Electrostatic Protein–Polysaccharide Assembly as a Potential Alternative to Ionic Gelation for Millimeter-Scale Hydrogel Beads: Insights into Accelerated Gelation from an Amaranth Protein–Xanthan Gum System

Electrostatic protein–polysaccharide hydrogels are attractive materials formed without thermal denaturation or chemical crosslinkers and at low biopolymer contents. Their broader application in foods, however, has been limited by slow gelation, with network development often requiring many hours (~18 h). In this study, millimeter-scale hydrogel beads were fabricated from amaranth proteins and xanthan gum by extrusion into glucono-δ-lactone (GDL) solutions (1–5 mg/mL) using hardening times of 10 or 30 min. Beads were successfully formed under all conditions (3.07–3.95 mm diameter), and their physicochemical properties, intermolecular interactions, microstructure, and gel strength were evaluated. Electrostatic attraction remained the dominant force driving gelation. Furthermore, 10 min hardening favored interpolymeric electrostatic interactions, whereas longer exposure reduced them and promoted hydrogen bonding and hydrophobic interactions. These molecular rearrangements were accompanied by a decreased size, lower water retention capacity (WRC), and higher mechanical strength. The mildest treatment (1 mg/mL GDL, 10 min) was post-loaded with a coffee pulp phenolic extract and showed reduced gel strength and electrostatic interactions, suggesting competition for binding sites within the macromolecular network. The extrusion of amaranth protein–xanthan gum mixtures into a GDL bath markedly shortens electrostatic gelation time, supporting this approach as a potential alternative to ionic gelation for the production of millimeter-scale hydrogel beads for food applications.