A novel chromatographic peak alignment method coupled with trilinear decomposition for three dimensional chromatographic data analysis to obtain the second-order advantage.

The alignment of chromatographic peaks and deconvolution of overlapped peaks still remain challenges in the field of complex sample analysis. In this paper, we highlight a strategy that employs a new time shift alignment method derived from the well-known Rank Minimization method for aligning chromatographic peak shifts among samples and then uses trilinear decomposition methodology to interpret the overlapped chromatographic peaks in order to quantify analytes of interest. The performance of this novel strategy for chromatographic data analysis was evaluated using simulated chromatographic data as well as real chromatographic data. The results indicate that the new time shift alignment method can accurately correct time shifts in test samples even in the presence of unexpected interferences, and thus the low-rank trilinearity of the same analyte can be obtained, which will be helpful for trilinear decomposition to achieve the second-order advantage. Moreover, the results showed that this new alignment method is more automated in comparison with the Rank Minimization method and will be suitable for the alignment of the time shifts of analytes that are completely overlapped by coeluted interferences.

Chromatographic background drift correction coupled with parallel factor analysis to resolve coelution problems in three-dimensional chromatographic data: quantification of eleven antibiotics in tap water samples by high-performance liquid chromatography coupled with a diode array detector.

Chromatographic background drift correction has been an important field of research in chromatographic analysis. In the present work, orthogonal spectral space projection for background drift correction of three-dimensional chromatographic data was described in detail and combined with parallel factor analysis (PARAFAC) to resolve overlapped chromatographic peaks and obtain the second-order advantage. This strategy was verified by simulated chromatographic data and afforded significant improvement in quantitative results. Finally, this strategy was successfully utilized to quantify eleven antibiotics in tap water samples. Compared with the traditional methodology of introducing excessive factors for the PARAFAC model to eliminate the effect of background drift, clear improvement in the quantitative performance of PARAFAC was observed after background drift correction by orthogonal spectral space projection.

Simultaneous determination of plant growth regulators in environmental samples using chemometrics-assisted excitation-emission matrix fluorescence: experimental study on the prediction quality of second-order calibration method.

In this work, with the purpose of developing an effective and inexpensive method, excitation-emission matrix fluorescence data and second-order calibration method based on the self-weighted alternating trilinear decomposition (SWATLD) algorithm were combined for simultaneous determination of 2-naphthoxyacetic acid (NOA) and 1-naphthaleneacetic acid methyl ester (NAAME) in environmental samples, i.e. soil and sewage samples. In order to investigate the prediction quality of the proposed method, different strategies, such as taking spectroscopic measurements in the presence of different matrix interferents and at different fluorescence spectrophotometers, were introduced to build calibration models and comparisons among them were done subsequently. The root-mean-square error of prediction and t-test were used to compare different SWATLD-based calibration models. The limits of detection obtained for NOA and NAAME were 0.36-0.95 ng mL(-1) and 1.32-2.69 ng mL(-1), respectively, for different models. Such a chemometrics-based protocol may possess great potential to be extended as a promising alternative for more practical applications in environment monitoring and for the design of small intelligent and field-portable analytical instruments that rely on statistical discrimination, not complete instrumental separation, of the target analytes even in the presence of unknown and uncalibrated interferences.

The maintenance of the second-order advantage: second-order calibration of excitation-emission matrix fluorescence for quantitative analysis of herbicide napropamide in various environmental samples.

A rapid non-separative spectrofluorometric method based on the second-order calibration of excitation-emission matrix (EEM) fluorescence was proposed for the determination of napropamide (NAP) in soil, river sediment, and wastewater as well as river water samples. With 0.10 mol L(-1) sodium citrate-hydrochloric acid (HCl) buffer solution of pH 2.2, the system of NAP has a large increase in fluorescence intensity. To handle the intrinsic fluorescence interferences of environmental samples, the alternating penalty trilinear decomposition (APTLD) algorithm as an efficient second-order calibration method was employed. Satisfactory results have been achieved for NAP in complex environmental samples. The limit of detection obtained for NAP in soil, river sediment, wastewater and river water samples were 0.80, 0.24, 0.12, 0.071 ng mL(-1), respectively. Furthermore, in order to fully investigate the performance of second-order calibration method, we test the second-order calibration method using different calibration approaches including the single matrix model, the intra-day various matrices model and the global model based on the APTLD algorithm with nature environmental datasets. The results showed the second-order calibration methods also enable one or more analyte(s) of interest to be determined simultaneously in the samples with various types of matrices. The maintenance of second-order advantage has been demonstrated in simultaneous determinations of the analyte of interests in the environmental samples of various matrices.

Quantitative analysis of levodopa, carbidopa and methyldopa in human plasma samples using HPLC-DAD combined with second-order calibration based on alternating trilinear decomposition algorithm.

