Interior of Amylopectin and Nano-Sized Amylopectin Fragments Probed by Viscometry, Dynamic Light Scattering, and Pyrene Excimer Fluorescence

Nano-sized amylopectin fragments (NAFs), prepared by extrusion of waxy corn starch, were investigated by viscometry, dynamic light scattering (DLS), and pyrene excimer fluorescence (PEF). NAF57, with a hydrodynamic diameter of 57 nm, was treated with nitric acid to yield three degraded NAFs, which appeared to share the same interior and structural features as amylopectin based on their measured intrinsic viscosity and hydrodynamic diameter. This conclusion was further supported by comparing the efficiency of forming excimer between an excited and a ground-state pyrenyl label covalently attached to the NAFs (Py-NAFs) using their I(E)/I(M) ratio of the fluorescence intensity of the excimer (I(E)) to that of the monomer (I(M)). The overlapping trends obtained for all Py-NAFs and the pyrene-labeled amylopectin samples by plotting the I(E)/I(M) ratio as a function of pyrene content provided further evidence that the interior of NAFs and amylopectin shared the same structural features and contained a similar amount of free volume as predicted by the Solution-Cluster (Sol-CL) model. The presence of free volume was validated by adding linear poly(ethylene glycol) (PEG) chains that could not penetrate the interior of Py-NAFs, thus subjecting the Py-NAFs to increased osmotic pressure, which induced their compression and resulted in an increase in I(E)/I(M).