Processing starch with polysaccharides promotes broader applications, and it is important to consider all possible structural interactions among the molecular ingredients. In this study, polysaccharides isolated from Lycium barbarum L. were chemically modified by sulphation (SLP) and carboxymethylation (CLP), and the effects on the gelatinisation, retrogradation, and digestibility properties of the potato starch were investigated. After chemical modification, the slope of the curve between the molar mass and molecular radius of polysaccharides decreased, revealing that the relatively rigid rod-like structure of native polysaccharide (0.78) changed to SLP's random linear chain (0.53) and CLP's spherical conformation (0.23), and the water solubility increased from 63.6% to 70.4% (SLP) and 84.1% (CLP) in distilled water at 25 degrees C. Moreover, testing polysaccharides as an additive indicated that both derivatives significantly decreased the peak viscosity, breakdown, and setback viscosity during potato starch pasting. Furthermore, the possible interactions could be further examined by structure analyses, suggesting the polysaccharide and SLP hydrogen bonds interacted with the surfaces of starch granules, while CLP penetrated the interiors of pasted starch granules, destroyed the helixes and backbone structure of starch, and formed type V crystallinity with amylose. The results of in vitro digestion analysis revealed that polysaccharides could decrease the amount of resistant starch and increase the amount of slowly digestible starch, which might be related to the inhibition of starch gelatinisation. These results facilitate the application of chemical derivatives in starch-based functional foods and understand the interaction mechanism between potato starch and polysaccharides.
