable.Satisfactory analytical results show that the three-dimensional fluorescence combined with the second-order correction method is a fast,efficient,and practically promising measurement method.