| Direct,rapid,simultaneous,and accurate quantitative analysis of multiple components of interest in complex systems with unknown interference are quite challenging.With the development of high-order analytical instruments and the in-depth study of chemometrics,chemical multiway calibration methods play an important role in solving this problem.Compared with traditional quantitative analysis methods,chemical multiway calibration methods combined with modern high-order analytical instruments has a unique “second-order or high-order advantage”,can replace or enhance traditional “physical or chemical separation” by green “mathematical separation”,avoid expensive separation equipment and cumbersome sample pretreatment steps and can obtain accurate quantitative results in a short period of time.At present,it has become a powerful strategy for accurate quantification of multi-target compounds in complex matrix.This analytical strategy has been accepted by more and more researchers in various fields at home and abroad and has been widely used in the quantitative analysis of complex systems such as biomedicine,food,cosmetics,and environment.Therefore,after in-depth investigation on the development trend,basic theory,and application of chemical multiway calibration methods,it is worth to do further research on continuing to develop efficient multiway calibration algorithms with better performance and applying multiway calibration methods to solve more complex quantitative problems in practical analysis systems.In addition,the theory and application research of chemical pattern recognition methods is also the focus of chemometrics research.At present,and it has broad application prospects in many directions such as food authenticity identification,food origin traceability and quality control of foods and cosmetics.Therefore,this paper focused on the innovative quantitative analysis applications of chemical multiway calibration methods combined with high-order chromatography instrument,the development of efficient multiway calibration and the innovative application of chemical pattern recognition method.The main contents of this paper are as follows:Part I: Chemical multiway calibration assisted high-order chromatography instrument for accurate quantitative analysis of multi-target analytes in cosmetics and foods.In Chapter 2,ATLD algorithm-assisted LC-MS strategy was proposed for the accurate quantification of 15 glucocorticoids illegally added into face masks.By virtue of “second-order advantage” provided by ATLD,the problems of overlapping peaks,unknown interferences and baseline drift in chromatographic analysis were successfully solved,and the accurate quantification of 15 glucocorticoids in facial mask was realized.At the same time,it is worth mentioning that the epimers,betamethasone and dexamethasone,could also be accurately determined by the proposed strategy under a simple elution procedure.The performance of the proposed method was investigated by using analytical figures of merits and statistical parameters.In addition,the classical LC-MS/MS method was also used to further verify the feasibility of the developed strategy.Compared with the classical LC-MS/MS method,the results suggest that the proposed strategy can be a simple,versatile,and accurate method for simultaneous determination of glucocorticoids in complex facial mask samples,without complicated pretreatment,optimizations of chromatographic and MS/MS conditions.Therefore,the proposed strategy can be used for rapid identification and quantification of illegally added substances in cosmetics.In Chapter 3,a smart analytical strategy that second-order calibration methods assisted liquid chromatography-mass spectrometry(LC-MS)was developed for simple and rapid determination of eleven polyphenols in Chinese propolis.The eleven polyphenols were fast eluted out within 7.0 min under a simple gradient condition.According to the characteristics of the acquired three-way data array,two commonly used second-order calibration methods,namely alternating trilinear decomposition algorithm(ATLD)and multivariate curve resolution-alternating least squares(MCRALS),were used to analyze it.With the excellent “second-order advantage” provided by the second-order calibration methods,the serious overlapping peaks,and variable unknown interference in the complex propolis matrix were successfully resolved,and satisfactory quantitative results were obtained.By comparing the quantitative results provided by the two second-order calibration methods and the LC-MS/MS method,the results show that second-order calibration methods assisted LC-MS analytical strategy is more timesaving,eco-friendly,and low-cost to achieve accurate determination of polyphenols in complex food matrices,without elaborate sample preparation steps,painstaking experimental condition optimization and advanced high-cost equipment.Therefore,the proposed method is expected to become a powerful tool for accurate quantitative analysis of multiple target analytes in complex food matrices and food quality monitoring.In Chapter 4,a simple and effective strategy that the combination of highperformance liquid chromatography-diode array detection(HPLC-DAD)and secondorder calibration method based on alternating trilinear decomposition algorithm(ATLD)was proposed for fast and simultaneous determination of twelve preservatives in a variety of cosmetic products.Under simple sample pretreatments and elution conditions,twelve preservatives were completely eluted within 10.5 minutes,which significantly reduced elution time.By using the green “mathematical separation” to replace or enhance conventional “physical or chemical separation”,the proposed method achieved accurate quantitative analysis of multiple preservatives in selected cosmetic samples in the presence of serious co-elution problems(chromatographic peak overlap)and variable unknown interference in cosmetics.In addition,the proposed method has successfully used to determine the preservatives in other cosmetics from different types.Compared with published methods,the proposed method has advantages of time-saving,environmentally friendly and low-cost,and is expected to be a general method for the quantitative analysis of multiple target analytes in complex systems.Part II: Development of efficient chemical multi-way calibration algorithms.In Chapter 5,a self-adaptive alternating quadrilinear decomposition(SAAQLD)algorithm with better comprehensive performance was proposed.By analyzing simulated data sets,the performance of SAAQLD and other common five iterative fourway calibration algorithms including FPARAFAC,AQLD,AWRCQLD,RSWAQLD and APQLD,were compared and discussed.The results show that SAAQLD has excellent comprehensive performance,mainly reflected in the fastest convergence speed,insensitive to the number of components and noise,and suitable for four-way data arrays with different sizes.In addition,SAAQLD algorithm was used to analyze two real fourway data arrays.The results indicate that SAAQLD algorithm can quickly and accurately extract the qualitative and quantitative information of each target analyte,even if there are unknown interference and peak overlap problems.Therefore,the proposed SAAQLD algorithm is expected to be widely used in four-way data analysis.Part III: Excitation-emission matrix fluorescence combined with chemometric methods for fast identification of the geographical origin of Gastrodia elata.In Chapter 6,a flexible strategy that excitation-emission matrix fluorescence spectroscopy combined with chemometrics was developed for the simple and rapid identification of the geographical origin of Gastrodia elata.After a simple sample extraction step,excitation-emission(EEM)spectra of all Gastrodia elata sample was quickly obtained.Then,three chemometric methods(including U-PLS-DA,N-PLS-DA and k NN)were used to classify Gastrodia elata samples.The results show that three chemometric methods have obtained satisfactory classification results.Therefore,Compared with traditional methods based on chromatographic technology,the proposed strategy can avoid chromatographic separation,reduce analysis time and consumption of toxic organic solvents.Therefore,the proposed strategy can be used as a promising alternative method to identify the geographic origin of other traditional Chinese medicines with endogenous fluorescent components. |
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