An HPLC method combined with second-order calibration based on alternating trilinear decomposition (ATLD) algorithm has been developed for the quantitative analysis of levodopa (LVD), carbidopa (CBD) and methyldopa (MTD) in human plasma samples. Prior to the analysis of the analytes by ATLD algorithm, three time regions of chromatograms were selected purposely for each analyte to avoid serious collinearity. Although the spectra of these analytes were similar and interferents coeluted with the analytes studied in biological samples, good recoveries of the analytes could be obtained with HPLC-DAD coupled with second-order calibration based on ATLD algorithm, additional benefits are decreasing times of analysis and less solvent consumption. The average recoveries achieved from ATLD with the factor number of 3 (N=3) were 100.1+/-2.1, 96.8+/-1.7 and 104.2+/-2.6% for LVD, CBD and MTD, respectively. In addition, elliptical joint confidence region (EJCR) tests as well as figures of merit (FOM) were employed to evaluate the accuracy of the method.

Quantitative analysis of triazine herbicides in environmental samples by using high performance liquid chromatography and diode array detection combined with second-order calibration based on an alternating penalty trilinear decomposition algorithm.

A novel application of second-order calibration method based on an alternating penalty trilinear decomposition (APTLD) algorithm is presented to treat the data from high performance liquid chromatography-diode array detection (HPLC-DAD). The method makes it possible to accurately and reliably analyze atrazine (ATR), ametryn (AME) and prometryne (PRO) contents in soil, river sediment and wastewater samples. Satisfactory results are obtained although the elution and spectral profiles of the analytes are heavily overlapped with the background in environmental samples. The obtained average recoveries for ATR, AME and PRO are 99.7±1.5, 98.4±4.7 and 97.0±4.4% in soil samples, 100.1±3.2, 100.7±3.4 and 96.4±3.8% in river sediment samples, and 100.1±3.5, 101.8±4.2 and 101.4±3.6% in wastewater samples, respectively. Furthermore, the accuracy and precision of the proposed method are evaluated with the elliptical joint confidence region (EJCR) test. It lights a new avenue to determine quantitatively herbicides in environmental samples with a simple pretreatment procedure and provides the scientific basis for an improved environment management through a better understanding of the wastewater-soil-river sediment system as a whole.

Interference-free determination of and in plant samples using excitation-emission matrix fluorescence based on oxidationderivatization coupled with second-order calibration methods.

A sensitive excitation-emission fluorescence method with a second-order calibration strategy is proposed to simultaneously determine abscisic acid (ABA) and gibberellin (GA) contents in extracts of leaves and buds of ginkgo. The methodology is based on the alternating normalization-weighed error (ANWE) and the parallel factor analysis (PARAFAC) algorithms, which make it possible that the ABA and GA concentration can be attained in extract of plants even in the presence of unknown interference from potential interfering matrix contaminants introduced during the simple pretreatment procedure. Satisfactory recoveries were obtained although the excitation and emission profiles of the analytes were heavily overlapped with each other and the background in the extracts. The limits of detection obtained for GA and ABA in leaf samples were 9.6 and 6.9 ng mL-1, respectively, which were in the concentration range (from hundreds to several ng g-1) for GA and ABA in leaves in different periods. Furthermore, in order to investigate the performance of the developed method, some statistical parameters and figures of merit of ANWE and PARAFAC are evaluated. The method proposed lights a new avenue to determine quantitatively phytohormones in extracts of plants with a simple pretreatment procedure, and may hold potential to be extended as a promising alternative for more practical applications in plant growth processes.

Determination of indole-3-acetic acid in soil using excitation-emission matrix fluorescence with trilinear decomposition-based calibration methods.

Indole-3-acetic acid (IAA) is a phytohormone of the auxin group and is capable of coordinating the overall processes of plant growth and development. IAA is active in the very low concentration range. Therefore, it is important to quantify IAA in the low concentration range in complex system. In this work, a new spectrofluorometric method for the direct determination of IAA in soil is proposed and discussed. It combines the fluorescence excitation-emission matrices (EEMs) with second-order calibration methods based on the alternating trilinear decomposition (ATLD) algorithm and the self-weighed alternating trilinear decomposition (SWATLD) algorithm. These methodologies fully exploit the second-order advantage of the three-way fluorescence data, allowing the analyte concentrations to be quantified even in the presence of unknown fluorescent interferents. IAA recoveries in soil were determined as 100.6 +/- 3.0 and 96.9 +/- 1.1% with ATLD and SWATLD, respectively. The limits of detection obtained were 17.6 and 4.6 ng mL(-1), and the limits of quantification were 52.9 and 13.9 ng mL(-1) with ATLD and SWATLD, respectively.