Alternating trilinear decomposition (ATLD) algorithm is a promising method for second-order calibration, which is based on an alternating least-squares principle to overcome some shortcomings of the traditional parallel factor analysis (PARAFAC) algorithms, such as the sensitivity to the estimated component numbers and slow convergence. It utilizes an iterative procedure involving Moore-Penrose generalized inverse computations based on singular value decomposition and can be applied to the simultaneous determination of several organic components even in the presence of unknown interfering components. The overlapped chromatogram and spectra system of dihydroxybenzenes were resolved by ATLD combined with reversed-phase high performance liquid chromatography (RP-HPLC)/ diode array detection (DAD). The elution time was set from 1.086 min to 1.399 min with an interval of 1/150 min and the ultraviolet wavelength from 268 nm to 298 nm with an interval of 1 nm. The resolved results were in agreement with the actual results excellently. Catechol (CAT), resorcinol (RES) and hydroquinone (HYD) in aqueous solution were determined simultaneously, whose recoveries were (100.1 +/- 1.0)%, (99.4 +/- 1.4)% and (100.5 +/- 1.7)%, respectively. The results showed this experiment can be easily performed without resorting to time-consuming and complicated procedures and quantified accurately. It successfully solved the resolving problem caused by chromatogram and spectra overlapping in the presence of interfering components. It also revealed the ATLD algorithm can be efficiently applied to solve the second-order calibration problem in HPLC-DAD.
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