Three-way Trilinear Decomposition Algorithms And Their Applications To Second-order Calibration Using High Performance Liquid Chromatography-Diode Array Detection

In this thesis, the developments of muitivariate resolution and calibration in chemometrics. especially the iterative trilinear decomposition algorithms for the three-way data analysis based on alternating least squares principles and their applications have been reviewed. The methods for three-way (cubic) trilinear decomposition have been applied to the second-calibration using high performance liquid chromatography-diode array detection (HPLC-DAD). The problems arising from the serious overlapping of spectra and chromatograms are successfully resolved during the analysis of environment contamination, remedies and their metabolites, and so on. The assume replacing or improving the "chemical separation" with ''mathematical separation" and the charming of three-way data analysis from "second-order advantage" is exhibited in second-order calibration. In addition, an improved iterative trilinear decomposition making use of the alternating least squares principles has been proposed to overcome the problems of slow convergence and being sensitive to die estimation of factor number of the traditional PARAFAC algorithm.In Chapter 1, die developments of muitivariate resolution and calibration in chemometrics, especially the trilinear decomposition algorithms for the three-way data analysis and their applications have been reviewed.It is realistic and important to determinate quantitatively phenols due to their pollution widely existing in nature. Dihydroxybenzenes are hard to be determined simultaneously by routine chemical or physical methods because of their similarities of physical and chemical properties. In Chapter 2, the overlapping chromatograms and spectra of dihydroxybenzenes were resolved by alternating trilinear decomposition (ATLD) algorithm combined with HPLC-DAD, determining catechol, resorcinol and hydroquinone in aqueous solution simultaneously with their corresponding recoveries being (100.6±1.4)%, (98.3±1.3)% and (101.3±2.0)%, respectively. The results showed the experiment could be easily performed without resorting to time-consuming and complicated procedures and quantified accurately, resolving the problem arising from the overlapping chromatograms and spectra of analytes of interest. It also showed the promising application of chemometrics in analytical sciences.Salicylic and gentisic acids are major metabolites of aspinn. which may coexist with pyrocatechuic acid in biological fluids that serves as another active pharmaceutical ingredient. In chapter 3, ATLD method combined with HPLC-DAD is used to simultaneously determinate salicylic and gentisic acids in the presence of unknown and uncalibrated pyrocatechuic with their chromatograms and spectra seriously overlapping. A satisfying result has been obtained. The method successfully accomplished the direct simultaneous determination of analytes of interest in the presence of interfering components without expensive or time-consuming procedures with their recoveries being (102.2 ± 6.7)% and (102.1 ± 4.1)%, respectively. It is indicated ATLD can be efficiently applied to the second-order calibration in HPLC-DAD.Sulfonamides exceedingly used in the treatment of edible animals will lead to their residue in products, which will do harm to human ultimately. Quality control of sulfonamide formulations and their monitoring in body fluids are important analytical tasks. In chapter 4, sulfadiazine and sulfamethoxazole in synthetic samples and pharmaceutical tablets were simultaneously determined in the presence of unknown sulfanilamide by HPLC-DAD with easy and fast performance and accurate quantity. The study showed the fast convergence and insensitive to the estimation of component number of the ATLD algorithm and "second-order advantage" of the second-order calibration in HPLC-DAD.In chapter 5, a novel algorithm, alternating simultaneously minimized diagonal and covariant matrices' errors (ASMDCME) algorithm has been proposed for three-way data analysis. Simulated and real HPLC-DAD data have been carried to investigate the performance o...