| Since traditional Chinese minority herbs are characterized by complex compsition andsynergistic effect, it is important to simultaneously determine the multi-bioactive ingredients.However, effective and reliable analysis methods for simultaneous and direct quantificationof the multi-bioactive ingredients are highly demanded because traditional Chinese herbsGentiana and body fluids are very complicated. Chemometrics can achieve useful chemicalinformation as much as possible from the enormous complex signals generated by the modernanalytical instruments, and accordingly provides novel and very powerful research tool forqualitative as well as quantitative analysis of complex multi-component chemical systems. Inparticular, the second-order calibration methods can offer the so-called “second-orderadvantage”, namely they can allow for the rapid, direct quantitative analysis of the analytes ofinterest in complex chemical systems even in the existence of unknown interferences. Studiespresented in the thesis primarily focused on multi-way quantitative analysis ofmulti-bioactive ingredients in traditional Chinese herb Gentiana and body fluids byHPLC-DAD with aid of second-order calibration methods.Chapter2: A novel method based on high performance liquid chromatography-diodearray detection (HPLC-DAD) coupled with self-weighted alternating trilinear decomposition(SWATLD algorithm is proposed for determination of multi-bioactive ingredients includingGentiopicroside, Swertiamarin, Loganic acid and orientin in15different plants ofGentianaceae samples. The method can handle thisproblem that the chromatographic andspectral peaks are heavily overlapped among the analytes andeven between the analytes andinterferences from the various Gentianaceae samples. the SWATLD algorithm utilized“mathematical separation”instead of partial“physical or chemical separation”to directlydetermine multi-bioactive ingredients. The satisfactory quantification results have beengained with simple chromatograph condition. In the analysis of real Chinese medicinesamples, the accuracy ofthe concentrations which were obtained by SWATLD was alsovalidated by the second-order standard addition method and HPLC–MS method.Chapter3: A simple, rapid, and effective method for quantitative analysis ofGentiopicroside, Swertiamarin, Loganic acid and orientin in body fluids using HPLC-DADcoupled with second-order calibration based on alternating penalty trilinear decomposition(APTLD) algorithm.With the aid of second-order advantage, after simple pretreatments, satisfactory results are obtained although the elution time and spectral profiles of GEN, SWE,LOG and ISO are overlapped with uncalibrated interferences from body fluids samples. Themethod proposed lights a new avenue to determine quantitatively. Moreover, the accuracy ofthe algorithm was also evaluated through elliptical joint confidence region (EJCR) tests aswell as figures of merit, such as sensitivity (SEN), selectivity (SEL) and limit of detection(LOD). This method also will be expected as a promising alternative strategy forsimultaneous and direct quantitative analysis of in vivo of multi-bioactive ingredients intraditional Chinese herbs.Chapter4: A comprehensive and systematic strategy for evaluating the performances ofseveral trilinear second-order calibration algorithms is presented, in particular with a view ofpractical applications. Several trilinear second-order calibration methods such as parallelfactor analysis (PARAFAC), alternating trilinear decomposition (ATLD), APTLD andSWATLD, which have the second-order advantage and are gaining widespread acceptance inthe field of chemometrics, were compared. Based on different input parameters includinginitial value, number of estimated components and collinearity in real data, the performancesof these methods were evaluated in terms of predicting ability, consistency of resolved andreal profiles, and fitness obtained by selected components. The obtained results give areevaluation of the position and role of these trilinear second-order calibration methods inchemometrics and provide guidance in practical applications for solving complicatedquantitative analysis problems in analytical chemistry. |
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