Five-way high performance liquid chromatography–diode array detection (HPLC–DAD)–kinetic-pH data were obtained by recording the kinetic evolution of HPLC–DAD signals of samples at different pH values and a new fourth-order calibration method, alternating quinquelinear decomposition (AQQLD) based on pseudo-fully stretched matrix forms of the quinquelinear model, was developed. Simulated data were analyzed to investigate the performance of AQQLD in comparison with five-way parallel factor analysis (PARAFAC). The tested results demonstrated that AQQLD has the advantage of faster convergence rate and being insensitive to the excess component number adopted in the model. Then, they have been successfully applied to investigate quantitatively the kinetics of naptalam (NAP) hydrolysis in two practical systems. Additionally, the serious chromatographic peak shifts were accurately corrected by means of chromatographic peak alignment method based on abstract subspace difference. The good recoveries of NAP were obtained in these samples by selecting the time region of chromatogram. The elution time, spectral, kinetic time and pH profiles resolved by the chemometric techniques were in good agreement with experimental observations. It demonstrates the potential for the utilization of fourth-order data for some complex systems, opening up a new approach to fourth-order data generation and subsequent fourth-order calibration.
Fu-Xin Wang,Yang Chen,Yan-Mei Liang,Min Yang,Chao Kang
Aromatic amino acids play an extremely important role in life activities and participate in many biological processes. Their concentration levels are associated with a variety of diseases, such as phenylketonuria and colorectal cancer. Therefore, the quantification of aromatic amino acids is an important task. In the present work, a novel and rapid three-way analytical method was proposed to detect the levels of aromatic amino acids in prostate cancer cells (PC3 cells) and Dulbecco's modified minimal essential medium (DMEM cell culture), by using the affordable ultraviolet–visible spectrophotometer. First, spectrum-pH second-order data were designed per sample; Second, properties of the resulted spectrum-pH-sample three-way data were investigated by utilizing the parallel factor analysis (PARAFAC), alternating trilinear decomposition (ATLD), and constrained alternating trilinear decomposition (CATLD) algorithms, and a flexible scanning approach for determining the constraint parameters of CATLD was proposed; Third, a three-way calibration method based on the CATLD algorithm with the proposed scanning approach was developed for interference-free quantification of aromatic amino acids in these systems. The average relative predictive errors of validation (ARPEV) for phenylalanine, tyrosine, and tryptophan were 1.4%, 3.0%, and 0.7% in prostate cancer cells, and ARPEV for phenylalanine, tyrosine, and tryptophan were 4.1%, 1.2%, and 0.7% in DMEM cell culture. The predicted contents of tyrosine and tryptophan in DMEM cell culture were 64.2 ± 2.9 μg mL −1 , 5.6 ± 0.3 μg mL −1 , there are no significant differences in the concentrations between the developed analytical method and high performance liquid chromatography method. The proposed spectrum-pH-sample three-way calibration method based on CATLD algorithm can provide an interesting analytical strategy with high selectivity and accuracy for ultraviolet–visible spectrophotometer.
危险品化学品经营许可证（带存储）