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Slowing starch digestibility can delay or even prevent the occurrence and development of type 2 diabetes. To explore the hypoglycemic potential of highland barley polyphenols (HBP), this study investigated the structural characteristics and starch digestibility of individual or mixed HBP-starch complexes. The results showed that a V-type structure was formed in HBP-starch complexes through non-covalent bonds, resulting in a decrease in rapidly digestible starch and an increase in resistant starch. Specially, the compounding of HBP extracted by acetone significantly reduced the rapidly digestible starch content in amylose from 41.11% to 36.17% and increased the resistant starch content from 6.15% to 13.27% (p &lt; 0.05). Moreover, due to different contents and types of monomer phenols, the HBP extracted with acetone were more effective in inhibiting starch digestion than those extracted with methanol. Ferulic acid and catechin were two key components of HBP. Further results indicated that with the increased content of ferulic acid and catechin (from 1% to 5%), they formed a more ordered structure with amylose, resulting in the lower digestibility of the complex. Collectively, this study suggested that highland barley polyphenols could effectively delay starch digestion by forming a more ordered starch crystal structure. Highland barley polyphenols can be used as functional ingredients in regulating the digestive properties of starchy foods.

Highland Barley Polyphenol Delayed the In Vitro Digestibility of Starch and Amylose by Modifying Their Structural Properties