Glyceride structure-induced interactions and nonlinear rheological behavior of starch-glyceride complexes under hydrothermal treatment and microwave-assisted 3D printing.

In this study, corn starch-glyceride complexes were prepared using hydrothermal treatment and microwave-assisted 3D printing, enabling systematic regulation of starch interactions through mono-, di-, and triglycerides with distinct saturation. Comparative analysis indicated that glyceride substitution degree played a dominant role in ordered structures and resistant starch (RS) content, whereas saturation exerted a secondary influence. Multi-scale structural characterization, combined with nonlinear rheology and molecular dynamics simulations, revealed that mono-/diglycerides formed single-helix inclusion complexes, resulting in increased ordered structures (V-type crystallinity >20%) and RS content near 20%. However, these systems exhibited rigid but less stable gel networks under large deformation, as reflected by pronounced nonlinear rheological responses. In contrast, triglyceride complexes showed limited helix inclusion (V-type crystallinity <5%) but enhanced RS content (up to 25%) through chain entanglement and hydrophobic shielding, resulting in improved attenuated nonlinear responses. Overall, this work provides basic data for starch-glyceride systems via hydrothermal and extrusion-based processing conditions.