Analysis of active compounds and geographical origin discrimination of Atractylodes macrocephala Koidz. by using high performance liquid chromatography-diode array detection fingerprints combined with chemometrics.

In this work, a simple and effective strategy for the determination of 12 active compounds of Atractylodes macrocephala Koidz. (AM) was proposed by using high performance liquid chromatography-diode array detection (HPLC-DAD) combined with alternating trilinear decomposition (ATLD) algorithm. Utilizing the "second-order advantage", three common problems in HPLC could be resolved, namely baseline drifts, peak overlaps, and unknown interferences. 12 compounds were rapidly eluted within 12.5 min, and the average spiked recoveries were 80.8-109.9%. The figures of merit reflected the feasibility of the proposed method. Compared with the results of the traditional univariate calibration method based on HPLC-UV technique, the proposed strategy further verified the reliability and simplicity of the mathematical separation. On this basis, partial least squares-discriminant analysis (PLS-DA) was applied to discriminate 113 AM samples from different geographical origins, and variable importance in projection (VIP) was used to further screen the main differential components that affect the regional division of AM. A series of results show that the AM samples from the three regions have obviously different clustering trends. Overall, the strategy is expected to provide a scientific basis for the modern research of medicinal materials, and it is also conducive to the clinical use and market supervision of AM.

Rapid determination of sulfamethoxazole and trimethoprim illegally added to health products using excitation-emission matrix fluorescence coupled with the second-order calibration method.

In this work, a simple and fast analytical method based on a self-weighted alternating trilinear decomposition (SWATLD) algorithm coupled with excitation-emission matrix (EEM) fluorescence was developed for the simultaneous determination of sulfamethoxazole (SMZ) and trimethoprim (TMP) illegally added to health products. With the second-order advantage, the proposed method obtained satisfactory results in the presence of peak overlap and unknown interferences. The analysis time for a single sample is only 0.8 minutes. The average spiked recoveries of SMZ and TMP in three health product spiked samples were in the range of 91.0-106.2% and 86.8-107.8%, respectively. The relative standard deviations (RSDs) were lower than 8.6%. In addition, verification parameters including sensitivity (SEN), selectivity (SEL), the limit of detection (LOD), the limit of quantification (LOQ), intra-day precision, and inter-day precision were calculated, and the results show that the proposed method is feasible. The quantitative results of the proposed method were further confirmed by the LC-MS/MS method, which proved that the proposed method was efficient and green for drug-abuse monitoring of SMZ and TMP in health products.

Simultaneous determination of nine tyrosine kinase inhibitors in three complex biological matrices by using high-performance liquid chromatography-diode array detection combined with a second-order calibration method.

An intelligent chemometric second-order calibration method called alternating trilinear decomposition- assisted multivariate curve resolution combined with high-performance liquid chromatography-diode array detection was used for the simultaneous quantification of nine tyrosine kinase inhibitors in three complex biological systems. The method allows simultaneous quantification of the components in different biological matrices without the need for cumbersome pre-treatment steps, complex elution conditions, and complete peak separation. Even with the varying time shift, severe peak overlap, and various unknown interferences, the proposed method can extract pure chromatographic and spectroscopic information for each analyte, while providing accurate qualitative and quantitative results of nine common tyrosine kinase inhibitors in three different biological matrices. All the drugs were eluted in 7 min. The results showed that the nine drugs in each matrix showed good linearity (r > 0.984) in the calibration range with a root mean square error of calibration less than 0.9 µg/mL. The average spiked recoveries of the target analytes were all in the range of 83.4-110.0%, with standard deviations less than 9.0%. Finally, the classical method was used to validate the proposed method. In comparison to the traditional method, the proposed strategy is accuracy, simultaneous, and interference-free.

Three efficient chemometrics assisted fluorimetric detection methods for interference-free, rapid, and simultaneous determination of ibrutinib and pralatrexate in various complicated biological fluids.

In this study, a series of green, interference-free fluorimetric detection methods of the excitation-emission matrix coupled with the second-order calibration methods were proposed for the determination of ibrutinib and pralatrexate in various complicated biological fluids. The second-order advantage of the proposed method can overcome the problem of poor selectivity caused by the wide spectra of the fluorescence method. Even in the presence of uncalibrated interferences and severe peak overlap, the signal of pure substance and accurate quantitative results were still obtained. The average recoveries of the three methods were 94.5-104.9% for Alternating Trilinear Decomposition (ATLD) algorithm, 95.5-105.8% for Alternating Normalization Weighted Error (ANWE) algorithm and 94.4-105.7% for Parallel Factor Analysis (PARAFAC) algorithm, respectively. For ATLD, ANWE and PARAFAC, the relative standard deviations (RSD) were lower than 9.2%, 6.8% and 9.2%, and the RMSEPs were less than 8.1, 8.4 and 8.6 ng mL-1, respectively. In addition, the elliptic joint confidence region (EJCR) was adopted to further prove the accuracy of the three methods. The results showed that the three methods can accurately be quantified without significant difference. Good figures of merit parameters were also obtained. Among them, the limit of detection (LOD) and limit of quantification (LOQ) of ibrutinib and pralatrexate were in the range of 0.11-0.76 ng mL-1 and 0.21-1.12 ng mL-1, respectively, which were lower than the corresponding blood concentrations. These results indicate that the proposed method provides a promising, alternative and universal analysis strategy for clinical drug monitoring.

Comparison of three chemometric methods for processing HPLC-DAD data with time shifts: Simultaneous determination of ten molecular targeted anti-tumor drugs in different biological samples.

Three intelligent chemometric multi-way calibration methods including alternating trilinear decomposition (ATLD), alternating trilinear decomposition assisted multivariate curve resolution (ATLD-MCR) and multivariate curve resolution-alternating least squares (MCR-ALS) combined with high performance liquid chromatography-diode array detection (HPLC-DAD) were used to quantify ten molecular targeted anti-tumor drugs in three complex biological matrices (plasma, urine and cell culture media matrices). All analytes can be successfully eluted in 6.5 min. In this experiment, various degrees of time shifts occurred in different samples. While slight time shifts exist in the chromatographic analysis, satisfactory results can be obtained by the three proposed methods. When the time shift was large (5.6 s), the average spiked recoveries obtained by ATLD analysis were in the range of 58.9%-116.5%, which was less than satisfactory. However, the average recoveries obtained by MCR-ALS and ATLD-MCR analysis were 89.8%-114.8% and 84.5%-106.1% respectively, and more satisfactory results were obtained. For further research, ATLD-MCR and MCR-ALS methods were compared, and the results were evaluated by statistical tests. Accuracies of concentrations obtained by them were considered to be no significant difference. In addition, compared with other methods currently published, the proposed chemometric methods combined with the HPLC-DAD can rapidly, simultaneously and accurately determine varieties of molecular targeted anti-tumor drugs in different complex biological matrices even in the presence of severe peak overlaps, severe time shifts, slight baseline drifts and different unknown background interferences.