Second-order Calibration Methods Coupled With Matrix Analytical Instruments For The Determination Of Analytes Of Interest In Functional Food And Other Systems

Owing to the growing availability of modern analytical instruments able to easilygenerate multidimensional arrays of experimental data per sample, the multi-way dataanalysis and tensorial calibration appear to be attractive research hotspots and aregaining widespread acceptance in many scientific fields, such as chemistry, biology,medicine, food, environment and metabonomics. Multi-way calibration methods inchemometrics, especially the second-or higher-order calibration can compensate forpotential interferences which are not included in the calibration set and can accuratelyachieve the concentrations of individual components of interest, Chemometricmethods fully extract the useful chemical information using “mathematicalseparation” instead of “physical and chemical separation”, thus simplifying thepretreatment and operation procedures, reducing the analysis time and labor, andimproving the sensitivity and selectivity and enhancing the power of analyticalmethods. Corresponding optimal chemometric method should be selected according tothe different types of data for decomposition. This thesis combines different chemicalsecond-order calibration methods with the three-dimensional fluorescence andhyphenated chromatographic techniques to carry out the applicable researches infunctional food and body fluids for determination of the analytes of interest.A fast method of second-order calibration based on the alternating trilineardecomposition (ATLD) algorithm combined with high performance liquidchromatography with a diode array detector (HPLC-DAD) was established for thesimultaneous determination of eight flavonoids (rutin, quercetin, luteolin, kaempferol,isorhamnetin, apigenin, galangin and chrysin) in propolis capsules samples in Chapter2. The chromatographic separation was implemented on a WondasilTMC18column(250mm×4.6mm,5μm) within13min with a binary mobile phase composed ofwater with1%formic acid and methanol after flavonoids were only extracted withmethanol by ultrasound extraction for15min. The baseline problem was overcome byconsidering background drift as additional compositions as well as the target analytes,and ATLD was employed to handle the overlapping peaks from analytes of interest orfrom analytes and co-eluting matrix compounds. The method was successfully appliedto propolis capsules samples and the satisfactory results were obtained, whichindicate that the HPLC-DAD method with the aid of ATLD is efficient, sensitive and cost-effective and can realize the resolution and accurate determination of flavonoidseven in the presence of interferences, thus providing an alternative method usedespecially when the complete separation is not easily accomplished.Melatonin exhibits a multitude of biological and physiologicalproperties especially in improving the quality of sleep. In Chapter3,three-dimensional fluorescence spectroscopy combined with second-order calibrationmethod based on the alternating trilinear decomposition (ATLD) algorithm wasutilized to determine melatonin cotent in functional food. When the number ofcomponents was set to2, the results were accurate, reliable, high sensitive andsatisfactory. Besides, the method was also validated by high performance liquidchromatography and the results obtained by the two methods were compared by t-testand were found to be in good agreement with each other. And this method was moreenvironmentally friendlier, easier and free of interferences and so can be as analternative method for the determination of melatonin and be used to qualitymonitoring for functional food containing melatonin.Rosiglitazone (ROS) and gemfibmzil (GEM) are often used in combination forthe therapy of type II diabetes and its metabolic syndrome to control the levels ofhepatic glucose and serum triglyceride. In Chapter4, fluorescence spectroscopycombined with the second-order calibration method based on the self-weightedalternating trilineat decomposition (SWATLD) algorithm was utilized to fastdetermine rosiglitazone and gemfibmzil in the human serum. There was no anypretreatment process except for the protein precipitation. The recoveries for ROS andGEM were (97.8±1.2)%and (103.6±3.1)%, respectively. And their limits of detectionwere0.72and22ng mL-1, respectively. The results indicate that the method is simple,accurate and reliable even in the present of the unknown interferences, and thus canbe applied for the simultaneous determination of rosiglitazone and gemfibmzil in thehuman serum.Pteridinic family derivatives are extensively present in the human and animalorganisms and are very important cofactors in several cell metabolisms. They areexcreted in urine and its levels are related with activation of the cellular immunesystem. Significant change in the urinary excretion of pteridines was found in patientsuffering from cancer and other disease as reported, therefore these compounds can beconsidered as potential biomarkers of the cancer and other diseases for clinicaldiagnosis and monitoring. Chapter5takes advantages of the native fluorescence andpresents a method combing the three-dimensional fluorescence spectroscopy with the second-order calibration method based on the self-weighted alternating normalizedresidue fitting decomposition (SWANRF) for the determination of xanthopterin inhuman urine. This method need no any pretreatment procedures and can still givesatisfactory results in the presence of unknown interferences.