Investigation of the effect of ultrasonication on starch-fatty acid complexes and the stabilization mechanism.

The complexation of physically modified starch with fatty acids is favorable for the production of resistant starch. However, there is a lack of information on the effect of ultrasonication (UC) on the structure and properties of starch complexes and the molecular mechanism of the stabilization. Here, the multi-scale structure and in vitro digestive properties of starch-fatty acid complexes before and after UC were investigated, and the stabilization mechanisms of starch and fatty acids were explored. The results showed that the physicochemical properties and multi-scale structure of the starch-fatty acid complexes significantly changed with the type of fatty acids. The solubility and swelling power of the starch-fatty acid complexes were significantly decreased after UC (P < 0.05), which facilitated the binding of starch with fatty acids. The XRD results revealed that after the addition of fatty acids, the starch-fatty acid complexes showed typical V-shaped complexes. In addition, the starch-fatty acid complexes showed a significant increase in complexing index, improved short-range ordering and enhanced thermal stability. However, the differences in the structure and properties of the fatty acids themselves resulted in no significant improvement in the multi-scale structure of maize starch-palmitic acid by UC. In terms of digestibility, especially the complexes after UC were more compact in structure, which increased the difficulty of enzymatic digestion and thus slowed down the digestion process. DFT calculations and combined with FT-IR analysis showed that non-covalent interactions such as hydrogen bonding and hydrophobic interactions were the main driving force for the formation of the complexes, with binding energies (lauric acid, myristic acid and palmitic acid) of -30.50, -22.14 and -14.10 kcal/mol, respectively. Molecular dynamics simulations further confirmed the molecular mechanism of inclusion complex formation and stabilization. This study is important for the regulation of starchy foods by controlling processing conditions, and provides important information on the role of fatty acids in the regulation of starch complexes and the binding mechanism.

Mechanism of interaction between L-theanine and maize starch in ultrasonic field based on DFT calculations: Rheological properties, multi-scale structure and in vitro digestibility.

The digestibility of starch-based foods is receiving increased attention. To date, the full understanding of how including L-theanine (THE) can modify the structural and digestive properties of starch has not been fully achieved. Here, we investigated the multi-scale structure and digestibility of maize starch (MS) regulated by THE in ultrasound field and the molecular interactions. Ultrasound disrupted the structure of starch granules and opened the molecular chains of starch, promoting increased THE binding and producing more low-order or disordered crystal structures. In this case, the aggregation of starch molecules, especially amylose, was reduced, leading to increased mobility of the systems. As a result, the apparent viscosity, G', and G" were significantly decreased, which retarded the starch regeneration. Density functional theory calculations indicated that there were mainly non-covalent interactions between THE and MS, such as hydrogen bonding and van der Waals forces. These interactions were the main factors contributing to the decrease in the short-range ordering, the helical structure, and the enthalpy change (ΔH) of MS. Interestingly, the rapidly digestible starch (RDS) content of THE modified MS (MS-THE-30) decreased by 17.89 %, while the resistant starch increased to 26.65 %. These results provide new strategies for the safe production of resistant starch.