| Chemometrics is an interdisciplinary field, which aims at handling the abundantinformation provided by modern analytical instruments. A lot of valuablechemometrics algorithms have been developed to extract the useful information ofanalytes in complex matrix systems efficiently. Particularly, owing to the“second-order advantage”, the three-way second-order calibration methods make thedirect qualitative and quantitative analysis of target analytes possible even in thepresence of unknown interferences. To gain more advantages, the four-waythird-order calibration methods have been put forward in recent years. Nowadays, theapplications of multi-way calibration methodologies in complex matrix have becomean active domain, such as pharmaceutical chemistry, food chemistry andenvironmental chemistry. In this paper, the authors focused attention on theapplications of multi-way calibration methodologies in quantitative analysis ofantihypertensives and local anesthesia in biological matrix and pharmaceuticalpreparations.1. Ligustrazine and Telmisartan can be used as a combination therapy for diabeticnephropathy, which have beneficial effects on cardiovascular system. In Chapter2,we proposed a new rapid approach for quantitative analysis of Ligustrazine andTelmisartan in human plasma samples by the incorporation of excitation-emissionmatrix fluorescence (EEM) and second-order calibration methodology based on thealternating normalization-weighted error (ANWE) algorithm. Meanwhile, the methodwas also utilized to quantify Telmisartan in tablets and the result was validated by thehigh-performance liquid chromatography with fluorescence detection. Thesatisfactory experimental results demonstrated that the proposed method may beexpected to provide a new powerful tool for clinical medicine analysis.2. Amlodipine, a calcium channel blocker (CCB), and Valsartan, an angiotensinII receptor blocker (ARB), are powerful long-term medicine for antihypertension andhave beneficial effects on cardiovascular and renal organs. Exforge is a fixed-dosecombination of Amlodipine and Valsartan, and also is the first ARB/CCB fixedpharmaceutical preparation, which is supposed to be an effective drug. However, themechanism of co-administrated drugs and their interactions with the target organ arenot well known. Besides, monitoring the qualities of pharmaceutical preparation inthe market is a work of great importance. In Chapter3, taking advantage of the fluorescent properties of the two agents, EEM coupled with second-order calibrationmethod was developed to qualitative and quantitative analysis of Amlodipine andValsartan in human plasma and Exforge.3. In Chapter4, a novel chemometric-assisted high performance liquidchromatography method coupled with diode array detector (HPLC-DAD) waspresented for the simultaneous determination of eleven antihypertensives frommultiple classes in most concerned matrix systems. With the aid of second-ordercalibration which enables specific information of analytes to be well extracted, theheavily overlapping profiles between analytes and the coeluting interferences can besuccessfully separated and thus accurately quantified. A great advantage of the novelstrategy lies in the fact that the analysis could be carried out with the same isocraticmobile phase (methanol/KH2PO4:58:42, v/v, pH=2.60) in a short time regardless ofthe changes of matrices, such as human serum, health product and Chinese patentmedicine. Both the qualitative and the quantitative results indicate that the hybridstrategy that using HPLC-DAD coupled with second-order chemometric methodwould be a high performance approach for the purpose of simultaneously quantifyingmultiple classes of antihypertensives in complex systems. Additionally, the analyticalstrategy can potentially benefit drug monitoring in both therapeutic research andpharmaceutical quality control. Moreover, the accuracy and reliability of the proposedmethodology has been evaluated using several statistical parameters such as rootmean squared error of prediction (RMSEP), figures of merit (FOM) andreproducibility of inter-day analysis.4. Procaine and Tetracaine are commonly used as ester local anesthetics. Due tothe similarity of the two agents, it is not an easy task to analyze them togetherespecially in complex biofluid system. Both of them are sensitive to changes in pHand their fluorescence intensities will change according to different pH values. InChapter5, we introduced pH dimension as the fourth dimension, Four-wayPARAFAC algorithm was utilized to resolve the excitation-emission-pH-samplesdataset recorded from human plasma matrix. This work may serve as anotherapplication example of third-order calibration methods as well as a complementary ofour previous work. |
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