The starch−phenolics complexes are widely fabricated as functional foods but with low phenolics retention limited by traditional liquid reaction and washing systems. In this study, ferulic acid (FA, 5%) was exogenously used in the crystalline form, and it reacted with starch in a high-solid extrusion environment, which was simultaneously controlled by thermostable α-amylase (0−252 U/g). Moderate enzymolysis (21 or 63 U/g) decreased the degree of the starch double helix and significantly increased the FA retention rate (>80%) with good melting and distribution. Although there were no significantly strong chemical bonds (with only 0.17−2.39% FA bound to starch hydrolysate), the noncovalent interactions, mainly hydrogen bonds, van der Waals forces, and electrostatic interactions, were determined by 1 H NMR and molecular dynamics simulation analyses. The phased release of total FA (>50% in the stomach and ∼100% in the intestines) from bioextrudate under in vitro digestion conditions was promoted, which gives a perspective for handing large loads of FA and other phenolics based on starch carrier.
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