Resistant starch formation through intrahelical V-complexes between polymeric proanthocyanidins and amylose

Reducing starch digestibility can significantly benefit efforts to combat obesity and associated chronic diseases. Polymeric proanthocyanidins (PA) form complexes with starch via unknown mechanisms, resulting in dramatically decreased starch digestibility. We hypothesized that V-type complexes are involved in these interactions. Sorghum derived PA was complexed with amylose, amylopectin, and granular maize starches in regular and deuterated solvents, and structural properties and in vitro digestibility of the complexes investigated. Based on iodine binding, X-ray diffraction patterns, crystallinity, and thermal properties, we demonstrated, for the first time, that type II semi-crystalline V-complexes are formed between amylose and PA. Furthermore, suppression of H-bonding led to amorphous complexes, suggesting extensive H-bonding facilitate and/or stabilize the V-complexes. We speculate that the complexation involves inclusion of B-rings of the PA units into the amylose helical cavity. The V-complex formation significantly increased resistant starch in gelatinized normal starch and pure amylose (by 35-45%), indicating likely physiological benefits.