Probing the Stoichiometry Dependence of Enzyme-Catalyzed Junction Zone Network Formation in Aiyu Pectin Gel via a Reaction Kinetics Model.

We investigate the enzymatic self-catalyzed gelation process in aiyu gel, a natural ion crosslinked polysaccharide gel. The gelation process depends on the concentration ratio ( R max ) of the crosslinking calcium ions and all galacturonic acid binding sites. The physical gel network formation relies on the assembly of calcium-polysaccharide crosslink bonds. The crosslinks are initially transient and through break-up/rebinding gradually re-organizing into long, stable junction zones. Our previous study formulated a reaction kinetics model to describe enzymatic activation, crosslinker binding, and crosslink microstructural reorganization, in order to model the complex growth of elasticity. In this study, we extend the theory for the time-dependent profile of complex moduli and examine the interplay of enzyme conversion, crosslink formation, and crosslink re-organization. The adjusted model captures how the gelation and structural rearrangement characteristic times vary with the polymer and calcium concentrations. Furthermore, we find that calcium ions act as both crosslinkers and dopants in the excess calcium ion scenario and the binding dynamics is determined by R max . This study provides perspectives on the dynamic binding behaviors of aiyu pectin gel system and the theoretical approach can be generalized to enzyme-catalyzed ionic gel systems.