Self-weighted Alternating Trilinear Decomposition Algorithm Research Articles

Interference-free spectrofluorometric quantification of aristolochic acid I and aristololactam I in five Chinese herbal medicines using chemical derivatization enhancement and second-order calibration methods

A rapid interference-free spectrofluorometric method combined with the excitation-emission matrix fluorescence and the second-order calibration methods based on the alternating penalty trilinear decomposition (APTLD) and the self-weighted alternating trilinear decomposition (SWATLD) algorithms, was proposed for the simultaneous determination of nephrotoxic aristolochic acid I (AA-I) and aristololactam I (AL-I) in five Chinese herbal medicines. The method was based on a chemical derivatization that converts the non-fluorescent AA-I to high-fluorescent AL-I, achieving a high sensitive and simultaneous quantification of the analytes. The variables of the derivatization reaction that conducted by using zinc powder in acetose methanol aqueous solution, were studied and optimized for best quantification results of AA-I and AL-I. The satisfactory results of AA-I and AL-I for the spiked recovery assay were achieved with average recoveries in the range of 100.4–103.8% and RMSEPs <0.78ngmL−1, which validate the accuracy and reliability of the proposed method. The contents of AA-I and AL-I in five herbal medicines obtained from the proposed method were also in good accordance with those of the validated LC-MS/MS method. In light of high sensitive fluorescence detection, the limits of detection (LODs) of AA-I and AL-I for the proposed method compare favorably with that of the LC-MS/MS method, with the LODs <0.35 and 0.29ngmL−1, respectively. The proposed strategy based on the APTLD and SWATLD algorithms by virtue of the “second-order advantage”, can be considered as an attractive and green alternative for the quantification of AA-I and AL-I in complex herbal medicine matrices without any prior separations and clear-up processes.

Detection of Methamphetamine and Morphine in Urine and Saliva Using Excitation–Emission Matrix Fluorescence and a Second-Order Calibration Algorithm

A new method was developed to determine the methamphetamine and morphine concentrations in urine and saliva based on excitation–emission matrix fluorescence coupled to a second-order calibration algorithm. In the case of single-drug abuse, the results showed that the average recoveries of methamphetamine and morphine were 95.3 and 96.7% in urine samples, respectively, and 98.1 and 106.2% in saliva samples, respectively. The relative errors were all below 5%. The simultaneous determination of methamphetamine and morphine in urine using two second-order algorithms was also investigated. Satisfactory results were obtained with a self-weighted alternating trilinear decomposition algorithm. The root-mean-square errors of the predictions were 0.540 and 0.0382 μg/mL for methamphetamine and morphine, respectively. The limits of detection of the proposed methods were very low and sufficient for studying methamphetamine and morphine in urine.

Identification and Determination of Oil Pollutants Based on 3-D Fluorescence Spectrum Combined with Self-weighted Alternating Trilinear Decomposition Algorithm

Oil pollution seriously endangers the biological environment and human health. Due to the diversity of oils and the complexity of oil composition, it is of great significance to identify the oil contaminants. The 3-D fluorescence spectrum combined with a second order correction algorithm was adopted to measure an oil mixture with overlapped fluorescence spectra. The self-weighted alternating trilinear decomposition (SWATLD) is a kind of second order correction, which has developed rapidly in recent years. Micellar solutions of #0 diesel, #93 gasoline and ordinary kerosene in different concentrations were made up. The 3-D fluorescence spectra of the mixed oil solutions were measured by a FLS920 fluorescence spectrometer. The SWATLD algorithm was applied to decompose the spectrum data. The predict concentration and recovery rate obtained by the experiment show that the SWATLD algorithm has advantages of insensitivity to component number and high resolution for mixed oils.

Advanced chemometric algorithm coupled to subspace projection technique between original and pseudo samples: A snapshot of chemical rank estimation for high-order data

A new method, “advanced chemometric algorithm coupled to subspace projection technique between original and pseudo samples (ACA-SPOPS)”, is proposed for the first time for chemical rank estimation of three-way data arrays. In ACA-SPOPS, self-weighted alternating trilinear decomposition (SWATLD) algorithm is used to create pseudo samples to produce a pseudo array. Singular value decomposition (SVD) is then performed on the unfolded matrices of both pseudo array and original array. The chemical rank can be accordingly determined via the subspace projection technique. The performance of ACA-SPOPS has been demonstrated by both simulated and experimental data arrays. By comparing with four other widely used methods, namely core consistency diagnostic (CORCONDIA) test, ADD-ONE-UP truncating and fitting (ADD-ONE-UP), two-mode subspace comparison (TMSC) and subspace projection of pseudo high-way data array (SPPH), the results showed that this new method possessed better analytical performance than many other ones, in terms of noise, collinearity, concentration and computation speed. Moreover, the ACA-SPOPS method may be further applied for processing higher-order data arrays by accordingly extending the SWATLD algorithm to higher dimensions.

Simultaneous determination of pre-emergence herbicides in environmental samples using HPLC-DAD combined with second-order calibration based on self-weighted alternating trilinear decomposition algorithm

This work presents a novel strategy for simultaneous and rapid quantitative analysis of three pre-emergence herbicides in environmental samples using HPLC-DAD combined with second-order calibration based on the self-weighted alternating trilinear decomposition (SWATLD) algorithm. The sample preparation procedure was simplified only by using water as solvent and methanol as extractant and data were measured in less than 4.2 min by applying an isocratic mode. Although the elution and spectral profiles of the analytes, prometryne (PRO), napropamide (NAP) and alachlor (ALA), are heavily overlapped with each other and with matrix constitutes, the method not only extracts the profiles of the analytes, but also simultaneously determines the concentrations of them in actual complex systems, i.e., river sediment and wastewater samples. In the analysis of river sediment and wastewater samples, the obtained average recoveries were 99 ± 6% and 98 ± 5% for PRO, 108 ± 6% and 100 ± 4% for NAP and 98 ± 5% and 97 ± 4% for ALA, respectively. Furthermore, the accuracy and precision of the proposed method was also evaluated through elliptical joint confidence region tests as well as figures of merit. Such a chemometrics-based protocol may be a very promising tool for more analytical applications in environment monitoring, due to its advantages of easy sample pretreatment, green, sufficient spectral resolution and concentration prediction even in the presence of unknown interferences.

Two different strategies for the fluorimetric determination of piroxicam in serum

Two different spectrofluorimetric methods for the determination of piroxicam (PX) in serum are presented and discussed. One of them is based on the use of three-way fluorescence data and multivariate calibration performed with parallel factor analysis (PARAFAC) and self-weighted alternating trilinear decomposition (SWATLD). This methodology exploits the so-called second-order advantage of the three-way data, allowing to obtain the concentration of the studied analyte in the presence of any number of uncalibrated (serum) components. The method was developed following two different procedures: internal standard addition and external calibration with standard solutions, which were compared and discussed. The second approach investigated is based on the combination of solid-phase extraction (SPE) and room temperature fluorimetry. Both methods here presented yield satisfactory results. The concentration range in which PX could be determined in serum was 1–10 μg ml −1. The limits of quantification for the experimental solutions using the chemometric approach were 0.09 μg ml −1 for the standard addition mode and 0.12 μg ml −1 using external calibration (both for PARAFAC and SWATLD algorithms). In the solid-surface fluorimetric method, the calibration graph was linear up to 0.22 μg ml −1 and the limit of quantification was 0.02 μg ml −1.