Starch retrogradation is a complex process involving changes in the multi-scale structure. In particular, the particle order of retrograded starch is unclear. In this study, we measured the radius of gyration (R_g) and radius of particles (R) of retrograded starch using small-angle X-ray scattering. Retrograded starch included various R_g, and the values of R_g depended on the length and state of the starch chains. With time, the standard deviations of R decreased due to the increase in particle uniformity. Based on these results, a new method for assessing the degree of starch retrogradation was established from the perspective of the particle order. The accuracy of the new method was verified through differential scanning calorimetry and scanning electron microscopy. The microstructures of the samples indicated that the retrograded starch granules contained substructures (primary particles) of different sizes. This study provides a new perspective for analyzing the structure of retrograded starch.

Starch–polyphenol interactions play a critical role in regulating the structural organization and thermal behavior of starch-based systems. In this study, maize starches with different amylose contents were used to systematically investigate how tea polyphenol (TP) complexation influences starch structure and thermal stability. Starch–TP complexes were prepared under thermal-induced conditions and characterized using thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). TGA results showed that increasing amylose content slightly reduced the thermal stability of native starches, whereas TP incorporation significantly enhanced thermal resistance, particularly in high-amylose systems. XRD analysis indicated that TP complexation did not affect the crystal structure of starch but led to a pronounced reduction in relative crystallinity, with low-amylose complexes exhibiting predominantly amorphous behavior and high-amylose complexes retaining partial nanocrystalline organization. FTIR spectra revealed reduced short-range molecular order and strengthened hydrogen bonding interactions after TP binding. DSC analysis demonstrated increased gelatinization temperatures accompanied by decreased enthalpy changes, reflecting restricted molecular mobility and delayed solvation of nanocrystalline domains. SEM observations further showed a transition toward denser and more interconnected micro–nano structures with increasing amylose content. Overall, TP preferentially interacts with amylose-rich regions through non-covalent interactions, promoting structural reorganization and enhanced thermal stability of the starch matrix. These findings provide new insight into amylose-dependent starch–polyphenol interactions and offer guidance for designing thermally stable starch-based functional materials.