Summary Liquid chromatography coupled with tandem mass spectrometry (LC–MS/MS) was employed to investigate free phenols that were released from purple sweet potato (PSP) by alkaline, acid and enzymatic hydrolysis. Four phenolic acids, including ferulic, isoferulic, 4‐hydroxybenzoic and caffeic acids, were identified. Based on their effects on the characteristics of purple sweet potato starch (PSPS), the four phenolic acids were studied. Furthermore, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT–IR) and X‐ray diffraction (XRD) techniques were employed to explore the microstructures of the complexes of the phenolic acids and PSPS. The obtained results demonstrated that the pasting, thermal, retrogradation, as well as digestive properties of PSPS were all influenced by the phenolic acids which interacted with PSPS through noncovalent hydrogen bonds. The influence of the four phenolic acids on the properties of PSPS was in the descending order: 4‐hydroxybenzoic acid > ferulic acid > caffeic acid > isoferulic acid.
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