Deciphering Biosynthesis Mechanism and Solution Properties of Cyclic Amylopectin

A novel cyclic amylopectin (CA) was synthesized from waxy corn starch (WCS) using branching enzyme (BstBE), providing insights into its biosynthesis mechanism and solution properties. During the first 4 h, BstBE partially cyclized WCS, producing 68.20% CA with a significantly reduced molecular weight (M), from 8.98 × 10⁶ to 3.19 × 10⁴ g/mol and a lower polymer dispersity index (PDI), decreasing from 1.97 to 1.12. This resulted in a uniform CA structure with shorter chain lengths, particularly increasing DP 3-13, especially DP 7-9. Over the subsequent 4-12 h, the PDI slightly increased to 1.18 as the CA content decreased to 50.48%, with an increase in small ring structures (DP 6-12) of CA, suggesting both ring-opening and ring-downsizing due to continued enzyme catalysis. These results propose a two-stage reaction model: initial cyclization followed bybranching and secondary cyclization. CA exhibited excellent solution properties, with BE-4 and BE-12 samples demonstrating high solubility (≥65 g/100 mL), low viscosity (<0.01 Pa·s), and over 90% light transmittance after 14 days at 4 °C, highlighting its broad application potential.